US20100033295A1 - High temperature thermal cutoff device - Google Patents

High temperature thermal cutoff device Download PDF

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Publication number
US20100033295A1
US20100033295A1 US12/512,369 US51236909A US2010033295A1 US 20100033295 A1 US20100033295 A1 US 20100033295A1 US 51236909 A US51236909 A US 51236909A US 2010033295 A1 US2010033295 A1 US 2010033295A1
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United States
Prior art keywords
temperature
cutoff device
temperature thermal
pellet
high temperature
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Abandoned
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US12/512,369
Inventor
Perry Kent
Truong Nguyen
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Therm O Disc Inc
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Therm O Disc Inc
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Priority to US12/512,369 priority Critical patent/US20100033295A1/en
Assigned to THERM-O-DISC, INCORPORATED reassignment THERM-O-DISC, INCORPORATED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Kent, Perry, NGUYEN, TRUONG
Priority to EP09167298.0A priority patent/EP2151846B1/en
Priority to CN201510726536.6A priority patent/CN105428176B/en
Priority to CN200910211606A priority patent/CN101685733A/en
Publication of US20100033295A1 publication Critical patent/US20100033295A1/en
Priority to HK16109208.1A priority patent/HK1221329A1/en
Priority to US13/352,181 priority patent/US8961832B2/en
Priority to US14/593,768 priority patent/US9779901B2/en
Abandoned legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H37/00Thermally-actuated switches
    • H01H37/74Switches in which only the opening movement or only the closing movement of a contact is effected by heating or cooling
    • H01H37/76Contact member actuated by melting of fusible material, actuated due to burning of combustible material or due to explosion of explosive material
    • H01H37/764Contact member actuated by melting of fusible material, actuated due to burning of combustible material or due to explosion of explosive material in which contacts are held closed by a thermal pellet
    • H01H37/765Contact member actuated by melting of fusible material, actuated due to burning of combustible material or due to explosion of explosive material in which contacts are held closed by a thermal pellet using a sliding contact between a metallic cylindrical housing and a central electrode
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H85/00Protective devices in which the current flows through a part of fusible material and this current is interrupted by displacement of the fusible material when this current becomes excessive
    • H01H85/02Details
    • H01H85/04Fuses, i.e. expendable parts of the protective device, e.g. cartridges
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H69/00Apparatus or processes for the manufacture of emergency protective devices
    • H01H69/02Manufacture of fuses
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H85/00Protective devices in which the current flows through a part of fusible material and this current is interrupted by displacement of the fusible material when this current becomes excessive
    • H01H85/02Details
    • H01H85/04Fuses, i.e. expendable parts of the protective device, e.g. cartridges
    • H01H85/05Component parts thereof
    • H01H85/055Fusible members
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H85/00Protective devices in which the current flows through a part of fusible material and this current is interrupted by displacement of the fusible material when this current becomes excessive
    • H01H85/02Details
    • H01H85/04Fuses, i.e. expendable parts of the protective device, e.g. cartridges
    • H01H85/05Component parts thereof
    • H01H85/055Fusible members
    • H01H85/06Fusible members characterised by the fusible material
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02HEMERGENCY PROTECTIVE CIRCUIT ARRANGEMENTS
    • H02H5/00Emergency protective circuit arrangements for automatic disconnection directly responsive to an undesired change from normal non-electric working conditions with or without subsequent reconnection
    • H02H5/04Emergency protective circuit arrangements for automatic disconnection directly responsive to an undesired change from normal non-electric working conditions with or without subsequent reconnection responsive to abnormal temperature
    • H02H5/047Emergency protective circuit arrangements for automatic disconnection directly responsive to an undesired change from normal non-electric working conditions with or without subsequent reconnection responsive to abnormal temperature using a temperature responsive switch
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H37/00Thermally-actuated switches
    • H01H37/74Switches in which only the opening movement or only the closing movement of a contact is effected by heating or cooling
    • H01H37/76Contact member actuated by melting of fusible material, actuated due to burning of combustible material or due to explosion of explosive material
    • H01H37/761Contact member actuated by melting of fusible material, actuated due to burning of combustible material or due to explosion of explosive material with a fusible element forming part of the switched circuit
    • H01H2037/762Contact member actuated by melting of fusible material, actuated due to burning of combustible material or due to explosion of explosive material with a fusible element forming part of the switched circuit using a spring for opening the circuit when the fusible element melts
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H37/00Thermally-actuated switches
    • H01H37/74Switches in which only the opening movement or only the closing movement of a contact is effected by heating or cooling
    • H01H37/76Contact member actuated by melting of fusible material, actuated due to burning of combustible material or due to explosion of explosive material
    • H01H2037/768Contact member actuated by melting of fusible material, actuated due to burning of combustible material or due to explosion of explosive material characterised by the composition of the fusible material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H2223/00Casings
    • H01H2223/008Casings metallic
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H2235/00Springs
    • H01H2235/004Two parallel coil springs
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H2235/00Springs
    • H01H2235/01Spiral spring
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49002Electrical device making
    • Y10T29/49105Switch making
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49002Electrical device making
    • Y10T29/49107Fuse making

Definitions

  • the present disclosure relates to electrical current interruption devices and more particularly to high-temperature electrical current interruption safety devices, or thermal cut-offs, that provide protection from over-temperature conditions.
  • Temperatures of operation for appliances, electronics, motors and other electrical devices typically have an optimum range.
  • the temperature range where damage can occur to system components or where the device becomes a potential safety hazard in the application or to the end-user serves as an important detection threshold.
  • Various devices are capable of sensing such over-temperature thresholds.
  • Certain devices which are capable of sensing over-temperature conditions and interrupting electrical current include electrical thermal fuses, which only operate in a narrow temperature range.
  • tin and lead alloys, indium and tin alloys, or other metal alloys which form a eutectic metal are unsuitable for appliance, electronic, electrical and motor applications due to undesirably broad temperature response thresholds and/or detection temperatures that are outside the desired range of safety.
  • TCO thermal cut-off
  • Such TCO devices are typically installed in an electrical application between the current source and electrical components, such that the TCO is capable of interrupting the circuit continuity in the event of a potentially harmful or potentially dangerous over-temperature condition.
  • TCOs are often designed to shut off the flow of electric current to the application in an irreversible manner, without the option of resetting the TCO current interrupting device.
  • High temperature appliances and applications require the use of robust over-temperature detection devices with high-holding temperatures exceeding the operating temperatures and/or holding temperatures of conventional TCO designs.
  • the present disclosure provides stable, reliable, and robust high-temperature TCO devices.
  • FIG. 1 is an enlarged cross sectional view of an exemplary thermal cutoff device construction
  • FIG. 2 illustrates the thermal cutoff construction of FIG. 1 after a thermal pellet has undergone a physical transition and a current interruption actuating assembly has caused electrical switching to break continuity and change the thermal cutoff device's operating condition;
  • FIG. 3 is a side perspective view illustrating the current interruption actuating assembly
  • FIG. 4 is a side view of a sliding contact member of the current interruption actuating assembly switch construction of FIG. 1 ;
  • FIG. 5 is a side view of one of the springs of the current interruption actuating assembly of FIG. 1 ;
  • FIG. 6 is a cross sectional view of a ceramic bushing of FIG. 1 ;
  • FIG. 7 is an elevation view of a thermal pellet of FIG. 1 .
  • TCOs thermal cut-off electrical current interruption safety devices
  • Various safety electrical current interruption devices include thermal cut-off electrical current interruption safety devices (TCOs)
  • TCOs thermal cut-off electrical current interruption safety devices
  • a threshold temperature or rating typically ranging from about 60° C. up to about 235° C.
  • conventional TCO devices are not rated for higher temperature applications, such as those greater than or equal to about 240° C.
  • conventional TCO devices have not sufficiently fulfilled the performance criteria, particularly stability and robustness, for long-term use in high-temperature applications as a safety device.
  • the present disclosure provides a high temperature thermal cutoff device (referred to herein as a “HTTCO”).
  • HTTCO high temperature thermal cutoff device
  • Such an HTTCO device is capable of switching continuity of an electrical circuit or electrical communication when the surrounding environment or operating temperature reaches a predetermined threshold temperature.
  • high-temperature thermal cutoff device it is meant that device has a threshold or actuation temperature of greater than about 235° C., optionally greater than or equal to about 240° C., optionally greater than or equal to about 245° C., optionally greater than or equal to about 250° C., optionally greater than or equal to about 255° C., optionally greater than or equal to about 260° C., optionally greater than or equal to about 265° C., optionally greater than or equal to about 270° C., optionally greater than or equal to about 275° C., optionally greater than or equal to about 280° C., optionally greater than or equal to about 285° C., optionally greater than or equal to about
  • the HTTCO exhibits switching behavior at a threshold or actuation temperature of greater than or equal to about 240° C. to less than or equal to about 270° C., optionally greater than or equal to about 240° C. to less than or equal to about 265° C., optionally greater than or equal to about 240° C. to less than or equal to about 260° C., optionally greater than or equal to about 240° C. to less than or equal to about 255° C., optionally greater than or equal to about 240° C. to less than or equal to about 250° C., optionally greater than or equal to about 240° C. to less than or equal to about 245° C., optionally greater than or equal to about 240° C.
  • the HTTCO exhibits switching behavior at a threshold temperature of about 240° C., optionally about 241° C., optionally about 242° C., optionally about 243° C., optionally about 244° C., optionally about 245° C., optionally about 246° C., optionally about 247° C., optionally about 248° C., optionally about 249° C., optionally about 250° C., optionally about 251° C., optionally about 252° C., optionally about 253° C., optionally about 254° C., optionally about 255° C., optionally about 256° C., optionally about 257° C., optionally about 258° C., optionally about 259° C., optionally about 260° C., optionally about 261° C., optionally about 262° C., optionally about 263° C., optionally about 264° C., optionally about
  • An illustrative test demonstrating the performance of a high temperature thermal pellet composition includes continuous aging of HTTCO devices formed in accordance with the present teachings for at least 1,000 hours at a sustained temperature of 235° C. While the HTTCO ideally meets or exceeds the aforementioned illustrative test protocol, it should be understood by those skilled in the art that the compositions are contemplated as being useful for both low voltage and high voltage applications. Further, in certain aspects, the high temperature thermal pellet compositions meet or exceed Underwriters' Laboratory test UL1020 or IEC/EN 60691 standards, which are respectively incorporated herein by reference. In certain embodiments, HTTCO devices meet one or more of such standards at the pre-selected high temperature rating for the device. While the performance criteria is fully outlined in each of these standards, salient aspects of performance tests that demonstrate conformance to the IEC 60691, Third Edition standard are summarized in Table 1.
  • a Samples are subjected to two complete conditioning cycles: i 24 hours at rated functioning temperature minus 15° C.; ii 96 hours at 35° C. (+/ ⁇ 2°) and 95% R.H. (+/ ⁇ 5 R.H.); iii 8 hours AT 0° C. (+/ ⁇ 2°).
  • B Samples are subjected to a third complete conditioning cycle: i 24 hours at rated functioning temperature minus 15° C.; ii 168 hours at 35° C. (+/ ⁇ 2°) and 95% R.H. (+/ ⁇ 5 R.H.); iii 8 hours AT 0° C. (+/ ⁇ 2°).
  • the HTTCO ot the present disclosure comprises a sealed housing having disposed therein a high-temperature thermal pellet having a transition temperature of greater than or equal to about 240° C.
  • the transition temperature of the high-temperature thermal pellet relates to the threshold temperature at which the HTTCO device switches or actuates, as will be described in greater detail below.
  • the high-temperature thermal pellet comprises at least one organic compound, which generally has a melting point or melting point range near the pre-selected or desired transition temperature.
  • the HTTCO has a high-temperature seal disposed in a portion of at least one opening of the housing that substantially seals the housing up to the transition temperature of the high-temperature thermal pellet.
  • the HTTCO also comprises a current interruption assembly that is at least partially disposed within the housing.
  • the current interruption assembly establishes electrical continuity in a first operating condition of the HTTCO, which corresponds to an operating temperature of less than the transition temperature of the high-temperature thermal pellet and that discontinues electrical continuity when the operating temperature exceeds the transition temperature.
  • a TCO 10 includes a conductive metallic housing or casing 11 having a first metallic electrical conductor 12 in electrical contact with a closed end 13 of the housing 11 .
  • An isolation bushing 14 such as a ceramic bushing, is disposed in an opening 15 of the housing 11 .
  • Housing 11 further includes a retainer edge 16 , which secures the ceramic bushing 14 within the end of the housing 11 .
  • Electric contact 17 passes through isolation bushing 14 and has an enlarged terminal end 18 disposed against one side 19 of isolation bushing 14 and a second end 20 projecting out of the outer end 21 of isolation bushing 14 .
  • a seal 28 is disposed over the opening 15 and can create sealing contact with the housing 11 and its retainer edge 16 , the isolation bushing 14 , and the exposed portion of the second end 20 of electric contact 17 . In this manner, an interior portion 29 of the housing 11 is substantially sealed from the external environment 30 .
  • substantially sealed it is meant that the while the barrier seal is optionally porous at a microscopic level, the barrier is capable of preventing escape or significant mass loss of the thermal pellet material, for example, the seal retains at least about 95% of the mass of the initial thermal pellet through 1,000 hours of continuous operation at 235° C., optionally about 96% of the mass of the initial thermal pellet, optionally greater than about 97% of the mass of the initial thermal pellet, optionally greater than or equal to about 98% of the mass of the initial thermal pellet, optionally greater than or equal to about 99% of the mass of the initial thermal pellet, optionally greater than or equal to about 99.5% of the mass of the initial thermal pellet and in certain aspects, greater than or equal to about 99.9% of the mass of the initial thermal pellet is retained within the housing through continuous operation.
  • the current interruption assembly 25 which actuates or switches to change continuity of an electrical circuit, further includes a sliding contact member 22 , formed of electrically conductive material, such as a metal is disposed inside the housing 11 and has resilient peripheral fingers 23 ( FIG. 4 ) disposed in sliding engagement with the internal peripheral surface 24 of the housing 11 to provide electrical contact there between. Moreover, when the TCO has an operating temperature that is below the predetermined threshold set-point temperature of the TCO device, the sliding contact member 22 is disposed in electrical contact with the terminal end 18 of electric contact 17 .
  • Current interruption assembly 25 also includes a tensioning mechanism, which may include a plurality of tensioning mechanisms.
  • the tensioning mechanism 25 biases the sliding contact member 22 against the terminal end 18 of electric contact 17 to establish electrical contact in the first operating condition (where operating temperatures are below the threshold temperature of the TCO device, as will be described below).
  • the tensioning mechanism includes a pair of springs 31 , which are respectively disposed on opposite sides of the sliding contact member 22 .
  • the springs 31 include a compression spring 26 and an expansion trip spring 27 .
  • a thermally responsive pellet or thermal pellet 25 is disposed in the housing 11 against the end wall 13 thereof.
  • the compression spring 26 is in a compressed state between the solid thermal pellet 25 and the sliding contact member 22 and in the exemplary design shown, generally has a stronger compressed force than the force of the expansion trip spring 27 , which is disposed between the contact member 22 and the isolation bushing 14 , such that the sliding contact member 22 is biased towards (e.g., held by the force of the spring 26 ) and in electrical contact with the enlarged end 18 of the electrical contact 17 .
  • an electrical circuit is established between the first electrical conductor 12 and electrical contact 17 through the conductive housing 11 and sliding contact member 22 .
  • TCO devices are designed to include a thermal pellet 25 that is reliably stable in the first operating condition (where the operating temperature, for example, the temperature of the surrounding environment 30 is below a threshold temperature); however reliably transitions to a different physical state when the operating temperature meets or exceeds such threshold temperature in a second operating condition.
  • the thermal pellet 25 melts, liquefies, softens, volatilizes, or otherwise transitions to a different physical state during an adverse heating condition, which is illustrated in FIG. 2 .
  • the springs 31 are adapted to expand and release, as illustrated by expansion trip spring 27 in FIG. 5 , and through the relationship of the particular forces and length of the compression spring 26 and expansion trip spring 27 , the sliding contact member 22 is moved out of electrical contact with the end 18 of the electric contact 17 in the manner shown in FIG. 2 , so that the electrical circuit between the terminal conductor 12 and electrical contact 17 through the thermal cutoff construction 10 (via the housing 11 and sliding contact member 22 ) is discontinued and broken, remaining open as illustrated in FIG. 2 .
  • thermal cutoff device described in the present disclosure are used for purposes of illustration are exemplary and in certain aspects, should not be construed to be limiting. In certain aspects, various components, designs, or operating principles may be varied in number or design. Various other thermal switching or cutoff devices are known in the art and likewise contemplated.
  • the high-temperature thermal pellet compositions of the present teachings are thermally and chemically stable, reliable, and robust for use in the HTTCO application.
  • the high-temperature thermal pellet composition will include one or more organic compounds, such as crystalline organic compounds.
  • the high-temperature thermal pellet compositions are designed to have a transition temperature that permits the HTTCO device to have a final temperature (T f ) (also referred to as actuation or threshold temperature) where the internal contact breaks electrical continuity due to structural changes in the pellet composition, which in turn causes opening of tensioning mechanisms, for example.
  • T f final temperature
  • the transition temperature of the high-temperature thermal pellet directly corresponds to the threshold temperature T f of the HTTCO device, whereby a switch in continuity is activated.
  • the transition temperature generally refers to the temperature at which a pellet melts, liquefies, softens, volatilizes, sublimates, or otherwise transitions to a different physical state to transform from a solid having structural rigidity to a form or phase that loses structural rigidity, either by contraction, displacement, or other physical changes, which cause the internal electrical contacts to separate due to the applied tension from the tensioning mechanism.
  • a tensioning mechanism such as a switch in a held-open or held-closed position, depending on the HTTCO device, for example.
  • this transition temperature is also referred to as a “melting-point”; however, the compounds in the pellet composition need not fully melt in a conventional sense to achieve separation of the electrical contacts to break the internal circuit and electrical continuity.
  • a melting-point temperature is one where compounds or compositions transform from solid to liquid phase, which may occur at a range of temperatures, rather than at a single discrete temperature point.
  • the high temperature thermal pellet may soften or sublimate rather than melting, by way of non-limiting example, to achieve the separation of electrical contacts to break the circuit. Melting-point temperatures can be measured in various apparatuses, such as those produced by Thomas Hoover, Mettler and Fisher-Johns companies.
  • Differential Scanning Colorimetry (DSC) techniques are also commonly used. Different measurement techniques may result in differing melting points, for example, optical analysis methods like Fisher-Johns measure light transmittance through a sample, a solid to liquid phase change. Early optical methods potentially suffered greater observer error versus more modern light beam transmittance melt point indicators. In addition, earlier techniques to determine melting point (before the use of digital high speed scan capabilities), rendered a broader range of results for melt points and other transitions.
  • melt point of a sample for example, measured by DSC, which measures heat flow behavior for example, crystallinity (solid-solid phase) changes as well as, solid to liquid phase changes, could show the solid-solid phase change of an impurity that may have been reported as a melt point, such as dehydration or breaking of hydroxyl bonds, as well as the solid-liquid phase change at the melt point for the material of interest.
  • a composition can be selected for use in the thermal pellet that empirically exhibits a desirable physical change that will enable a pellet's physical transition without necessarily correlating to the predicted melting point ranges.
  • the thermal pellet 25 has a relatively rapid and repeatable collapse rate, meaning once the environment 30 reaches a threshold temperature, the rate at which the thermal pellet composition 25 physically collapses is relatively high.
  • a pellet collapse rate is via thermomechanical analysis (TMA) where a pellet is heated at a rapid rate to within about 10° C.-15° C. of the predicted melting point temperature, then a heating rate is selected, for example about 0.5° C./min through the predicted melting point temperature range.
  • TMA thermomechanical analysis
  • the physical height of the pellet is likewise measured at the beginning of the test and throughout this heating process, so that an amount of displacement from the top surface of the pellet to the underlying substrate (on which the pellet is initially placed) is measured.
  • the rate, measured in micrometer per ° C., at which the pellet height collapses at the onset through to the end of the transition temperature correlates to the pellet collapse rate, for example, a 75% reduction of a pellet's height from a threshold temperature within about 100 micrometer/° C., optionally about 500 micrometer/° C., optionally about 1000 micrometer/° C.
  • both the solid liquid phase transition temperature and pellet collapse rate are salient features of the thermal pellet 25 , as the rapidity with which the pellet collapses ensures sufficient separation of electrical contacts in the HTTCO to avoid excessive arcing, which could melt various components and potentially impact HTTCO performance. Methods of testing and quantifying such a pellet collapse rate will be described in further detail below.
  • the thermal pellet comprises one or more organic compounds having a melting-point temperature (mp) that occurs in a range of temperatures corresponding to the desired transition temperature.
  • the high-temperature thermal pellet has one or more organic compounds that have a melting point temperature (mp) within about 5° C. below the transition temperature and within about 2° C. above the transition temperature (i.e., where T ⁇ 5° C. ⁇ mp ⁇ T+2° C.), where T is the transition temperature.
  • the high-temperature thermal pellet compositions comprise organic compounds or materials that are selected to meet one or more of the following criterion.
  • the organic compositions selected for use in the high-temperature thermal pellet have a relatively high chemical purity.
  • desirable chemical candidates for the high temperature thermal pellet compositions have a range of purity levels from about 95% up to 99+%.
  • the organic compositions selected for use in the high temperature thermal pellets are particularly suitable for processing, handling, and toxicity characteristics.
  • the organic chemical compounds or compositions selected for use in the high-temperature pellet compositions have a median lethal dose toxicity value (LD 50 ) less than or equal to about 220 mg/kg (ppm) for a mouse; less than or equal to about 400 mg/kg (ppm) for a rabbit; and less than or equal to about 350 mg/kg (ppm) for a rat.
  • LD 50 median lethal dose toxicity value
  • the selected organic chemical compositions for the high-temperature thermal pellet desirably do not have documented carcinogenicity effects, mutagenicity effects, neurotoxicity effects, reproductive effects, teratogenicity effects, and/or other harmful health or epidemiological effects.
  • the organic components for the high temperature thermal pellet compositions are selected such that alternate reactive residuals, reaction products formed during manufacture, decomposition products, or other species that might be formed during manufacture, storage, or use are absent, minimized, or are capable of purification and removal of such undesired species.
  • compositions selected for use in the high temperature thermal pellet composition exhibit long-term stability.
  • compositions are optionally selected to possess temperature or thermal stability, in other words, chemical compounds that show decomposition or volatility behavior within about 10° C., optionally within about 20° C., optionally within about 30° C., optionally within about 40° C., optionally within about 50° C., optionally within about 60° C., optionally within about 75° C., and in certain aspects, optionally within about 100° C. of the transition temperature or melting point of the organic compound may be rejected as viable candidates.
  • chemical compositions suitable for use as high-temperature thermal pellet compositions will not show a strong likelihood of heat-induced and age-progressive oxidation or decomposition.
  • suitable compositions for high-temperature thermal pellets include those that are “electrically non-conductive,” meaning that the composition is capable of withstanding a 240 volt, 60 Hz sinusoidal potential between two electrodes at least about 5° C. above the T f final temperature for at least one minute without conducting greater than 250 mA.
  • the select composition should be capable of withstanding a 240 volt, 60 Hz sinusoidal potential at least 10° C. above the T f final temperature for at least about one minute without conducting greater than 250 mA.
  • the high-temperature thermal cutoff compositions are optionally capable of withstanding a 240 volt, 60 Hz sinusoidal potential at least 50° C. above the final transition temperature T f for at least about one minute without conducting greater than 250 mA of current.
  • the organic chemical compositions that are selected for use in the high temperature thermal composition have an initial melting point temperature of at least about 240° C., optionally about 241° C., optionally about 242° C., optionally about 243° C., optionally about 244° C., optionally about 245° C., optionally about 246° C., optionally about 247° C., optionally about 248° C., optionally about 249° C., optionally about 250° C., optionally about 251° C., optionally about 252° C., optionally about 253° C., optionally about 254° C., optionally about 255° C., optionally about 256° C., optionally about 257° C., optionally about 258° C., optionally about 259° C., optionally about 260° C., optionally about 261° C., optionally about 262° C., optionally about 263° C., optionally about 264° C., optionally about 2
  • the melting point of the organic composition for the high-temperature thermal pellet is greater than 275° C. and in certain aspects, optionally greater than 300° C.
  • organic compounds that meet the above selection criteria and that can remain a solid at temperatures ranging from 50° C. to at least 235° C. are desirable.
  • organic compounds that can remain a stable solid up to about 236° C., optionally up to about 237° C., optionally up to about 238° C., optionally up to about 239° C., optionally up to about 240° C., optionally up to about 245° C., optionally up to about 250° C., optionally up to about 255° C., optionally up to about 260° C., optionally up to about 265° C., optionally up to about 270° C., optionally up to about 275° C., optionally up to about 280° C., optionally up to about 285° C., optionally up to about 290° C., optionally up to about 295° C., and in certain aspects, optionally up to or exceeding about 300° C.
  • Suitable organic compound candidates for the high-temperature thermal pellets of the HTTCO devices of the present disclosure optionally include the following additional characteristics.
  • organic chemicals having acidic structures such as structures with multiple hydroxides or structures which might have ionic activity in an electrical field may be avoided or minimized.
  • organic compounds having side groups comprising sulfur can be avoided, as are compounds having bond structures that easily break down in an electrical field in certain applications.
  • the selection of organic compounds useful as a thermal cutoff composition herein can be made based on the chemical's behavior in relation to and interaction with the seal material for the housing of the HTTCO, which often is a porous polymeric structure.
  • Suitable organic chemical compounds for the high-temperature thermal pellet include those having a relatively large molecular size, for example, organic molecules having ring structures, such as those that occupy dimensional space due to bending or side groups.
  • suitable chemical candidates having flat or unbent conformations or chemical structures which may have shear mobility or a relatively unimpaired navigation path through the pores in the seal material, are avoided.
  • the organic chemical compounds selected for use in the high-temperature thermal pellet compositions have relative molecular complexity, such as organic polycyclic ring structures with complex bond orientations that create irregular dimensional space filling configurations or conformations.
  • organic polycyclic ring structures with complex bond orientations that create irregular dimensional space filling configurations or conformations.
  • certain chemical structures that “tangle” at high energy states are desirable, as are relatively large organic species having complex side chains.
  • suitable chemical compounds for the high-temperature thermal compositions of the present disclosure include those that have high molecular bond strength, for example, in ring structures like polyaromatic, polyalkyl, heteroalkyl rings, including fused ring structures that share one or more common bonds.
  • Chemical structures having high intrabond strength with other rings or side groups are also suitable organic species.
  • chemical compounds having intermolecular bond strength, including non-polar or relatively low polar strength structures with high instantaneous polarizability are also suitable.
  • structures with side groups that have “bond affinities” for the parent ring or side groups of other molecular groups are desirable.
  • the thermal cutoff composition can include one or more aromatic compounds, one or more five-membered ring compounds, polymers, co-polymers, and mixtures thereof.
  • the high-temperature thermal pellets may comprise a plurality of organic compounds as primary components.
  • the high-temperature pellet compositions for the HTTCO devices of the present disclosure optionally comprise one or more organic compounds that will provide a transition temperature of greater than or equal to about 240° C.
  • a plurality of such organic compositions can be used, such that the resulting melting point of the mixture provides the predetermined desired transition temperature for the pellet composition.
  • T x thermal pellet transition temperature expressed by the following relationship of
  • the pellet composition may comprise a single organic composition as the primary ingredient to arrive at a T x of greater than or equal to about 240° C.
  • the pellet composition may comprise a plurality of organic compositions, for example two or more organic compounds, to arrive at a T x of greater than or equal to about 240° C.
  • Such organic compounds may have different melting point temperatures or other properties and are can be combined by co-precipitation, co-crystallization, mixing, blending, milling, or otherwise combined in a suitable manner known in the art.
  • a high-temperature thermal pellet composition comprises one or more compounds, which includes compounds with a chemical structure having one or more six-member rings that has a basic backbone of carbon with side constituent groups that may be the same or different.
  • the thermal cutoff composition can include one or more chemical entities generally described by a structural repeating unit (SRU): (-PhRR′—) n where R and R′ may be the same or different side constituent groups, and wherein n may also be a value or greater than or equal to 1, designating the repetition of the structure repeating unit (SRU).
  • SRU structural repeating unit
  • the high temperature thermal pellet composition can include one or more 5 member ring structures, where the side groups and/or SRU may have may be the same or different entities (e.g., having different side constituent groups) such as, for example, where the thermal cutoff composition is described as an example, by the nominal SRU formula, (-Ph-RR 1 ) n -(-Ph-R 2 R 3 ) m , wherein R and R 1 are distinct side groups from R 2 and R 3 .
  • R and R 1 may be the same or different, and similarly, R 2 and R 3 may be the same or different.
  • hydrocarbyl is used herein to refer generally to organic groups comprised of carbon chains to which hydrogen and optionally other elements are attached. CH 2 or CH groups and C atoms of the carbon chains of the hydrocarbyl may be replaced with one or more heteroatoms (i.e., non-carbon atoms). Suitable heteroatoms include but are not limited to O, S, P and N atoms. Illustrative hydrocarbyl groups can include, but are not limited to.
  • alkyl alkenyl, alkynyl, ether, polyether, thioether, straight chain or cyclic saccharides, ascorbate, aminoalkyl, hydroxylalkyl, thioalkyl, aryl and heterocyclic aryl groups, optionally substituted tricyclic molecules, amino acid, polyalcohol, glycol, groups which have a mixture of saturated and unsaturated bonds, carbocyclic rings and combinations of such groups.
  • the term also includes straight-chain, branched-chain and cyclic structures or combinations thereof.
  • Hydrocarbyl groups are optionally substituted. Hydrocarbyl substitution includes substitution at one or more carbons in the group by moieties containing heteroatoms.
  • Suitable substituents for hydrocarbyl groups include but are not limited to halogens, including chlorine, fluorine, bromine and iodine, OH, SH, —N—OH, NH, NH 2 , —C—NH 2 ⁇ S, CH, —CH—O, C ⁇ N, —C—N ⁇ O, —C—NH 2 ⁇ O, C ⁇ O, COH, —C—NH 2 ⁇ S, CO 2 , H, —CHBN, —CHP, OR 1 , SR 1 NR 1 , R′′, CONR 1 R 2 , and combinations thereof, where R 1 and R 2 independently are alkyl, unsaturated alkyl or aryl groups.
  • alkyl takes its usual meaning in the art and is intended to include straight-chain, branched and cycloalkyl groups.
  • the term includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2-ethylbutyl, 1-ethylbutyl, 1,3-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl,
  • cycloalkyl refers to alkyl groups having a hydrocarbon ring, particularly to those having rings of 3 to 7 carbon atoms. Cycloalkyl groups include those with alkyl group substitution on the ring. Cycloalkyl groups can include straight-chain and branched-chain portions. Cycloalkyl groups include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclononyl. Cycloalkyl groups can optionally be substituted.
  • Aryl groups may be substituted with one, two or more simple substituents including, but not limited to, lower alkyl, e.g., C 1 -C 4 , methyl, ethyl, propyl, butyl; halo, e.g., chloro, bromo; nitro; sulfato; sulfonyloxy; carboxy; carbo-lower-alkoxy, e.g., carbomethoxy, carbethoxy; amino; mono- and di-lower-alkylamino, e.g., methylamino, ethylamino, dimethylamino, methylethylamino; amido; hydroxy; lower-alkoxy, e.g., methoxy, ethoxy; and lower-alkanoyloxy, e.g., acetoxy.
  • lower alkyl e.g., C 1 -C 4
  • unsaturated alkyl group is used herein generally to include alkyl groups in which one or more single carbon-carbon bonds are double or triple carbon-carbon bonds.
  • the term includes alkenyl and alkynyl groups in their most general sense.
  • the term is intended to include groups having more than one double or triple bond, or combinations of double and triple bonds.
  • Unsaturated alkyl groups include, without limitation, unsaturated straight-chain, branched or cycloalkyl groups.
  • Unsaturated alkyl groups include without limitation: vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, hexadienyl, heptenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, 1-propenyl, 2-butenyl, 2-methyl-2-butenyl, ethynyl, propynyl, 3-methyl-1-pentynyl, and 2-heptynyl. Unsaturated alkyl groups can optionally be substituted.
  • Substitution of alkyl, cycloalkyl and unsaturated alkyl groups includes substitution at one or more carbons in the group by moieties containing heteroatoms.
  • Suitable substituents for these groups include but are not limited to OH, SH, NH 2 , COH, CO 2 H, OR 3 , SR 3 , P, PO, NR 3 R 4 , CONR 3 R 4 , and halogens, particularly chlorines and bromines where R 3 and R 4 , independently are alkyl, unsaturated alkyl or aryl groups.
  • Suitable alkyl and unsaturated alkyl groups are the lower alkyl, alkenyl or alkynyl groups having from 1 to about 5 carbon atoms.
  • aryl is used herein generally to refer to aromatic groups which have at least one ring having a conjugated pi electron system and includes without limitation carbocyclic aryl, aralkyl, heterocyclic aryl, biaryl groups and heterocyclic biaryl, all of which can be optionally substituted. Preferred aryl groups have one or two aromatic rings.
  • Carbocyclic aryl refers to aryl groups in which the aromatic ring atoms are all carbons and includes without limitation phenyl, biphenyl and napthalene groups.
  • Alkyl refers to an alkyl group substituted with an aryl group. Suitable aralkyl groups include among others benzyl, phenethyl, and may be optionally substituted, such as picolyl substituted with nitrogen. Aralkyl groups include those with heterocyclic and carbocyclic aromatic moieties.
  • Heterocyclic aryl groups refers to groups having at least one heterocyclic aromatic ring with from 1 to 3 heteroatoms in the ring, the remainder being carbon and hydrogen atoms. Suitable heteroatoms include without limitation oxygen, sulfur, and nitrogen. Heterocyclic aryl groups include among others furanyl, thienyl, pyridyl, pyrrolyl, N-alkyl pyrrolo, pyrimidyl, pyrazinyl, imidazolyl, benzofuranyl, quinolinyl, and indolyl, all optionally substituted.
  • Heterocyclic biaryl refers to heterocyclic aryls in which a phenyl group is substituted by a heterocyclic aryl group ortho, meta or para to the point of attachment of the phenyl ring to the decalin or cyclohexane. Heterocyclic biaryl includes among others groups which have a phenyl group substituted with a heterocyclic aromatic ring. The aromatic rings in the heterocyclic biaryl group can be optionally substituted.
  • Biaryl refers to carbocyclic aryl groups in which a phenyl group is substituted by a carbocyclic aryl group ortho, meta or para to the point of attachment of the phenyl ring to the decalin or cyclohexane.
  • Biaryl groups include among others a first phenyl group substituted with a second phenyl ring ortho, meta or para to the point of attachment of the first phenyl ring to the decalin or cyclohexane structure. Para substitution is preferred.
  • the aromatic rings in the biaryl group can be optionally substituted.
  • Aryl group substitution includes substitutions by non-aryl groups (excluding H) at one or more carbons or where possible at one or more heteroatoms in aromatic rings in the aryl group.
  • Unsubstituted aryl in contrast, refers to aryl groups in which the aromatic ring carbons are all substituted with H, e.g. unsubstituted phenyl (—C 6 H 5 ), or naphthyl (—C 10 H 7 ).
  • Suitable substituents for aryl groups include among others, alkyl groups, unsaturated alkyl groups, halogens, OH, SH, NH 2 , COH, CO 2 H, OR 5 , SR 5 , NR 5 R 6 , CONR 5 R 6 , where R 5 and R 6 independently are alkyl, unsaturated alkyl or aryl groups.
  • Preferred substituents are OH, SH, OR 5 , and SR 5 where R 5 is a lower alkyl, i.e., an alkyl group having from 1 to about 5 carbon atoms.
  • Other preferred substituents are halogens, more preferably chlorine or bromine, and lower alkyl and unsaturated lower alkyl groups having from 1 to about 5 carbon atoms.
  • Substituents include bridging groups between aromatic rings in the aryl group, such as —CO 2 —, —CO—, —O—, —S—, —P—, —NH—, —CH ⁇ CH— and —(CH 2 ) 1 — where I is an integer from 1 to about 5, and particularly —CH 2 — where I is 1.
  • aryl groups having bridging substituents include phenylbenzoate.
  • Substituents also include moieties, such as —(CH 2 ) J —, —O—(CH 2 ) J — or —OCO— (CH 2 ) J —, where J is an integer from about 2 to 7, as appropriate for the moiety, which bridge two ring atoms in a single aromatic ring as, for example, in a 1,2,3,4-tetrahydronaphthalene group.
  • Alkyl and unsaturated alkyl substituents of aryl groups can in turn optionally be substituted as described supra for substituted alkyl and unsaturated alkyl groups.
  • alkoxy group and “thioalkoxy group” (also known as mercaptide groups, the sulfur analog of alkoxy groups) take their generally accepted meaning.
  • Alkoxy groups include but are not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, neopentyloxy, 2-methylbutoxy, 1-methylbutoxy, 1-ethylpropoxy, 1,1-dimethylpropoxy, n-hexyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 3,3-dimethylbutoxy, 2,2-dimethoxybutoxy, 1-1-dimethylbutoxy, 2-ethylbutoxy, 1-ethylbutoxy, 1,3-dimethylbutoxy, n-pentyloxy, 5-methylhexyloxy, 4-methylhexy
  • the R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 side groups in the 5 and 6 member ring can be independently selected from any of the aforementioned hydrocarbyl substituents, for example, —CH, —CH—O, —CH—OH, —NH 2 , —NH, —CH—N, —CH ⁇ O, —N—OH, —CHBN, —CHP or mixtures thereof.
  • one particularly suitable organic compounds for use in a high-temperature thermal pellet composition of the present teachings is triptycene or tryptycene (9,10-dihydro-9,10-o-benzeno-9,10-dihydroanthracene—CAS Registry No. 477-75-8), which has a transition temperature of about 255° C. and a melting point temperature range of 255° C. to about 257° C.
  • Triptycene is generally classified as a polycyclic aromatic hydrocarbon and is generally represented by the exemplary Formula (I):
  • Triptycene can be prepared by the reduction of the anthracene-benzoquinone adduct with lithium aluminum hydride or sodium borohydride, among other methods known to those in the art. Tryptycene, or triptycene (also known as) is described in Organic Syntheses, Coll. Vol. 4, p. 964 (1963), the relevant portions of which are incorporated herein by reference.
  • a particularly suitable organic compound for use in a high-temperature thermal pellet composition of the present teachings is 1-aminoanthraquinone (also known as 1-Amino-9,10-anthracenedione—CAS Registry No. 82-45-1), which is classified as a polycyclic aromatic hydrocarbon with constituent side groups —C ⁇ O and C—NH 2 as represented in Formula (II):
  • 1-Aminoanthraquinone has an expected transition temperature of about 253° C., with a melting point range of 253° C. to about 257° C.
  • 1-Aminoanthraquinone (1-AAQ) can be prepared by the reaction of 2-chlorobenzyl chloride and xylene in the presence of a solid acid catalyst, or other methods known in the art.
  • 1-aminoanthraquinone also known as 1-Amino-9,10-anthracenedione described in U.S. Pat. Nos. 4,006,170 and 4,695,407, the relevant portions of which are incorporated herein by reference.
  • Tropine isobutyrate [(1S,5R)-8-methyl-8- 495-80-7 azabicyclo[3.2.1]octan-3-yl] 2- methylpropanoate 15 242° C.
  • 1,4-Dihydro-5H-tetrazol-5-one 1,2-dihydrotetrazol-5-one 16421-52-6 25 242.5-243° C.
  • 2,2′-Diamino-1,1′-binaphthyl 1-(2-aminonaphthalen-1- 18741-85-0 yl)naphthalen-2-amine 26 243° C.
  • Tri-3-indolylmethane 3-[bis(1H-indol-3-yl)methyl]- 518-06-9 1H-indole 39 245° C. 6-Benzyl-1,3,5-triazine-2,4- 6-(phenylmethyl)-1,3,5- 1853-88-9 diamine triazine-2,4-diamine 40 245° C.
  • Methisazone [(1-methyl-2-oxoindol-3- 1910-68-5 ylidene)amino]thiourea 44 245-247° C.
  • Emd 56431 (3R,4S)-3-hydroxy-2,2- 123595-75-5 dimethyl-4-(2-oxopyridin-1- yl)chroman-6-carbonitrile 46 245-246.5° C.
  • 1-Aminothioxanthen-9-one 1-aminothioxanthen-9-one 40021-31-6 76 249-250° C.
  • 4,4′-Diaminoazobenzene 4-(4- 538-41-0 aminophenyl)diazenylaniline 82 250-253° C.
  • N,N-Dimethyl-4-t-butylaniline 4-tert-butyl-N,N- 2909-79-7 dimethylaniline 83 250-251° C.
  • 2-Methyl-4(5)-nitroimidazole 2-methyl-4-nitro-3H-imidazole 696-23-1 114 255-257° C.
  • 1H-imidazo[5,4-b]pyrazine 1H-imidazo[5,4-b]pyrazine 273-94-9 129 258-260° C.
  • Magnosprengerine 4-(2-dimethylaminoethyl)-2- 35266-63-8 methoxyphenol 130 258-259° C.
  • Papyriogenin A (4aR,6aR,6aS,6bR,8aR,12aS)- 59076-79-8 2,2,6a,6b,9,9,12a- heptamethyl-3,10-dioxo- 1,4,5,6,6a,7,8,8a,11,12- decahydropicene-4a- carboxylic acid 166 262-264° C.
  • 1,3-Di-p-tolylurea 1,3-bis(4-methylphenyl)urea 621-00-1 168 263-265° C.
  • Propanetetracarboxamide tetracarboxamide 169 263° C.
  • Paxillarine A [(4R,8R,10R,13S,17S)-3- 145022-89-5 (benzoyl-methylamino)-17-(1- dimethylaminoethyl)-16- hydroxy-10,13-dimethyl- 2,3,4,5,6,7,8,9,11,12,14,15,16,- 17-tetradecahydro-1H- cyclopenta[a]phenanthren-4-yl] acetate 175 263-267° C.
  • hernandonine deriv 3-methoxy 155944-22-2 204 265° C. 3-hydroxy-6-methylisoquinoline 51463-11-7 205 265° C. hexahydro-1,2,4-ethanylylidene- 110243-21-5 1H-cyclobuta[cd]pentalene-3,5,7- trione 206 265° C. 2,6-anthracenediol,- 13979-53-8 di-Ac form 207 265° C. 1H,9H-pyrrolo[3,2- 147345-48-0 b][1,4]benzoxazin-2(3H)-one 208 265° C.
  • the one or more organic compounds or chemicals are processed to minimize evaporative loss, enhance crystallinity, and to obtain high purity levels.
  • the one or more organic compounds are processed into compacted shapes, such as pellets or grains, by application of pressure in a die or mold, by way of example.
  • the structural integrity of pellets is desirably sufficient to withstand compressive forces of the HTTCO device, for example to withstand the applied force and bias to the HTTCO springs and encasement in a HTTCO assembly.
  • HTTCO's to maintain physical rigidity and spring compression and therefore maintain electrical continuity at TCO operating temperatures in a high temperature device, yet further having the ability to physically transition and open the circuit at a rated threshold temperature is an important feature of the high-temperature thermal pellet compositions of the present teachings.
  • certain HTTCOs are capable of withstanding extended exposure to operating temperatures up to about 5° C. below the threshold or actuation temperature without breaking the electrical continuity of the circuit.
  • the high temperature thermal pellet compositions can be manufactured into any commercially available form suitable for use inside a housing of a TCO, including granules, pellets, spheres and any geometric shape known to those in the art.
  • the high temperature thermal cutoff pellet compositions of the present disclosure may optionally include one or more components selected from the group consisting of: a binder, a press aid, a release agent, a pigment, or mixtures thereof.
  • the binder component which generally softens (melts) at a temperature below the melting point of the organic component, is primarily utilized to assist in the production of pellets.
  • suitable binders include polyethylene glycol, 1,3-benzenediol, epoxies, polyamides and mixtures thereof.
  • the binder is generally present in amounts up to about 10 wt. % based on the total composition.
  • a lubricant or pressing aid to aid in flowing and fill properties when processing the thermal pellets.
  • a lubricant or pressing aid for example, among the numerous lubricants or press aids which have proven useful are calcium stearate, boron nitride, magnesium silicate and polytetrafluoroethylene (Teflon®), among others.
  • the lubricant is generally present in an amount up to about 5 wt. % based on the total pellet composition.
  • coloring agents such as pigments into the thermal cutoff composition to allow for rapid visual inspection of the pellets condition. Virtually any known pigment which is compatible with the aforementioned thermal cutoff composition components may be employed. Pigments, when employed, are typically present in an amount up to about 2 wt. % of the pellet composition.
  • the pellet composition may consist essentially of a single organic composition as the primary ingredient to arrive at a transition temperature of greater than or equal to about 240° C., and optionally a binder, optionally a press aid, optionally a release agent, and/or optionally a pigment.
  • a pellet composition may comprise minimal amount of diluents or impurities that do not substantially affect the transition temperature of the pellet composition or the performance of the HTTCO at operating temperatures above the threshold temperature.
  • a first high-temperature thermal pellet sample can be prepared with the objective of obtaining a product having an expected transition temperature (e.g., melting point temperature or melt transition temperature) of about 240° C.
  • the sample is processed to enhance the crystallinity and then prepared by mixing between about 90% to about 100% by weight of chemical either alone or with 10% to about 0.25% by weight of additives such as binders in a hammermill mixer.
  • additives such as binders in a hammermill mixer.
  • Added to the aforementioned organic compounds may be 5% to 0.25% by weight of a binders, such as polyamide binder, among others and 1% to 0.05% by weight of an organic azo pigment.
  • the resulting composition exhibits a transition temperature/melting point temperature of about 236° C.
  • Additional samples can be prepared to make a HTTCO product having a melting point temperature of about 257° C.
  • the sample is processed to enhance the crystallinity and then prepared by mixing between about 90% to about 100% by weight of chemical either alone or with 10% to about 0.25% by weight of additives, such as binders, in a hammermill mixer.
  • additives such as binders
  • Added to the aforementioned organic compounds may be 5% to 0.25% by weight of binders, such as polyamide binder, among others and 1% to 0.05% by weight of an organic azo pigment.
  • the sample may be analyzed using differential scanning calorimetry (DSC). The resulting composition has a transition temperature/melting point temperature of about 257° C.
  • high-temperature thermal cutoff compositions of the present disclosure are also expected to exhibit clean current interrupt properties, decreased material and processing costs, and should have flexibility to permit customized design of predetermined thermal cutoffs to specific customer needs.
  • high melting point organic compositions can be formulated by use of computer software to calculate melting points of organic compounds for example, such as the computer program sold under the tradename PROMA2000®, manufactured by Daijin Technologies Corp. South Korea.
  • transition temperatures/melting points of the various compositions to be used in the thermal cutoff composition in the present disclosure can be measured using ThermoGravimetric Analyzers coupled with and without Mass Spectrometer (TGA-MS), differential scanning colorimetry (DSC) and differential thermal analysis (DTA), by way of example.
  • TGA-MS ThermoGravimetric Analyzers coupled with and without Mass Spectrometer
  • DSC differential scanning colorimetry
  • DTA differential thermal analysis
  • Devices for performing these qualitative and quantitative assays are commercially available, for example, from TA Instruments, New Castle, Del. USA, Model Q2000 (DSC), and Mettler STARe ThermoGravimetric Analyzer, TGA/sDTA851 e, coupled to a Balzers ThermoStar Mass Spectrometer from Mettler-Toledo, Columbus, Ohio.
  • the compositions of the present teachings can be quantitatively analyzed using known techniques such as proton or carbon nuclear magnetic resonance, mass spectroscopy or
  • the high temperature TCO device comprises a high-temperature sealant system that is used over one of more openings in the housing to provide a barrier between the interior of the HTTCO and the external atmosphere.
  • the high temperature sealant system or seal is robust, reliable, and maintains integrity as high operating temperatures of the HTTCO device.
  • the seal is an important aspect of the reliability and longevity of the HTTCO device, in that selection of an appropriate seal material provides a barrier that maintains chemical equilibrium inside the HTTCO, even at the high operating temperatures of the HTTCO and prevents substantial loss of the pellet materials through the seal or barrier.
  • the seal material system provides a strong sealing mechanism over one or more openings in the housing to prevent undesirable thermal pellet sublimation, and thus, loss of pellet material.
  • the reliability of the HTTCO sealing system can be related to the lifespan of the HTTCO device, where a predetermined life span is at least 1,000 hours or longer at 235° C. (reflecting the operating temperatures of about 5° C. than the threshold rating temperature of 240° C.).
  • the high-temperature seal system is an epoxy-based system that is cured to provide a durable, high-temperature, strong sealing mechanism.
  • One particularly suitable high temperature resistant epoxy system is formed from precursors comprising one or more diglycidyl ether of bisphenol A resins, which are combined with a hardener, for example a modified imidazole hardener or epichlorhydrin.
  • the epoxy systems of the present invention are generally prepared in accordance with the manufacturer's recommendations.
  • the epoxy systems are prepared in a modified manner to facilitate curing of the epoxy system in a manner that produces a strong mechanical seal between the HTTCO components (both metal and ceramic), which can withstand temperatures above about 235° C., optionally above about 240° C., optionally above about 245° C., optionally above about 250° C., optionally above about 260° C., optionally above about 265° C., optionally above about 270° C., optionally above about 275° C., optionally above about 280° C., optionally above about 285° C., optionally above about 290° C., and in certain aspects, optionally up to about 300° C., in a manner capable of retaining a stable thermal pellet composition and preventing substantial sublimation of the thermal pellet composition.
  • the epoxy systems of the present invention are cured to B-stage and/or full advanced or accelerated cure stage at various temperatures and relative humidity suitable to create the desired barrier seal.
  • the B-stage epoxy cure is a low temperature cure typically performed at less than or equal to about 60° C. at various relative humidities ranging from about 0% to about 85%, optionally at about 0 to about 75%, optionally about 0 to about 50%, optionally about 0 to about 40%, and in certain aspects about 0 to about 35%.
  • a polymer seal is generally considered to be B-stage cured when the seal has a hardness shown by impression of a permanent indent mark at Shore Durometer 75.
  • the curing is conducted to achieve a hardness of at least Shore D 75.
  • an accelerated or advanced cure is conducted after B-stage curing of the HTTCO device at an elevated temperature, for example from about 150° C. to about 175° C. for 3 to 5 hours, by way of example.
  • one suitable high-temperature epoxy-based sealant system to form a seal in the HTTCO comprises precursors comprising a diglycidyl ether bisphenol A resin and a hardener.
  • a hardener comprises a modified imidazole compound.
  • the hardener comprises a 2-ethyl-4-methyl-1H-imidazole.
  • the epoxy-based sealant is formed by combining at least two epoxy precursors, where a first precursor comprises at least one epoxy resin, such as a bisphenol A diglycidyl ether, an elastomer polymer, and neopentyl glycol diglycidyl ether; and a second precursor comprises 2-ethyl-4-methyl-1H-imidazole as the hardener.
  • a commercially available diglycidyl ether of bisphenol A and modified imidazole hardener system is commercially available from Henkel Loctite as the following: Loctite® Hysol® 210210 Epoxy Resin Part A (Item No.
  • Loctite® Hysol® 210210 Epoxy Resin Part A contains about 60-100% by weight of a first proprietary epoxy resin, which is believed to be a modified bisphenol A diglycidyl ether epoxy resin 10-30% of a second proprietary epoxy resin, which is also believed to be a modified bisphenol A diglycidyl ether, 10-30% of neopentyl glycol diglycidyl ether (CAS No.
  • Loctite® Hysol® 210211 Epoxy Resin Part B contains 60-100% by weight of a proprietary modified imidazole, which is believed to be 2-ethyl-4-methyl-1H-imidazole.
  • Epoxy Resin Part C contains 30-60% by weight titanium dioxide, 10-30% of a first proprietary epoxy resin, which is believed to be a modified bisphenol A diglycidyl ether epoxy resin, 10-30% of a second proprietary epoxy resin, which is also believed to be a modified bisphenol A diglycidyl ether, and 1-5% of a third proprietary epoxy resin, which is also believed to be a modified bisphenol A diglycidyl ether epoxy, 1-5% neopentyl glycol diglycidyl ether, 1-5% alkyl glycidyl ether, 1-5% aluminum oxide, 1-5% fumed amorphous silica, and lastly 1-5% of a proprietary elastomeric polymer.
  • a first proprietary epoxy resin which is believed to be a modified bisphenol A diglycidyl ether epoxy resin
  • 10-30% of a second proprietary epoxy resin which is also believed to be a modified bisphenol A diglycidyl ether
  • 1-5% of a third proprietary epoxy resin which is also believed to be
  • Part A 80-100 parts by weight of the resin Part A is mixed with 0-20 parts by weight for the hardener Part B.
  • Part C is optional and can be added at 0-20 parts by weight to form the final C5 epoxy to be applied to the TCO components for sealing the device containing the thermal pellet composition.
  • an epoxy-based sealant is formed by combining at least two precursors, wherein a first precursor comprises an epoxy resin or bisphenol A diglycidyl ether polymer; a second precursor comprises a hardener or curing agent, such as 1-(2-cyanoethyl)-2-ethyl-4-methyl imidazole; and a third precursor comprises catalysts including benzenetetracarboxylic-1,2,4,5-dianhydride, hexahydrophthalic anhydride, and phthalic anhydride.
  • a first precursor comprises an epoxy resin or bisphenol A diglycidyl ether polymer
  • a second precursor comprises a hardener or curing agent, such as 1-(2-cyanoethyl)-2-ethyl-4-methyl imidazole
  • a third precursor comprises catalysts including benzenetetracarboxylic-1,2,4,5-dianhydride, hexahydrophthalic anhydride, and phthalic anhydride.
  • the epoxy-based sealant system is optionally cured. Curing can be conducted by any means known in the art, including by application of heat, actinic radiation, and the like.
  • the epoxy sealant materials are subjected to a B-stage cure, where the epoxy system is heated to a temperature range of about 45° C. to about 65° C. in a controlled atmosphere having relative humidity ranging from 0% to 80%.
  • a full advanced cure can be conducted after B-stage curing.
  • An advanced cure is optionally conducted at a temperature range of about 150° C. to about 200° C.
  • the C5 epoxy seal material is cured by placing the HTTCO device in an oven and heating the TCO at 248° C. for about 3 to about 9 hours at 0% relative humidity.
  • the HTTCOs can be sealed with a suitable epoxy-based system commercially available from Emerson & Cuming Corp., Billerica, Mass. USA, which is a bisphenol A diglycidyl ether polymer (Part A); an epichlorohydrin hardener (Part B); and a catalyst (Part C) sold under the trade name Stycast® W 66 epoxy system (herein referred to as the “W66 epoxy system”).
  • the W66 epoxy system includes Part A comprising Bisphenol A diglycidyl ether polymer having an average molecular weight of less than 700 at 100 wt.
  • Part B comprising 1-(2-cyanoethyle)-2-ethyl-4-methyl Imidazole hardener at greater than 99 wt. % in less than 0.1% acrylonitrile carrier.
  • Part C of the W66 comprises a catalyst of Benzenetetracarboxylic-1,2,4,5-Dianhydride (35-50% by weight), Hexahydrophthalic anhydride (35-50% by weight) and phthalic anhydride (1-5% by weight).
  • part A in an amount ranging from 50% to about 80% by weight is mixed with part B in an amount ranging from 50% to about 20% by weight and mixed.
  • the W66 epoxy is optionally cured to a B-stage and/or advanced cure.
  • the W66 seal system is applied and cured by placing the device in a controlled atmosphere and heating the TCO at 40° C. for about 48 to about 96 hours at 35% to 85% relative humidity.
  • a high temperature TCO device is formed as follows.
  • a pellet is formed by mixing 980 g to 1000 g of triptycene (commercially available from Sigma-Aldrich manufacturer at 95% to 99% purity) with 20 g to 0.5 g of colorants, binders, and or release agents.
  • the homogenized mixture is processed on a standard powder compaction press widely available from pharmaceutical equipment suppliers.
  • the powder is fed through a gated powder flow control system and spread evenly over a rotary die table.
  • the powder fills the dies and punches press the powder in the dies under approximately 1 ton to 4 tons pressure to form a compacted powder pellet having a density of 29 pellets per gram to 50 pellets per gram.
  • the pellet is placed into a high-conductivity metal, closed-end cylinder with an inner diameter approximately the outer diameter of the TCO pellet.
  • the closed end of the cylinder is staked shut with an axial conductive metal lead protruding out of the cylinder.
  • Other components are loaded atop the pellet in a stacked fashion depending on the end-use requirements of the TCO.
  • a sub-assembly comprised of a non-conductive ceramic bushing with an axial bore hole and a conductive metal lead which has been inserted in the open bore and mechanically restrained into a permanent one-piece assembly by deformation of the metal lead is inserted into the open end of the TCO cylinder.
  • the stacked components noted earlier in paragraph 0018 are compressed into the cylinder by the ceramic, isolated lead assembly and the rim of the open end of the cylinder is mechanically rolled over the ceramic bushing to permanently enclose the internal components in the TCO cylinder.
  • the closed TCO is then sealed with a high temperature, epoxy sealant.
  • An epoxy-based sealant is prepared at 25° C.
  • LOCTITE® HYSOL® 210210 Epoxy resin Part A an epoxy resin comprising bisphenol A and diglycidyl ether
  • 14 g of LOCTITE® HYSOL® 210211 Epoxy hardener Part B an imidazole hardener
  • 13 g of LOCTITE® HYSOL® 210209 Epoxy pigment Part C epoxy resins, neopentyl glycol diglycidyl ether, pigment, . . .
  • the assembled TCO having the epoxy sealing compound applied is then cured for 9 hours at 48° C. to 60° C. under 0% RH to 85%.
  • the B-staged TCO assemblies are then cured in a controlled over at a temperature of 150° C. optionally up to 235° C. in 0% RH to 35% RH for 3 hours up to 6 hours.
  • the C5 epoxy system is studied to demonstrate the high-temperature performance of the sealant system, as well as the ability to retain polycyclic organic compounds of the pellet of the HTTCO device.
  • the high-temperature thermal pellet contained triptycene and a polytetrafluoroethylene release agent, which was retained by the C5 epoxy seal during continuous exposure to 247° C.
  • the melting points of the two pellet organic compounds, triptycene and pentaerythritol are similar, and, are known to have similar volatile evolution behavior.
  • the C5 sealing system is able to retain the triptycene inside the sealed HTTCO housing significantly better than the pentaerythritol.
  • the pellet height of the pentaerythritol at Day 1 goes from an initial pellet height of 101 thousandths of an inch to 0.00 thousandths of an inch.
  • TCOs having the pentaerythritol open continuity or exhibited resistance greater than 200 kOhm (actuate) almost immediately.
  • the HTTCO having a pellet containing triptycene has an initial pellet height of about 98 thousandths of an inch and retains at least 80 thousandths of an inch pellet height for at least 13 weeks and does not exhibit resistance of greater than 200 kOhm until over 2,100 hours of performance for 9 out of 10 HTTCO samples.
  • the difference in retention is believed to be attributed to functionality or size of the molecule, or a combination of both.
  • the sizes (radii) of the compounds are calculated.
  • triptycene has a radius of 0.46 nm while pentaerythritol has a radius of 0.33 nm.
  • the triptycene molecule is fairly rigid given the steric hindrance of the three benzene rings. When viewed along the end of the molecule, the 3 benzene molecules separate at 120° from each other for maximum spacing.
  • the pentaerythritol has significantly more molecular freedom to twist and reorient itself.
  • the triptycene has little functionality other than the double bonds present in the aromatic ring.
  • the aromatic rings have the ability to pi-pi stack with other aromatic rings in the epoxy structure, which could immobilize them in the pores thus blocking the pore.
  • the pentaerythritol has four polar hydroxyl bonds that have hydrogen bond accepting/donating capability.
  • a 1-aminoanthraquinone [CAS # 82-45-1] pellet is also examined for its behavior in a C5 epoxy sealing system.
  • the 1-aminoanthraquinone has a melting point in the same range as the pentaerythritol and triptycene, so once again the size and functionality are examined to provide insight into the interaction of the organic compound with the cured epoxy seal material.
  • the 1-aminoanthraquinone molecule lies in a single plane and is a rigid molecule due to the benzene rings and the carbonyl bonds that bond them together—all of which require planar orientation.
  • the radius of the 1-aminoanthraquinone is 0.45 nm, which is similar in size to the triptycene.
  • the 1-aminoanthraquinone has the added advantage of having more functionality present with which to interact with the epoxy seal material.
  • the carbonyl bonds can accept hydrogen donation and the amine group can hydrogen donate/accept.
  • 1-aminoanthraquinone Based on its steric similarity to triptycene and its functionality similarity to pentaerythritol, 1-aminoanthraquinone has even greater retention by the epoxy seal that the triptycene or pentaerythritol.
  • Specimens of the C5 system are produced by reacting the components at temperatures and humidities listed below. All specimens are exposed to the same temperature programming for B-staged and advanced cure levels. B-staged specimens are heated at 48° C. for 5 hours and then at 58° C. for 4 hours. The B-staging is performed in two different relative humidity environments (0% and 35% RH) to determine the effect of water on the B-stage curing. Specimens exposed to 35% RH are B-staged in a humidity chamber that maintains the humidity at 35% while following the temperature program. Specimens prepared in 0% RH are B-staged in an oven.
  • a compressed air source with two water traps is employed to ensure that no water is exposed to the epoxy system during B-staging.
  • the humidity is not monitored during advanced curing, but the specimens are still identified by their B-stage humidity level for labeling purposes.
  • both cured epoxy seal samples have very low surface areas (approximately 0.09 m 2 /g), and the shapes of the adsorption plots indicate a very nonporous structure.
  • the average pore width is determined.
  • Two different techniques are employed for pore width determination—the BET value and the BJH value.
  • the C5 epoxy sample cured at 35% humidity showed a larger pore width than the C5 epoxy cured with 0% humidity (25.53 as opposed to 0.312 nm with BET, 39.53 as opposed to 27.16 nm with BJH).
  • Part A epoxy resin has the six components listed above, including the two proprietary epoxy resins and a proprietary elastomeric polymer; Part B has a single a proprietary imidazole hardener, and Part C is an optional component for colorant and includes nine components, including three proprietary epoxy resins and a proprietary elastomer. Analysis of the materials indicates that the hardener of Part B is 2-ethyl-4-methyl-1H-imidazole.
  • the silica and titanium dioxide are believed to be relatively inert and do not play a significant role in the cured epoxy chemistry.
  • the neopentyl glycol diglycidyl ether (CAS #17557-23-2) of Part A has two epoxide groups, so it does not reduce the crosslink density and is believed to provide structural flexibility in between the larger, more rigid aromatic epoxy resins. This increased mobility allows the material to desirably flow and increases the pot life.
  • the two proprietary epoxy resins are major constituents of the Part A precursor.
  • the elastomeric polymer is not believed to react with the epoxies during curing, although unsaturated double bonds may participate in some cross-linking. Generally, where the elastomeric polymer does not react, it forms a separate phase within the epoxy which provides more impact resistance and increased mobility.
  • the present teachings provide high-temperature thermal cutoff devices and methods of making such devices, by forming high-temperature stable seals and high temperature thermal pellets comprising one or more organic compounds that are substantially retained by the seal barrier.
  • the HTTCOs are highly stable, robust, and are capable of use as switching devices in a variety of high-temperature applications that were previously not possible, such as high-temperature clothing and hair styling irons.

Abstract

The present disclosure provides high temperature thermal cutoff devices having a high-temperature thermal pellet with a transition temperature of greater than or equal to about 240° C. and comprising at least one organic compound. The pellet is disposed in a housing, which is sealed with a high-temperature seal that provides substantial sealing up to at least the transition temperature. The high-temperature TCO also has a current interruption assembly, which establishes electrical continuity in a first operating condition corresponding to an operating temperature of less than said transition temperature and discontinues electrical continuity when the operating temperature exceeds the transition temperature. Methods of making such high-temperature thermal cut off devices are also provided.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application claims the benefit of U.S. Provisional Application No. 61/086,330, filed Aug. 5, 2008. The entire disclosure of the above application is incorporated herein by reference.
  • FIELD
  • The present disclosure relates to electrical current interruption devices and more particularly to high-temperature electrical current interruption safety devices, or thermal cut-offs, that provide protection from over-temperature conditions.
  • BACKGROUND
  • The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
  • Temperatures of operation for appliances, electronics, motors and other electrical devices typically have an optimum range. The temperature range where damage can occur to system components or where the device becomes a potential safety hazard in the application or to the end-user serves as an important detection threshold. Various devices are capable of sensing such over-temperature thresholds. Certain devices which are capable of sensing over-temperature conditions and interrupting electrical current include electrical thermal fuses, which only operate in a narrow temperature range. For example, tin and lead alloys, indium and tin alloys, or other metal alloys which form a eutectic metal, are unsuitable for appliance, electronic, electrical and motor applications due to undesirably broad temperature response thresholds and/or detection temperatures that are outside the desired range of safety.
  • One type of device particularly suitable for over-temperature detection is an electrical current interruption safety device, known as a thermal cut-off (TCO), which is capable of temperature detection and simultaneous interruption of current, when necessary. Such TCO devices are typically installed in an electrical application between the current source and electrical components, such that the TCO is capable of interrupting the circuit continuity in the event of a potentially harmful or potentially dangerous over-temperature condition. TCOs are often designed to shut off the flow of electric current to the application in an irreversible manner, without the option of resetting the TCO current interrupting device. High temperature appliances and applications require the use of robust over-temperature detection devices with high-holding temperatures exceeding the operating temperatures and/or holding temperatures of conventional TCO designs. Thus, in various aspects, the present disclosure provides stable, reliable, and robust high-temperature TCO devices.
  • DRAWINGS
  • The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.
  • FIG. 1 is an enlarged cross sectional view of an exemplary thermal cutoff device construction;
  • FIG. 2 illustrates the thermal cutoff construction of FIG. 1 after a thermal pellet has undergone a physical transition and a current interruption actuating assembly has caused electrical switching to break continuity and change the thermal cutoff device's operating condition;
  • FIG. 3 is a side perspective view illustrating the current interruption actuating assembly;
  • FIG. 4 is a side view of a sliding contact member of the current interruption actuating assembly switch construction of FIG. 1;
  • FIG. 5 is a side view of one of the springs of the current interruption actuating assembly of FIG. 1;
  • FIG. 6 is a cross sectional view of a ceramic bushing of FIG. 1; and
  • FIG. 7 is an elevation view of a thermal pellet of FIG. 1.
  • DETAILED DESCRIPTION
  • The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses.
  • Various safety electrical current interruption devices, including thermal cut-off electrical current interruption safety devices (TCOs), meet a broad range of application temperatures and break electrical current above a threshold temperature or rating, typically ranging from about 60° C. up to about 235° C. However, conventional TCO devices are not rated for higher temperature applications, such as those greater than or equal to about 240° C. In other words, conventional TCO devices have not sufficiently fulfilled the performance criteria, particularly stability and robustness, for long-term use in high-temperature applications as a safety device.
  • In various aspects, the present disclosure provides a high temperature thermal cutoff device (referred to herein as a “HTTCO”). Such an HTTCO device is capable of switching continuity of an electrical circuit or electrical communication when the surrounding environment or operating temperature reaches a predetermined threshold temperature. By use of the term “high-temperature” thermal cutoff device, it is meant that device has a threshold or actuation temperature of greater than about 235° C., optionally greater than or equal to about 240° C., optionally greater than or equal to about 245° C., optionally greater than or equal to about 250° C., optionally greater than or equal to about 255° C., optionally greater than or equal to about 260° C., optionally greater than or equal to about 265° C., optionally greater than or equal to about 270° C., optionally greater than or equal to about 275° C., optionally greater than or equal to about 280° C., optionally greater than or equal to about 285° C., optionally greater than or equal to about 290° C., optionally greater than or equal to about 295° C., optionally greater than or equal to about 300° C., and in certain aspects, greater than or equal to about 305° C. In certain aspects, the HTTCO exhibits switching behavior at a threshold or actuation temperature of greater than or equal to about 240° C. to less than or equal to about 270° C., optionally greater than or equal to about 240° C. to less than or equal to about 265° C., optionally greater than or equal to about 240° C. to less than or equal to about 260° C., optionally greater than or equal to about 240° C. to less than or equal to about 255° C., optionally greater than or equal to about 240° C. to less than or equal to about 250° C., optionally greater than or equal to about 240° C. to less than or equal to about 245° C., optionally greater than or equal to about 240° C. to less than or equal to about 243° C. In certain aspects, the HTTCO exhibits switching behavior at a threshold temperature of about 240° C., optionally about 241° C., optionally about 242° C., optionally about 243° C., optionally about 244° C., optionally about 245° C., optionally about 246° C., optionally about 247° C., optionally about 248° C., optionally about 249° C., optionally about 250° C., optionally about 251° C., optionally about 252° C., optionally about 253° C., optionally about 254° C., optionally about 255° C., optionally about 256° C., optionally about 257° C., optionally about 258° C., optionally about 259° C., optionally about 260° C., optionally about 261° C., optionally about 262° C., optionally about 263° C., optionally about 264° C., optionally about 265° C., optionally about 266° C., optionally about 267° C., optionally about 268° C., optionally about 269° C., and in certain embodiments, optionally about 270° C.
  • An illustrative test demonstrating the performance of a high temperature thermal pellet composition includes continuous aging of HTTCO devices formed in accordance with the present teachings for at least 1,000 hours at a sustained temperature of 235° C. While the HTTCO ideally meets or exceeds the aforementioned illustrative test protocol, it should be understood by those skilled in the art that the compositions are contemplated as being useful for both low voltage and high voltage applications. Further, in certain aspects, the high temperature thermal pellet compositions meet or exceed Underwriters' Laboratory test UL1020 or IEC/EN 60691 standards, which are respectively incorporated herein by reference. In certain embodiments, HTTCO devices meet one or more of such standards at the pre-selected high temperature rating for the device. While the performance criteria is fully outlined in each of these standards, salient aspects of performance tests that demonstrate conformance to the IEC 60691, Third Edition standard are summarized in Table 1.
  • TABLE 1
    IEC 60691, 3rd Edition Tests
    I Clause 7 Ink Rub Test:
    A Rub test sample with a cotton “wheel”
    soaked in water.
    B Take a photo.
    C After tensile, thrust, temperature/
    humidity, transient over load, temperature
    check, and dielectric/insulation testing
    repeat steps A and B.
    II Clause 9.2 Tensile (pull) Test:
    A Place sample in the fixture and apply 3.7 lbs
    tensile for one minute.
    B Release force and remove.
    III Clause 9.3 Thrust (push) Test:
    A Place sample in the fixture and apply 0.9 lbs
    thrust for one minute.
    B Release force and remove
    IV Clause 9.4 Twist/Bend Test:
    A Bend contact lead 90°, twist lead 180°,
    and check for epoxy breakage.
    V Clause 10.2 Temperature/
    Humidity Test:
    A Samples are subjected to two complete
    conditioning cycles:
    i 24 hours at rated functioning temperature
    minus 15° C.;
    ii 96 hours at 35° C. (+/−2°) and 95% R.H. (+/−5
    R.H.);
    iii 8 hours AT 0° C. (+/−2°).
    B Samples are subjected to a third complete
    conditioning cycle:
    i 24 hours at rated functioning temperature
    minus 15° C.;
    ii 168 hours at 35° C. (+/−2°) and 95% R.H.
    (+/−5 R.H.);
    iii 8 hours AT 0° C. (+/−2°).
    VI Clause 10.6 Current Interrupt
    Test:
    A Sample is placed in a kiln at rated
    functioning temperature minus 10° C. for
    three minutes.
    B Sample is tested at 110% of rated voltage
    and 150% of rated current until sample
    interrupts the test current.
    VII Clause 10.7 Transient Overload
    (pulse) Test:
    A Samples are place in the current path of
    D.C. current pulses, with an amplitude of
    15 times rated current for a duration of 3 ms
    with 10 s intervals are applied for 100
    cycles.
    VIII Clause 11.2 Temperature Check
    (Tf):
    A Samples are placed in an oven at rated
    functioning temperature minus 10° C. until
    stable, the temperature is then increased
    steadily at 0.5° C./minute until all samples
    are opened, recording the temperature of
    opening to pass +0/−5° C..
    IX Clause 11.3 Maximum
    Temperature (Tm):
    A Samples are placed in a kiln at a specified
    temperature (470° C. +0/−5° for a 257° C.
    TCO) for 10 minutes, with the samples
    maintained at Tm a dielectric test at 500
    Vac with no breakdown, and an insulation
    resistance test at 500 Vdc with a minimum
    of 0.2 MΩ.
    X Clause 11.4 Aging:
    A Samples are placed in a kiln at 200° C. for
    three weeks. At the conclusion of this test
    at least 50% of samples shall not have
    functioned.
    B Samples are then placed in a kiln at rated
    functioning temperature minus 15° C. for
    three weeks. At the conclusion of this test
    at least 50% of samples shall not have
    functioned.
    C Samples are then placed in a kiln at rated
    functioning temperature minus 10° C. for
    two weeks.
    D Samples are then placed in a kiln at rated
    functioning temperature minus 5° C. for one
    week.
    E Samples are then placed in a kiln at rated
    functioning temperature minus 3° C. for one
    week.
    F Samples are then placed in a kiln at rated
    functioning temperature plus 3° C. for 24
    hours.
    G This test is considered successful if all
    samples have functioned at the conclusion
    of step X(F).
    XI Clause 10.3/10.4 Room
    Temperature Dielectric and
    Insulation Resistance:
    A All test samples must complete and
    comply with a dielectric test at 500 Vac
    with no breakdown, and an insulation
    resistance test at 500 Vdc with a minimum
    of 0.2 MΩ.
  • In various aspects, the HTTCO ot the present disclosure comprises a sealed housing having disposed therein a high-temperature thermal pellet having a transition temperature of greater than or equal to about 240° C. The transition temperature of the high-temperature thermal pellet relates to the threshold temperature at which the HTTCO device switches or actuates, as will be described in greater detail below. The high-temperature thermal pellet comprises at least one organic compound, which generally has a melting point or melting point range near the pre-selected or desired transition temperature. Further, the HTTCO has a high-temperature seal disposed in a portion of at least one opening of the housing that substantially seals the housing up to the transition temperature of the high-temperature thermal pellet. The HTTCO also comprises a current interruption assembly that is at least partially disposed within the housing. The current interruption assembly establishes electrical continuity in a first operating condition of the HTTCO, which corresponds to an operating temperature of less than the transition temperature of the high-temperature thermal pellet and that discontinues electrical continuity when the operating temperature exceeds the transition temperature.
  • By way of background, an exemplary TCO device is described herein, as set forth in FIGS. 1 and 2. In general, a TCO 10 includes a conductive metallic housing or casing 11 having a first metallic electrical conductor 12 in electrical contact with a closed end 13 of the housing 11. An isolation bushing 14, such as a ceramic bushing, is disposed in an opening 15 of the housing 11. Housing 11 further includes a retainer edge 16, which secures the ceramic bushing 14 within the end of the housing 11. An electric current interrupter assembly 25 for actuating the device in response to a high temperature, for example, by breaking continuity of an electrical circuit, includes an electric contact 17, such as a metallic electrical conductor, at least partially disposed within the housing 11 through opening 15. Electric contact 17 passes through isolation bushing 14 and has an enlarged terminal end 18 disposed against one side 19 of isolation bushing 14 and a second end 20 projecting out of the outer end 21 of isolation bushing 14. A seal 28 is disposed over the opening 15 and can create sealing contact with the housing 11 and its retainer edge 16, the isolation bushing 14, and the exposed portion of the second end 20 of electric contact 17. In this manner, an interior portion 29 of the housing 11 is substantially sealed from the external environment 30. By “substantially sealed” it is meant that the while the barrier seal is optionally porous at a microscopic level, the barrier is capable of preventing escape or significant mass loss of the thermal pellet material, for example, the seal retains at least about 95% of the mass of the initial thermal pellet through 1,000 hours of continuous operation at 235° C., optionally about 96% of the mass of the initial thermal pellet, optionally greater than about 97% of the mass of the initial thermal pellet, optionally greater than or equal to about 98% of the mass of the initial thermal pellet, optionally greater than or equal to about 99% of the mass of the initial thermal pellet, optionally greater than or equal to about 99.5% of the mass of the initial thermal pellet and in certain aspects, greater than or equal to about 99.9% of the mass of the initial thermal pellet is retained within the housing through continuous operation.
  • The current interruption assembly 25, which actuates or switches to change continuity of an electrical circuit, further includes a sliding contact member 22, formed of electrically conductive material, such as a metal is disposed inside the housing 11 and has resilient peripheral fingers 23 (FIG. 4) disposed in sliding engagement with the internal peripheral surface 24 of the housing 11 to provide electrical contact there between. Moreover, when the TCO has an operating temperature that is below the predetermined threshold set-point temperature of the TCO device, the sliding contact member 22 is disposed in electrical contact with the terminal end 18 of electric contact 17.
  • Current interruption assembly 25 also includes a tensioning mechanism, which may include a plurality of tensioning mechanisms. The tensioning mechanism 25 biases the sliding contact member 22 against the terminal end 18 of electric contact 17 to establish electrical contact in the first operating condition (where operating temperatures are below the threshold temperature of the TCO device, as will be described below). As shown in FIGS. 1 and 2, the tensioning mechanism includes a pair of springs 31, which are respectively disposed on opposite sides of the sliding contact member 22. The springs 31 include a compression spring 26 and an expansion trip spring 27.
  • A thermally responsive pellet or thermal pellet 25, as best illustrated in FIG. 3, is disposed in the housing 11 against the end wall 13 thereof. The compression spring 26 is in a compressed state between the solid thermal pellet 25 and the sliding contact member 22 and in the exemplary design shown, generally has a stronger compressed force than the force of the expansion trip spring 27, which is disposed between the contact member 22 and the isolation bushing 14, such that the sliding contact member 22 is biased towards (e.g., held by the force of the spring 26) and in electrical contact with the enlarged end 18 of the electrical contact 17. In this manner, an electrical circuit is established between the first electrical conductor 12 and electrical contact 17 through the conductive housing 11 and sliding contact member 22.
  • As noted above, TCO devices are designed to include a thermal pellet 25 that is reliably stable in the first operating condition (where the operating temperature, for example, the temperature of the surrounding environment 30 is below a threshold temperature); however reliably transitions to a different physical state when the operating temperature meets or exceeds such threshold temperature in a second operating condition. In such conditions, where the operating temperature meets or exceeds a threshold temperature, the thermal pellet 25 melts, liquefies, softens, volatilizes, or otherwise transitions to a different physical state during an adverse heating condition, which is illustrated in FIG. 2.
  • The springs 31 are adapted to expand and release, as illustrated by expansion trip spring 27 in FIG. 5, and through the relationship of the particular forces and length of the compression spring 26 and expansion trip spring 27, the sliding contact member 22 is moved out of electrical contact with the end 18 of the electric contact 17 in the manner shown in FIG. 2, so that the electrical circuit between the terminal conductor 12 and electrical contact 17 through the thermal cutoff construction 10 (via the housing 11 and sliding contact member 22) is discontinued and broken, remaining open as illustrated in FIG. 2.
  • The thermal cutoff device described in the present disclosure are used for purposes of illustration are exemplary and in certain aspects, should not be construed to be limiting. In certain aspects, various components, designs, or operating principles may be varied in number or design. Various other thermal switching or cutoff devices are known in the art and likewise contemplated.
  • In various aspects, the high-temperature thermal pellet compositions of the present teachings are thermally and chemically stable, reliable, and robust for use in the HTTCO application. Preferably, the high-temperature thermal pellet composition will include one or more organic compounds, such as crystalline organic compounds. In various aspects, the high-temperature thermal pellet compositions are designed to have a transition temperature that permits the HTTCO device to have a final temperature (Tf) (also referred to as actuation or threshold temperature) where the internal contact breaks electrical continuity due to structural changes in the pellet composition, which in turn causes opening of tensioning mechanisms, for example. Thus, the transition temperature of the high-temperature thermal pellet directly corresponds to the threshold temperature Tf of the HTTCO device, whereby a switch in continuity is activated. As noted above, the transition temperature generally refers to the temperature at which a pellet melts, liquefies, softens, volatilizes, sublimates, or otherwise transitions to a different physical state to transform from a solid having structural rigidity to a form or phase that loses structural rigidity, either by contraction, displacement, or other physical changes, which cause the internal electrical contacts to separate due to the applied tension from the tensioning mechanism. Thus, as used herein, once the thermal pellet material reaches it transition temperature, it means that the material no longer possesses the structural integrity required to maintain a tensioning mechanism, such as a switch in a held-open or held-closed position, depending on the HTTCO device, for example.
  • As referred to herein, this transition temperature is also referred to as a “melting-point”; however, the compounds in the pellet composition need not fully melt in a conventional sense to achieve separation of the electrical contacts to break the internal circuit and electrical continuity. As recognized by those of skill in the art, a melting-point temperature is one where compounds or compositions transform from solid to liquid phase, which may occur at a range of temperatures, rather than at a single discrete temperature point. In certain aspects, the high temperature thermal pellet may soften or sublimate rather than melting, by way of non-limiting example, to achieve the separation of electrical contacts to break the circuit. Melting-point temperatures can be measured in various apparatuses, such as those produced by Thomas Hoover, Mettler and Fisher-Johns companies. Differential Scanning Colorimetry (DSC) techniques are also commonly used. Different measurement techniques may result in differing melting points, for example, optical analysis methods like Fisher-Johns measure light transmittance through a sample, a solid to liquid phase change. Early optical methods potentially suffered greater observer error versus more modern light beam transmittance melt point indicators. In addition, earlier techniques to determine melting point (before the use of digital high speed scan capabilities), rendered a broader range of results for melt points and other transitions. Likewise, before the advent of HPLC and other precise analytical techniques for determination of purity, the melt point of a sample, for example, measured by DSC, which measures heat flow behavior for example, crystallinity (solid-solid phase) changes as well as, solid to liquid phase changes, could show the solid-solid phase change of an impurity that may have been reported as a melt point, such as dehydration or breaking of hydroxyl bonds, as well as the solid-liquid phase change at the melt point for the material of interest. Thus, in various aspects, a composition can be selected for use in the thermal pellet that empirically exhibits a desirable physical change that will enable a pellet's physical transition without necessarily correlating to the predicted melting point ranges.
  • In certain aspects, the thermal pellet 25 has a relatively rapid and repeatable collapse rate, meaning once the environment 30 reaches a threshold temperature, the rate at which the thermal pellet composition 25 physically collapses is relatively high. By way of example, one method of testing a pellet collapse rate is via thermomechanical analysis (TMA) where a pellet is heated at a rapid rate to within about 10° C.-15° C. of the predicted melting point temperature, then a heating rate is selected, for example about 0.5° C./min through the predicted melting point temperature range. The physical height of the pellet is likewise measured at the beginning of the test and throughout this heating process, so that an amount of displacement from the top surface of the pellet to the underlying substrate (on which the pellet is initially placed) is measured. The rate, measured in micrometer per ° C., at which the pellet height collapses at the onset through to the end of the transition temperature correlates to the pellet collapse rate, for example, a 75% reduction of a pellet's height from a threshold temperature within about 100 micrometer/° C., optionally about 500 micrometer/° C., optionally about 1000 micrometer/° C. In various aspects, both the solid liquid phase transition temperature and pellet collapse rate are salient features of the thermal pellet 25, as the rapidity with which the pellet collapses ensures sufficient separation of electrical contacts in the HTTCO to avoid excessive arcing, which could melt various components and potentially impact HTTCO performance. Methods of testing and quantifying such a pellet collapse rate will be described in further detail below.
  • In certain aspects, the thermal pellet comprises one or more organic compounds having a melting-point temperature (mp) that occurs in a range of temperatures corresponding to the desired transition temperature. By way of example, in certain aspects, the high-temperature thermal pellet has one or more organic compounds that have a melting point temperature (mp) within about 5° C. below the transition temperature and within about 2° C. above the transition temperature (i.e., where T−5° C.≦mp≦T+2° C.), where T is the transition temperature.
  • In various aspects, the high-temperature thermal pellet compositions comprise organic compounds or materials that are selected to meet one or more of the following criterion. In certain aspects, the organic compositions selected for use in the high-temperature thermal pellet have a relatively high chemical purity. For example, in certain embodiments, desirable chemical candidates for the high temperature thermal pellet compositions have a range of purity levels from about 95% up to 99+%. In certain aspects, the organic compositions selected for use in the high temperature thermal pellets are particularly suitable for processing, handling, and toxicity characteristics. In certain embodiments, the organic chemical compounds or compositions selected for use in the high-temperature pellet compositions have a median lethal dose toxicity value (LD50) less than or equal to about 220 mg/kg (ppm) for a mouse; less than or equal to about 400 mg/kg (ppm) for a rabbit; and less than or equal to about 350 mg/kg (ppm) for a rat. Further, in certain aspects, the selected organic chemical compositions for the high-temperature thermal pellet desirably do not have documented carcinogenicity effects, mutagenicity effects, neurotoxicity effects, reproductive effects, teratogenicity effects, and/or other harmful health or epidemiological effects. In yet other aspects, the organic components for the high temperature thermal pellet compositions are selected such that alternate reactive residuals, reaction products formed during manufacture, decomposition products, or other species that might be formed during manufacture, storage, or use are absent, minimized, or are capable of purification and removal of such undesired species.
  • In certain aspects, the compositions selected for use in the high temperature thermal pellet composition exhibit long-term stability. By way of example, compositions are optionally selected to possess temperature or thermal stability, in other words, chemical compounds that show decomposition or volatility behavior within about 10° C., optionally within about 20° C., optionally within about 30° C., optionally within about 40° C., optionally within about 50° C., optionally within about 60° C., optionally within about 75° C., and in certain aspects, optionally within about 100° C. of the transition temperature or melting point of the organic compound may be rejected as viable candidates. Further, in certain embodiments, chemical compositions suitable for use as high-temperature thermal pellet compositions will not show a strong likelihood of heat-induced and age-progressive oxidation or decomposition.
  • Further, suitable compositions for high-temperature thermal pellets include those that are “electrically non-conductive,” meaning that the composition is capable of withstanding a 240 volt, 60 Hz sinusoidal potential between two electrodes at least about 5° C. above the Tf final temperature for at least one minute without conducting greater than 250 mA. In certain aspects, the select composition should be capable of withstanding a 240 volt, 60 Hz sinusoidal potential at least 10° C. above the Tf final temperature for at least about one minute without conducting greater than 250 mA. In yet other aspects, the high-temperature thermal cutoff compositions are optionally capable of withstanding a 240 volt, 60 Hz sinusoidal potential at least 50° C. above the final transition temperature Tf for at least about one minute without conducting greater than 250 mA of current.
  • In various aspects, the organic chemical compositions that are selected for use in the high temperature thermal composition have an initial melting point temperature of at least about 240° C., optionally about 241° C., optionally about 242° C., optionally about 243° C., optionally about 244° C., optionally about 245° C., optionally about 246° C., optionally about 247° C., optionally about 248° C., optionally about 249° C., optionally about 250° C., optionally about 251° C., optionally about 252° C., optionally about 253° C., optionally about 254° C., optionally about 255° C., optionally about 256° C., optionally about 257° C., optionally about 258° C., optionally about 259° C., optionally about 260° C., optionally about 261° C., optionally about 262° C., optionally about 263° C., optionally about 264° C., optionally about 265° C., optionally about 266° C., optionally about 267° C., optionally about 268° C., optionally about 269° C., optionally about 270° C., optionally about 271° C., optionally about 272° C., optionally about 273° C., optionally about 274° C., optionally about 275° C., optionally about 276° C., optionally about 277° C., optionally about 278° C., optionally about 279° C., optionally about 280° C., optionally about 281° C., optionally about 282° C., optionally about 283° C., optionally about 284° C., optionally about 285° C., optionally about 286° C., optionally about 287° C., optionally about 288° C., optionally about 289° C., optionally about 290° C., optionally about 291° C., optionally about 292° C., optionally about 293° C., optionally about 294° C., optionally about 295° C., optionally about 296° C., optionally about 297° C., optionally about 298° C., optionally about 299° C., optionally about 300° C., and in certain embodiments, optionally about 301° C. In certain aspects, the melting point of the organic composition for the high-temperature thermal pellet is greater than 275° C. and in certain aspects, optionally greater than 300° C. In certain embodiments, organic compounds that meet the above selection criteria and that can remain a solid at temperatures ranging from 50° C. to at least 235° C. are desirable. In certain aspects, organic compounds that can remain a stable solid up to about 236° C., optionally up to about 237° C., optionally up to about 238° C., optionally up to about 239° C., optionally up to about 240° C., optionally up to about 245° C., optionally up to about 250° C., optionally up to about 255° C., optionally up to about 260° C., optionally up to about 265° C., optionally up to about 270° C., optionally up to about 275° C., optionally up to about 280° C., optionally up to about 285° C., optionally up to about 290° C., optionally up to about 295° C., and in certain aspects, optionally up to or exceeding about 300° C.
  • Suitable organic compound candidates for the high-temperature thermal pellets of the HTTCO devices of the present disclosure optionally include the following additional characteristics. In certain embodiments, organic chemicals having acidic structures, such as structures with multiple hydroxides or structures which might have ionic activity in an electrical field may be avoided or minimized. Further, certain organic compounds having side groups comprising sulfur can be avoided, as are compounds having bond structures that easily break down in an electrical field in certain applications.
  • In certain embodiments, the selection of organic compounds useful as a thermal cutoff composition herein can be made based on the chemical's behavior in relation to and interaction with the seal material for the housing of the HTTCO, which often is a porous polymeric structure. Suitable organic chemical compounds for the high-temperature thermal pellet include those having a relatively large molecular size, for example, organic molecules having ring structures, such as those that occupy dimensional space due to bending or side groups. In certain aspects, suitable chemical candidates having flat or unbent conformations or chemical structures, which may have shear mobility or a relatively unimpaired navigation path through the pores in the seal material, are avoided. As such, in certain aspects, the organic chemical compounds selected for use in the high-temperature thermal pellet compositions have relative molecular complexity, such as organic polycyclic ring structures with complex bond orientations that create irregular dimensional space filling configurations or conformations. For example, certain chemical structures that “tangle” at high energy states are desirable, as are relatively large organic species having complex side chains.
  • Furthermore, suitable chemical compounds for the high-temperature thermal compositions of the present disclosure include those that have high molecular bond strength, for example, in ring structures like polyaromatic, polyalkyl, heteroalkyl rings, including fused ring structures that share one or more common bonds. Chemical structures having high intrabond strength with other rings or side groups are also suitable organic species. Further, chemical compounds having intermolecular bond strength, including non-polar or relatively low polar strength structures with high instantaneous polarizability are also suitable. For example, structures with side groups that have “bond affinities” for the parent ring or side groups of other molecular groups are desirable.
  • High melting point aromatic compounds have been shown to provide unique bond strength, relatively large molecule size and electronegativity characteristics desirable to perform as high-temperature thermal cutoff organic compounds when formulated into solid shapes such as pellets and the like. In certain embodiments, the thermal cutoff composition can include one or more aromatic compounds, one or more five-membered ring compounds, polymers, co-polymers, and mixtures thereof.
  • In certain aspects, the high-temperature thermal pellets may comprise a plurality of organic compounds as primary components. Thus, the high-temperature pellet compositions for the HTTCO devices of the present disclosure optionally comprise one or more organic compounds that will provide a transition temperature of greater than or equal to about 240° C. In certain aspects, a plurality of such organic compositions can be used, such that the resulting melting point of the mixture provides the predetermined desired transition temperature for the pellet composition. As recognized by those of skill in the art, the combination of various organic compositions or other components will result in a thermal pellet transition temperature Tx expressed by the following relationship of
  • n 1 X n × mp n ( ° C . ) = T x ,
  • where Xn is the mass fraction of each respective component present in the pellet composition (where n is greater than 1) and “mpn” is the initial melting point temperature for each respective component. In this manner, a transition temperature of the thermal pellet can be predicted based on the respective melting points of a plurality of organic compounds present in the thermal pellet composition. In certain aspects, the pellet composition may comprise a single organic composition as the primary ingredient to arrive at a Tx of greater than or equal to about 240° C. In other aspects, the pellet composition may comprise a plurality of organic compositions, for example two or more organic compounds, to arrive at a Tx of greater than or equal to about 240° C. Such organic compounds may have different melting point temperatures or other properties and are can be combined by co-precipitation, co-crystallization, mixing, blending, milling, or otherwise combined in a suitable manner known in the art.
  • In some embodiments, a high-temperature thermal pellet composition comprises one or more compounds, which includes compounds with a chemical structure having one or more six-member rings that has a basic backbone of carbon with side constituent groups that may be the same or different. In some embodiments, the thermal cutoff composition can include one or more chemical entities generally described by a structural repeating unit (SRU): (-PhRR′—)n where R and R′ may be the same or different side constituent groups, and wherein n may also be a value or greater than or equal to 1, designating the repetition of the structure repeating unit (SRU). In some embodiments, the high temperature thermal pellet composition can include one or more 5 member ring structures, where the side groups and/or SRU may have may be the same or different entities (e.g., having different side constituent groups) such as, for example, where the thermal cutoff composition is described as an example, by the nominal SRU formula, (-Ph-RR1)n-(-Ph-R2R3)m, wherein R and R1 are distinct side groups from R2 and R3. In some embodiments, R and R1 may be the same or different, and similarly, R2 and R3 may be the same or different.
  • In some embodiments, the term “hydrocarbyl” is used herein to refer generally to organic groups comprised of carbon chains to which hydrogen and optionally other elements are attached. CH2 or CH groups and C atoms of the carbon chains of the hydrocarbyl may be replaced with one or more heteroatoms (i.e., non-carbon atoms). Suitable heteroatoms include but are not limited to O, S, P and N atoms. Illustrative hydrocarbyl groups can include, but are not limited to. alkyl, alkenyl, alkynyl, ether, polyether, thioether, straight chain or cyclic saccharides, ascorbate, aminoalkyl, hydroxylalkyl, thioalkyl, aryl and heterocyclic aryl groups, optionally substituted tricyclic molecules, amino acid, polyalcohol, glycol, groups which have a mixture of saturated and unsaturated bonds, carbocyclic rings and combinations of such groups. The term also includes straight-chain, branched-chain and cyclic structures or combinations thereof. Hydrocarbyl groups are optionally substituted. Hydrocarbyl substitution includes substitution at one or more carbons in the group by moieties containing heteroatoms.
  • Suitable substituents for hydrocarbyl groups include but are not limited to halogens, including chlorine, fluorine, bromine and iodine, OH, SH, —N—OH, NH, NH2, —C—NH2═S, CH, —CH—O, C═N, —C—N═O, —C—NH2═O, C═O, COH, —C—NH2═S, CO2, H, —CHBN, —CHP, OR1, SR1 NR1, R″, CONR1R2, and combinations thereof, where R1 and R2 independently are alkyl, unsaturated alkyl or aryl groups. The term “alkyl” takes its usual meaning in the art and is intended to include straight-chain, branched and cycloalkyl groups. The term includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2-ethylbutyl, 1-ethylbutyl, 1,3-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylbexyl, 2-methylhexyl, 1-methylhexyl, 3-ethylpentyl, 2-ethylpentyl, 1-ethylpentyl, 4,4-dimethylpentyl, 3,3-dimethylpentyl, 2,2-dimethylpentyl, 1,1-dimethylpentyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 3-ethylhexyl, 5,5-dimethylhexyl, 4,4-dimethylhexyl, 2,2-diethylbutyl, 3,3-diethylbutyl, and 1-methyl-1-propylbutyl. Alkyl groups are optionally substituted. Lower alkyl groups are C1-C6 alkyl and include among others methyl, ethyl, n-propyl, and isopropyl groups.
  • The term “cycloalkyl” refers to alkyl groups having a hydrocarbon ring, particularly to those having rings of 3 to 7 carbon atoms. Cycloalkyl groups include those with alkyl group substitution on the ring. Cycloalkyl groups can include straight-chain and branched-chain portions. Cycloalkyl groups include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclononyl. Cycloalkyl groups can optionally be substituted.
  • Aryl groups may be substituted with one, two or more simple substituents including, but not limited to, lower alkyl, e.g., C1-C4, methyl, ethyl, propyl, butyl; halo, e.g., chloro, bromo; nitro; sulfato; sulfonyloxy; carboxy; carbo-lower-alkoxy, e.g., carbomethoxy, carbethoxy; amino; mono- and di-lower-alkylamino, e.g., methylamino, ethylamino, dimethylamino, methylethylamino; amido; hydroxy; lower-alkoxy, e.g., methoxy, ethoxy; and lower-alkanoyloxy, e.g., acetoxy.
  • The term “unsaturated alkyl” group is used herein generally to include alkyl groups in which one or more single carbon-carbon bonds are double or triple carbon-carbon bonds. The term includes alkenyl and alkynyl groups in their most general sense. The term is intended to include groups having more than one double or triple bond, or combinations of double and triple bonds. Unsaturated alkyl groups include, without limitation, unsaturated straight-chain, branched or cycloalkyl groups. Unsaturated alkyl groups include without limitation: vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, hexadienyl, heptenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, 1-propenyl, 2-butenyl, 2-methyl-2-butenyl, ethynyl, propynyl, 3-methyl-1-pentynyl, and 2-heptynyl. Unsaturated alkyl groups can optionally be substituted.
  • Substitution of alkyl, cycloalkyl and unsaturated alkyl groups includes substitution at one or more carbons in the group by moieties containing heteroatoms. Suitable substituents for these groups include but are not limited to OH, SH, NH2, COH, CO2 H, OR3, SR3, P, PO, NR3R4, CONR3R4, and halogens, particularly chlorines and bromines where R3 and R4, independently are alkyl, unsaturated alkyl or aryl groups. Suitable alkyl and unsaturated alkyl groups are the lower alkyl, alkenyl or alkynyl groups having from 1 to about 5 carbon atoms.
  • The term “aryl” is used herein generally to refer to aromatic groups which have at least one ring having a conjugated pi electron system and includes without limitation carbocyclic aryl, aralkyl, heterocyclic aryl, biaryl groups and heterocyclic biaryl, all of which can be optionally substituted. Preferred aryl groups have one or two aromatic rings. “Carbocyclic aryl” refers to aryl groups in which the aromatic ring atoms are all carbons and includes without limitation phenyl, biphenyl and napthalene groups.
  • “Aralkyl” refers to an alkyl group substituted with an aryl group. Suitable aralkyl groups include among others benzyl, phenethyl, and may be optionally substituted, such as picolyl substituted with nitrogen. Aralkyl groups include those with heterocyclic and carbocyclic aromatic moieties.
  • “Heterocyclic aryl groups” refers to groups having at least one heterocyclic aromatic ring with from 1 to 3 heteroatoms in the ring, the remainder being carbon and hydrogen atoms. Suitable heteroatoms include without limitation oxygen, sulfur, and nitrogen. Heterocyclic aryl groups include among others furanyl, thienyl, pyridyl, pyrrolyl, N-alkyl pyrrolo, pyrimidyl, pyrazinyl, imidazolyl, benzofuranyl, quinolinyl, and indolyl, all optionally substituted.
  • “Heterocyclic biaryl” refers to heterocyclic aryls in which a phenyl group is substituted by a heterocyclic aryl group ortho, meta or para to the point of attachment of the phenyl ring to the decalin or cyclohexane. Heterocyclic biaryl includes among others groups which have a phenyl group substituted with a heterocyclic aromatic ring. The aromatic rings in the heterocyclic biaryl group can be optionally substituted.
  • “Biaryl” refers to carbocyclic aryl groups in which a phenyl group is substituted by a carbocyclic aryl group ortho, meta or para to the point of attachment of the phenyl ring to the decalin or cyclohexane. Biaryl groups include among others a first phenyl group substituted with a second phenyl ring ortho, meta or para to the point of attachment of the first phenyl ring to the decalin or cyclohexane structure. Para substitution is preferred. The aromatic rings in the biaryl group can be optionally substituted.
  • Aryl group substitution includes substitutions by non-aryl groups (excluding H) at one or more carbons or where possible at one or more heteroatoms in aromatic rings in the aryl group. Unsubstituted aryl, in contrast, refers to aryl groups in which the aromatic ring carbons are all substituted with H, e.g. unsubstituted phenyl (—C6H5), or naphthyl (—C10H7). Suitable substituents for aryl groups include among others, alkyl groups, unsaturated alkyl groups, halogens, OH, SH, NH2, COH, CO2H, OR5, SR5, NR5 R6, CONR5 R6, where R5 and R6 independently are alkyl, unsaturated alkyl or aryl groups. Preferred substituents are OH, SH, OR5, and SR5 where R5 is a lower alkyl, i.e., an alkyl group having from 1 to about 5 carbon atoms. Other preferred substituents are halogens, more preferably chlorine or bromine, and lower alkyl and unsaturated lower alkyl groups having from 1 to about 5 carbon atoms. Substituents include bridging groups between aromatic rings in the aryl group, such as —CO2—, —CO—, —O—, —S—, —P—, —NH—, —CH═CH— and —(CH2)1— where I is an integer from 1 to about 5, and particularly —CH2— where I is 1. Examples of aryl groups having bridging substituents include phenylbenzoate. Substituents also include moieties, such as —(CH2)J—, —O—(CH2)J— or —OCO— (CH2)J—, where J is an integer from about 2 to 7, as appropriate for the moiety, which bridge two ring atoms in a single aromatic ring as, for example, in a 1,2,3,4-tetrahydronaphthalene group. Alkyl and unsaturated alkyl substituents of aryl groups can in turn optionally be substituted as described supra for substituted alkyl and unsaturated alkyl groups.
  • The terms “alkoxy group” and “thioalkoxy group” (also known as mercaptide groups, the sulfur analog of alkoxy groups) take their generally accepted meaning. Alkoxy groups include but are not limited to methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, neopentyloxy, 2-methylbutoxy, 1-methylbutoxy, 1-ethylpropoxy, 1,1-dimethylpropoxy, n-hexyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 3,3-dimethylbutoxy, 2,2-dimethoxybutoxy, 1-1-dimethylbutoxy, 2-ethylbutoxy, 1-ethylbutoxy, 1,3-dimethylbutoxy, n-pentyloxy, 5-methylhexyloxy, 4-methylhexyloxy, 3-methylhexyloxy, 2-methylhexyloxy, 1-methylhexyloxy, 3-ethylpentyloxy, 2-ethylpentyloxy, 1-ethylpentyloxy, 4,4-dimethylpentyloxy, 3,3-dimethylpentyloxy, 2,2-dimethylpentyloxy, 1,1-dimethylpentyloxy, n-octyloxy, 6-methylheptyloxy, 5-methylheptyloxy, 4-methylheptyloxy, 3-methylheptyloxy, 2-methylheptyloxy, 1-methylheptyloxy, 1-ethylhexyloxy, 1-propylpentyloxy, 3-ethylhexyloxy, 5,5-dimethylhexyloxy, 4,4-dimethylhexyloxy, 2,2-diethylbutoxy, 3,3-diethylbutoxy, 1-methyl-1-propylbutoxy, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, sec-butoxymethyl, isobutoxymethyl, (1-ethylpropoxy)methyl, (2-ethylbutoxy)methyl, (1-ethylbutoxy)methyl, (2-ethylpentyloxy)methyl, (3-ethylpentyloxy)methyl, 2-methoxyethyl, 1-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 2-methoxypropyl, 1-methoxypropyl, 2-ethoxypropyl, 3-(n-propoxy)propyl, 4-methoxybutyl, 2-methoxybutyl, 4-ethoxybutyl, 2-ethoxybutyl, 5-ethoxypentyl, and 6-ethoxyhexyl. Thioalkoxy groups include but are not limited to the sulfur analogs of the alkoxy groups specifically listed supra.
  • In some embodiments, the R, R1, R2, R3, R4, R5 and R6 side groups in the 5 and 6 member ring can be independently selected from any of the aforementioned hydrocarbyl substituents, for example, —CH, —CH—O, —CH—OH, —NH2, —NH, —CH—N, —CH═O, —N—OH, —CHBN, —CHP or mixtures thereof.
  • In certain aspects, one particularly suitable organic compounds for use in a high-temperature thermal pellet composition of the present teachings is triptycene or tryptycene (9,10-dihydro-9,10-o-benzeno-9,10-dihydroanthracene—CAS Registry No. 477-75-8), which has a transition temperature of about 255° C. and a melting point temperature range of 255° C. to about 257° C. Triptycene is generally classified as a polycyclic aromatic hydrocarbon and is generally represented by the exemplary Formula (I):
  • Figure US20100033295A1-20100211-C00001
  • Triptycene can be prepared by the reduction of the anthracene-benzoquinone adduct with lithium aluminum hydride or sodium borohydride, among other methods known to those in the art. Tryptycene, or triptycene (also known as) is described in Organic Syntheses, Coll. Vol. 4, p. 964 (1963), the relevant portions of which are incorporated herein by reference.
  • In certain other aspects, a particularly suitable organic compound for use in a high-temperature thermal pellet composition of the present teachings is 1-aminoanthraquinone (also known as 1-Amino-9,10-anthracenedione—CAS Registry No. 82-45-1), which is classified as a polycyclic aromatic hydrocarbon with constituent side groups —C═O and C—NH2 as represented in Formula (II):
  • Figure US20100033295A1-20100211-C00002
  • 1-Aminoanthraquinone has an expected transition temperature of about 253° C., with a melting point range of 253° C. to about 257° C. 1-Aminoanthraquinone (1-AAQ) can be prepared by the reaction of 2-chlorobenzyl chloride and xylene in the presence of a solid acid catalyst, or other methods known in the art. 1-aminoanthraquinone (also known as 1-Amino-9,10-anthracenedione) described in U.S. Pat. Nos. 4,006,170 and 4,695,407, the relevant portions of which are incorporated herein by reference.
  • By way of non-limiting example, other representative organic compounds, such as the exemplary compounds set forth in Table 2 below are also believed to be highly suitable candidates for the high-temperature thermal pellet compositions for the HTTCO devices of the present disclosure, based on the criteria discussed above and the estimated melting point temperature ranges set forth below. However, the present disclosure further contemplates various other organic compounds, which while not listed herein, fulfill one or more of the criteria listed above including the melting point data that corresponds to a transition temperature above about 240° C. As noted above, predicted melting point ranges may differ based on analytic techniques used (thus certain compounds have multiple or differing melting points) and such compositions are selected to have an empirical transition temperature that performs in a thermal pellet to physically transition and change electrical continuity at a desired threshold temperature.
  • TABLE 2
    CAS Registry
    Example Melting Point Name IUPAC Name No.
    1 241° C. Zaprinast 5-(2-propoxyphenyl)-2,3- 37762-06-4
    dihydrotriazolo[4,5-e]pyrimidin-
    7-one
    2 241-243° C. Ropinirole hydrochloride 4-[2-(dipropylamino)ethyl]-1,3- 91374-20-8
    dihydroindol-2-one
    hydrochloride
    3 241° C. Triphenylguanidine (N,N′-diphenylcarbamimidoyl)- 59283-92-0
    hydrochloride phenylazanium chloride
    4 241-242° C. Naphthacene,- 1,4,5,6,7,10,11,12- 60700-47-2
    1,4,5,6,7,10,11,12-octahydro- octahydrotetracene
    5 241-244° C. 3-Ethoxybenzonitrile 3-ethoxybenzonitrile 25117-75-3
    6 241-242° C. Cis-1,2,3,4-Tetrahydro-1- (1S,4S)—N-methyl-4-phenyl- 52371-38-7
    amino-N-methyl-4- 1,2,3,4-tetrahydronaphthalen-
    phenylnaphthalene 1-amine hydrochloride
    hydrochloride
    7 241° C. 2,7-Dimethylanthracene 2,7-dimethylanthracene 782-23-0
    8 240-243° C. Sesbanine 3′-hydroxyspiro[2,7- 70521-94-7
    naphthyridine-4,1′-
    cyclopentane]-1,3-dione
    9 241-243° C. 1,3,4-Oxadiazole, 2-amino-5- 5-phenyl-1,3,4-oxadiazol-2- 1612-76-6
    phenyl- amine
    10 241° C. Acenaphtho(1,2- acenaphthyleno[1,2- 207-11-4
    b)quinoxaline b]quinoxaline
    11 242° C. Oxyphenisatin [4-[3-(4-acetyloxyphenyl)-2- 115-33-3
    Acetate oxo-1H-indol-3-yl]phenyl]acetate
    12 242° C. 4-Nitrobenzimidazole 4-nitro-1H-benzimidazole 10597-52-1
    13 242-244° C. Biotinamide 5-[(3aR,6S,6aS)-2-oxo- 6929-42-6
    1,3,3a,4,6,6a-
    hexahydrothieno[3,4-
    d]imidazol-6-yl]pentanamide
    14 242° C. Tropine isobutyrate [(1S,5R)-8-methyl-8- 495-80-7
    azabicyclo[3.2.1]octan-3-yl] 2-
    methylpropanoate
    15 242° C. Phenol, 2-(1H-benzimidazol- 6-(1,3-dihydrobenzimidazol-2- 2963-66-8
    2-yl)- ylidene)cyclohexa-2,4-dien-1-
    one
    16 242-245° C. Bufalone 5- 4029-65-6
    [(5R,8R,9S,10S,13R,14S,17R)-
    14-hydroxy-10,13-dimethyl-3-
    oxo-
    2,4,5,6,7,8,9,11,12,15,16,17-
    dodecahydro-1H-
    cyclopenta[a]phenanthren-17-
    yl]pyran-2-one
    17 242-244° C. Difenoximide hydrochloride (2,5-dioxopyrrolidin-1-yl) 1-(3- 37800-79-6
    cyano-3,3-diphenylpropyl)-4-
    phenylpiperidine-4-carboxylate
    hydrochloride
    18 242-244° C. Levcromakalim (3S,4R)-3-hydroxy-2,2- 94535-50-9
    dimethyl-4-(2-oxopyrrolidin-1-
    yl)chroman-6-carbonitrile
    19 242-243° C. Bandrowski's base 3,6-bis[(4- 20048-27-5
    aminophenyl)imino]cyclohexa-
    1,4-diene-1,4-diamine
    20 242° C. pyrazino[2,3-f] quinoxaline pyrazino[2,3-f]quinoxaline 231-23-2
    21 243-245° C. 2,4,6-Tri-2-pyridinyl-1,3,5- 2,4,6-tri(pyridin-2-yl)-1,3,5- 3682-35-7
    triazine triazine
    22 243-245° C. 3,3′,5,5′-Tetra-tert-butyl[di- 2,6-ditert-butyl-4-(3,5-ditert- 2455-14-3
    2,5-cyclohexadien-1-ylidene]- butyl-4-oxo-1-cyclohexa-2,5-
    4,4′-dione dienylidene)cyclohexa-2,5-
    dien-1-one
    23 243-245° C. 6-Methyl-8- 6-methyl-8-nitrophenanthridine 51381-78-3
    nitrophenanthridine
    24 243-245° C. 1,4-Dihydro-5H-tetrazol-5-one 1,2-dihydrotetrazol-5-one 16421-52-6
    25 242.5-243° C. 2,2′-Diamino-1,1′-binaphthyl 1-(2-aminonaphthalen-1- 18741-85-0
    yl)naphthalen-2-amine
    26 243° C. Violerythrin 3,5,5-trimethyl-4- 22453-06-1
    (236-238°) [(1E,3E,5E,7E,9E,11E,13E,15E,-
    17E)-3,7,12,16-tetramethyl-
    18-(2,5,5-trimethyl-3,4-dioxo-
    1-cyclopentenyl)octadeca-
    1,3,5,7,9,11,13,15,17-
    nonaenyl]cyclopent-3-ene-1,2-
    dione
    27 243-245° C. Acenapththenequinone acenaphthene-1,2-dione 82-86-0
    28 243° C. Duryl aldehyde 2,4,5-trimethylbenzaldehyde 5779-72-6
    29 244-245.5° C. Longimammatine 6-methoxy-1,2,3,4- 42923-77-3
    tetrahydroisoquinoline
    30 244-245° C. Proguanil Hydrochloride (1Z)-1-[amino-[(4- 637-32-1
    chlorophenyl)amino]methylidene]-
    2-propan-2-ylguanidine
    hydrochloride
    31 244-247° C. 2H-1-Benzopyran-2-one, 5- 5-hydroxychromen-2-one 6093-67-0
    hydroxy-
    32 244-245° C.; N,N′-Diphenylbenzidine N-phenyl-4-[4- 531-91-9
    251-252° C. (phenylamino)phenyl]aniline
    33 244-245° C. Methanone,- bis(4-aminophenyl)methanone 611-98-3
    bis(4-aminophenyl)-
    34 244° C. Dapitant (2S)-1-[(3aS,4S,7aS)-4- 153438-49-4
    hydroxy-4-(2-methoxyphenyl)-
    7,7-di(phenyl)-1,3,3a,5,6,7a-
    hexahydroisoindol-2-yl]-2-(2-
    methoxyphenyl)propan-1-one
    35 244-245° C. Cytosinine 3-amino-6-(4-amino-2- 1860-84-0
    oxopyrimidin-1-yl)-3,6-dihydro-
    2H-pyran-2-carboxylic acid
    36 244-245° C. Biurea (carbamoylamino)urea 110-21-4
    37 244-245° C. 9,10- anthracene-9,10- 7044-91-9
    Anthracenedicarboxaldehyde dicarbaldehyde
    38 244-246° C. Tri-3-indolylmethane 3-[bis(1H-indol-3-yl)methyl]- 518-06-9
    1H-indole
    39 245° C. 6-Benzyl-1,3,5-triazine-2,4- 6-(phenylmethyl)-1,3,5- 1853-88-9
    diamine triazine-2,4-diamine
    40 245° C. Taraxerone (4aR,6aR,6aS,8aR,12aS,14aR,- 514-07-8
    14bR)-
    4,4,6a,6a,8a,11,11,14b-
    octamethyl-
    2,4a,5,6,8,9,10,12,12a,13,14,14a-
    dodecahydro-1H-picen-3-
    one
    41 245-246° C. 1,7-Dihydro-1,7-dimethyl-6H- 1,7-dimethylpurin-6-one 33155-83-8
    purin-6-one
    42 245-246° C. 1-Phenazinecarboxamide phenazine-1-carboxamide 550-89-0
    43 245° C. Methisazone [(1-methyl-2-oxoindol-3- 1910-68-5
    ylidene)amino]thiourea
    44 245-247° C. 3-Indazolinone 1,2-dihydroindazol-3-one 7364-25-2
    45 245-246° C. Emd 56431 (3R,4S)-3-hydroxy-2,2- 123595-75-5
    dimethyl-4-(2-oxopyridin-1-
    yl)chroman-6-carbonitrile
    46 245-246.5° C. Dimoxamine hydrochloride 1-(2,5-dimethoxy-4- 52663-86-2
    methylphenyl)butan-2-amine
    hydrochloride
    47 245-247° C. 9H-Carbazol-2-amine (9Cl) 9H-carbazol-2-amine 4539-51-9
    48 245-247° C. (1,2,4)Triazolo(4,3-a)pyridin- [1,2,4]triazolo[4,5-a]pyridin-3- 767-62-4
    3(2H)-imine amine
    49 246-248° C. Carbanilide 1,3-di(phenyl)urea 102-07-8
    (239-240° C.)
    50 246-247° C. 1H-1,2,3-Triazlo(4,5- 2H-triazolo[4,5-c]pyridine 273-05-2
    c)pyridine
    51 246-248° C. Hexamethylbenzene- [4-(hydroxymethyl)-2,3,5,6- 7522-62-5
    alpha1,alpha4-diol tetramethylphenyl]methanol
    52 246-247° C. 6-Thiocaffeine 1,3,7-trimethyl-6- 13182-58-6
    sulfanylidenepurin-2-one
    53 246-249° C. 1,2,3,4-Tetrahydro-9H- 1,2,3,4-tetrahydrocarbazole-9- 67242-61-9
    carbazole-9-carboxamide carboxamide
    54 246-248° C. 9,10-Diphenylanthracene 9,10-di(phenyl)anthracene 1499-10-1
    55 246° C. O 129 6,7-di(propan-2-yl)pteridine- 3810-29-5
    2,4-diamine
    56 246° C. 9,9′-Bi-9H-fluorene 9-(9H-fluoren-9-yl)-9H-fluorene 1530-12-7
    57 246-248° C. 2-[4-(dicyanomethyl)phenyl]propanedinitrile 2-[4- 18643-56-6
    (dicyanomethyl)phenyl]propanedinitrile
    58 247-248° C. Sulfaquinoxaline 4-amino-N-quinoxalin-2- 59-40-5
    ylbenzenesulfonamide
    59 247° C. Metaldehyde 2,4,6,8-tetramethyl-1,3,5,7- 108-62-3
    tetraoxocane
    60 247-250° C. 1-Azaspiro(5.5)undecan-8-ol,- 7-[(E)-but-1-en-3-ynyl]-2-pent- 63983-63-1
    7-(1-buten-3-ynyl)-2-(4- 4-ynyl-1-
    pentynyl)-, (6R- azaspiro[5.5]undecan-8-ol
    (6alpha(R*),7beta(Z),8alpha))-
    61 247-249° C. 9H-Pyrido(3,4-b)indole-3- N-ethyl-9H-pyrido[5,4-b]indole- 78538-80-4
    carboxamide, N-ethyl- 3-carboxamide
    62 247-248° C. Apazone 5-dimethylamino-9-methyl-2- 13539-59-8
    propylpyrazolo[1,2-
    a][1,2,4]benzotriazine-1,3-
    dione
    63 247-251° C. 4,4′,5,5′-Tetraphenyl-Δ2,2′-bi- N-[(4- 14551-06-5
    2H-imidazole carbamimidoylphenyl)methyl]-
    2-[5-chloro-3-(3-
    hydroxypropylamino)-2-oxo-6-
    phenylpyrazin-1-yl]acetamide
    64 247° C. 2-Hydroxy-3- 3-phenyl-1H-quinoxalin-2-one 1504-78-5
    phenylquinoxaline
    65 247-249° C. 3-Hydroxy-19-norpregna- 1-[(8S,9S,13S,14S,17S)-3- 1667-98-7
    1,3,5(10)-trien-20-one hydroxy-13-methyl-
    6,7,8,9,11,12,14,15,16,17-
    decahydrocyclopenta[a]phenanthren-
    17-yl]ethanone
    66 248° C. CP 93129 3-(1,2,3,6-tetrahydropyridin-4- 127792-75-0
    yl)-1,4-dihydropyrrolo[2,3-
    e]pyridin-5-one
    67 248° C. 6-Benzyl-1,3,5-triazine-2,4- 6-(phenylmethyl)-1,3,5- 1853-88-9
    (238-299°) diamine triazine-2,4-diamine
    68 248-250° C. 6-Hydroxychrysene chrysen-6-ol 37515-51-8
    69 248° C. Tetraphenylpyrazine 2,3,5,6-tetra(phenyl)pyrazine 642-04-6
    70 249-251° C. 2,4,6-Pyrimidinetriamine pyrimidine-2,4,6-triamine 1004-38-2
    71 249° C. Pyrazino[2,3-b]quinoxaline pyrazino[2,3-b]quinoxaline 261-67-6
    72 249-250° C. 6-Hydrazino-3- 6-hydrazinylpyridazine-3- 3614-47-9
    pyridazinecarboxamide carboxamide
    73 249° C. 4-Nitrophenylhydrazone N-[(2- 14295-17-1
    chlorophenyl)methylideneamino]-
    4-nitroaniline
    74 249-253° C. N1,N4-Di-E- 3-phenyl-N-[4-(3-phenylprop- 37946-56-8
    cinnamoylputrescine 2-enoylamino)butyl]prop-2-
    enamide
    75 249-250° C. 1-Aminothioxanthen-9-one 1-aminothioxanthen-9-one 40021-31-6
    76 249-250° C. 1-Naphthylamine, 5-methoxy- (5-methoxy-1,2,3,4- 41566-70-5
    1,2,3,4-tetrahydro- tetrahydronaphthalen-1-
    hydrochloride yl)azanium chloride
    77 250° C. NCS404824 7H-[1,2,4]triazolo[5,1-f]purine 4022-94-0
    78 250-252° C. 2,4-Quinazolinediamine quinazoline-2,4-diamine 1899-48-5
    79 250° C. Prioxodan 3-methyl-6-(6-oxo-4,5-dihydro- 111786-07-3
    1H-pyridazin-3-yl)-1,4-
    dihydroquinazolin-2-one
    80 250° C. 2,6-dimethylanthracene 2,6-dimethylanthracene 613-26-3
    81 250° C. 4,4′-Diaminoazobenzene 4-(4- 538-41-0
    aminophenyl)diazenylaniline
    82 250-253° C. N,N-Dimethyl-4-t-butylaniline 4-tert-butyl-N,N- 2909-79-7
    dimethylaniline
    83 250-251° C. Acetamide N-chrysen-5-ylacetamide 34441-00-4
    84 230°; 1-Acridinol 10H-acridin-1-one 5464-73-3
    250° C.
    85 251-252° C. 2-Phenyl-1H-indole-3- 2-phenyl-1H-indole-3- 25365-71-3
    carboxaldehyde carbaldehyde
    86 251° C. Fluorene-9-carboxamide 9H-fluorene-9-carboxamide 7471-95-6
    87 251-253° C. 2,3-Dimethylcarbazole 2,3-dimethyl-9H-carbazole 18992-70-6
    88 251-253° C. 9,10-bis(2- 9,10-bis(2- 10075-85-1
    phenylethynyl)anthracene phenylethynyl)anthracene
    89 251-253° C. 6-Dimethyladenine N,N-dimethyl-7H-purin-6- 938-55-6
    amine
    90 252-254° C. 6-Quixoxalinol 4H-quinoxalin-6-one 7467-91-6
    91 252-254° C. Oxalanilide N,N′-di(phenyl)oxamide 620-81-5
    92 252-255° C. 3-(Hydroxyimino)-7- 3-(hydroxyamino)-7- 13208-96-3
    methylindolin-2-one methylindol-2-one
    93 252° C. 2,3-Dimethylanthracene 2,3-dimethylanthracene 613-06-9
    94 252-255° C. 2,4-Dinitrophenylhydrazone 2,4-dinitro-N-[(2- 16281-65-5
    phenylchroman-4-
    ylidene)amino]aniline
    95 252-252.5° C. Cyclopent(b)indol-3-one,- 2,4-dihydro-1H- 16244-15-8
    1,2,3,4-tetrahydro- cyclopenta[b]indol-3-one
    96 253-254° C. 1-Aminoanhraquinone 1-aminoanthracene-9,10-dione 82-45-1
    97 253° C. 2-Benzothiazolamine, 6-nitro- 6-nitro-1,3-benzothiazol-2- 6285-57-0
    amine
    98 253° C. 2H-1,3-Benzoxazine-2,4(3H)- 2-sulfanylidene-1,3- 10021-35-9
    dione, 2-thio- benzoxazin-4-one
    99 254-255° C. 7H-Pyrido(3,4-c)carbazole 7H-pyrido[3,4-c]carbazole 205-27-6
    100 254-255° C. Tetrahydroharmol 1-methyl-2,3,4,9-tetrahydro- 17952-75-9
    hydrochloride 1H-pyrido[3,4-b]indol-7-ol
    hydrochloride
    101 254-256° C. Dibenz(a,h)anthracen-7-ol naphtho[1,2-b]phenanthren-7- 63041-68-9
    ol
    102 254-256° C. Glycosminine 2-(phenylmethyl)-1H- 4765-56-4
    (248-249°) quinazolin-4-one
    103 254° C. 2-Anthracenol (9Cl) anthracen-2-ol 613-14-9
    104 254-256° C. 4-Amino-5-cyanopyrimidine 4-aminopyrimidine-5- 16357-69-0
    carbonitrile
    105 254° C.; 2-Amino-4-nitrobenzothiazole 4-nitro-1,3-benzothiazol-2- 6973-51-9
    (233°) amine
    106 255-256° C. 2,4,6,8-Tetraphenyl-3,7- 2,4,6,8-tetra(phenyl)-3,7- 37123-09-4
    (250-252°) diazabicyclo [3.3.1]nonan-9- diazabicyclo[3.3.1]nonan-9-
    one one
    107 255-257° C. Tetrahydro-5,5-dimethyl- 5,5-dimethyl-1,3-diazinan-2- 17496-93-4
    2(1H)-pyrimidinone one
    108 255° C. Benzoic acid 2- (benzoylamino)urea 2845-79-6
    (aminocarbonyl)hydrazide,-
    9Cl
    109 255-258° C. 2,4,6-Quinazolinetriamine quinazoline-2,4,6-triamine 13741-90-7
    110 255-256° C. 3-Cyanothioxanthone 9-oxothioxanthene-3- 51762-90-4
    carbonitrile
    111 255-256° C. 6-Nitrobenzo[a]pyrene 6-nitrobenzo[b]pyrene 63041-90-7
    112 255° C. 3-Methyl-1,2,4-triazolo[4,3- 3-methyl-[1,2,4]triazolo[4,5- 65267-32-5
    a]pyrimidine a]pyrimidine
    113 255° C. 2-Methyl-4(5)-nitroimidazole 2-methyl-4-nitro-3H-imidazole 696-23-1
    114 255-257° C. 4-Hydroxy-2-phenylquinoline 2-phenyl-1H-quinolin-4-one 14802-18-7
    115 255-256° C. Halfordinol 4-(2-pyridin-3-yl-1,3-oxazol-5- 4210-82-6
    yl)phenol
    116 256-258° C. Tetra-4-pyridinylthiophene 4-[2,4,5-tri(pyridin-4- 64048-12-0
    yl)thiophen-3-yl]pyridine
    117 256-258° C. Nifenazone N-(1,5-dimethyl-3-oxo-2- 2139-47-1
    phenylpyrazol-4-yl)pyridine-3-
    carboxamide
    118 256-257° C. Indisetron N-(3,9-dimethyl-3,9- 141549-75-9
    diazabicyclo[3.3.1]nonan-7-yl)-
    1H-indazole-3-carboxamide
    119 256° C. 1,2,3-Indanetrione indene-1,2,3-trione 938-24-9
    (241-243°)
    120 256-258° C. 1,4-dimethylquinoxaline-2,3- 1,4-dimethylquinoxaline-2,3- 58175-07-8
    dione dione
    121 256-258° C. 2-aminopyridin-1-ium-4- 2-aminopyridin-1-ium-4- 13538-42-6
    carboxamide carboxamide
    122 257-258° C. Terosite 4-phenyl-2,6-bis(4- 24368-63-6
    phenylpyridin-2-yl)pyridine
    123 257° C. Pentaphene Pentaphene 222-93-5
    124 258-259° C. Tetrahydrolathyrine 2-amino-3-(2-amino-3,4,5,6- 72748-96-0
    tetrahydropyrimidin-4-
    yl)propanoic acid
    125 258-260° C. Quinezamide N-(5-methylpyrazolo[1,5- 77197-48-9
    c]quinazolin-1-yl)acetamide
    126 258° C. 1,10-Phenanthroline-5,6- 1,10-phenanthroline-5,6-dione 27318-90-7
    dione
    127 258° C. 2-Nitrobenzimidazole 2-nitro-1H-benzimidazole 5709-67-1
    128 258-259° C. 1H-imidazo[5,4-b]pyrazine 1H-imidazo[5,4-b]pyrazine 273-94-9
    129 258-260° C. Magnosprengerine 4-(2-dimethylaminoethyl)-2- 35266-63-8
    methoxyphenol
    130 258-259° C. Dibenz(a,h)anthracen-6-ol naphtho[4,3-b]phenanthren- 83710-52-5
    13-ol
    131 258-260° C. 6-Amino-5,8-quinolinedione 6-aminoquinoline-5,8-dione 24149-57-3
    132 259-260° C. 7h-Pyrido[4,3-c]carbazole 7H-pyrido[4,3-c]carbazole 205-29-8
    133 259° C. 2-Methyl-9H-carbazole 2-methyl-9H-carbazole 3652-91-3
    134 259-260° C. 4,6-dimethyl-2-sulfanylidene- 4,6-dimethyl-2-sulfanylidene- 54585-47-6
    1H-pyridine-3-carbonitrile 1H-pyridine-3-carbonitrile
    135 259-261° C. CV 399 4-methoxy-6-methyl-1,3,5- 1668-54-8
    triazin-2-amine
    136 259-260° C. 6-(4-aminobutyl-ethylamino)- 6-(4-aminobutyl-ethylamino)- 66612-29-1
    2,3-dihydro-1,4- 2,3-dihydrophthalazine-1,4-
    phthalazinedione dione
    137 259-260° C. 2-(1(2H)- 2-acenaphthen-1- 477-77-0
    Acenaphthylenylidene)-1(2H)- ylideneacenaphthen-1-one
    acenaphthylenone
    138 260-261° C. Diphenylene dioxide 2,3- oxanthrene-2,3-dione 6859-47-8
    quinone
    139 260° C. Benzo(a)pyrene-7,8-dione benzo[a]pyrene-7,8-dione 65199-11-3
    140 260-265° C. 2-Adamantanol adamantan-2-ol 700-57-2
    141 260-263° C. Friedelan-7-one (4S,4aR,6aS,6aS,6bR,8aR,12aR,- 18671-54-0
    14aS,14bR)-
    4,4a,6a,6b,8a,11,11,14a-
    octamethyl-
    2,3,4,5,6a,7,8,9,10,12,12a,13,-
    14,14b-tetradecahydro-1H-
    picen-6-one
    142 260-261° C. 1,2-Chrysenedione chrysene-1,2-dione 2304-83-8
    143 260-262° C. benzo[a]anthracene-5,6- benzo[c]anthracene-5,6-dione 18508-00-4
    dione
    144 260° C. Pentaerythritol 2,2- 115-77-5
    bis(hydroxymethyl)propane-
    1,3-diol
    145 260-265° C. 1-Methylcytosine 4-amino-1-methylpyrimidin-2- 1122-47-0
    one
    146 260° C. 2,8-Dihydroxyquinoline 8-hydroxy-1H-quinolin-2-one 15450-76-7
    (297-299°)
    147 260-262° C. N(beta)-Alanyl-1-methyl- 3-aminopropanoyl (2S)-2- 331-38-4
    histidine amino-3-(1-methylimidazol-4-
    yl)propanoate
    148 261-263° C. Sporidesmolide I 4,19-dimethyl-3,12-bis(2- 2900-38-1
    methylpropyl)-6,9,15-
    tri(propan-2-yl)-1,10-dioxa-
    4,7,13,16-tetrazacycloicosane-
    2,5,8,11,14,17-hexone
    149 261-264° C. Picodralazine [4-(pyridin-4- 17692-43-2
    ylmethyl)phthalazin-1-
    yl]hydrazine
    150 261-262° C. 8-Phenyl-1H-purine 8-phenyl-7H-purine 4776-14-1
    151 261° C. Furagin 1-[[(E)-3-(5-nitrofuran-2- 1672-88-4
    yl)prop-2-
    enylidene]amino]imidazolidine-
    2,4-dione
    152 261° C. 4,8-Dibenzoyl-5-methoxy-1- 2-(piperidin-1-ylmethyl)- 372520-17-7
    naphthalenol 10,10a-dihydro-5H-
    imidazo[1,5-b]isoquinoline-1,3-
    dione
    153 261-262° C. beta-Carboline-3-carboxylic methyl 9H-pyrido[5,4-b]indole- 69954-48-9
    acid methyl ester 3-carboxylate
    154 261° C. 1,4-Bis(2- 2-methyl-N′-(2-oxoindol-3- 5153-65-1
    benzothiazolyl)benzene yl)benzohydrazide
    155 261° C. 12H-[1]Benzopyrano[2,3- chromeno[3,2-b]quinoxalin-12- 82501-03-9
    b]quinoxalin-12-one one
    156 261-262° C. Indeno(1,2-c)isochromene- indeno[3,2-c]isochromene- 5651-60-5
    5,11-dione 5,11-dione
    157 261-263° C. Benzene-1,3,5-tricarbonitrile benzene-1,3,5-tricarbonitrile 10365-94-3
    (254-258°)
    213.5-214°
    (210-212°)
    158 262-263° C. Guanazine 1,2,4-triazole-3,4,5-triamine 473-96-1
    159 262° C. Razobazam 3,8-dimethyl-4-phenyl-2H- 78466-98-5
    pyrazolo[3,4-b][1,4]diazepine-
    5,7-dione
    160 262° C. 1-Phenylbarbituric acid 1-phenyl-1,3-diazinane-2,4,6- 15018-50-5
    trione
    161 262-263° C. 6-Methoxypurine 6-methoxy-7H-purine 1074-89-1
    162 262° C. N-(4-chloro-2- N-(4-chloro-2- 5356-56-9
    (283-286°) nitrophenyl)thiophene-2- nitrophenyl)thiophene-2-
    carboxamide carboxamide
    163 262-262.5° C. 9H-Fluorene-4-carboxylic 7-nitro-9-oxofluorene-4- 42523-38-6
    acid, 7-nitro-9-oxo- carboxylic acid
    164 262° C. 4-Nitroacridone 4-nitro-10H-acridin-9-one 4261-62-5
    165 262-264° C. Papyriogenin A (4aR,6aR,6aS,6bR,8aR,12aS)- 59076-79-8
    2,2,6a,6b,9,9,12a-
    heptamethyl-3,10-dioxo-
    1,4,5,6,6a,7,8,8a,11,12-
    decahydropicene-4a-
    carboxylic acid
    166 262-264° C. N-[(1R,3S)-3- N-[(1R,3S)-3- 32189-20-1
    acetamidocyclohexyl]acetamide acetamidocyclohexyl]acetamide
    167 262-263° C. 1,3-Di-p-tolylurea 1,3-bis(4-methylphenyl)urea 621-00-1
    168 263-265° C. 1,1,3,3- propane-1,1,3,3- 10550-79-5
    Propanetetracarboxamide tetracarboxamide
    169 263° C. 5-Hydroxy-4-methyl-2H-1- 5-hydroxy-4-methylchromen-2- 2373-34-4
    benzopyran-2-one one
    170 263-264° C. 1,3-Dihydro-5-methoxy-2H- 5-methoxy-1,3- 37052-78-1
    benzimidazole-2-thione dihydrobenzimidazole-2-thione
    171 263° C. 9,10-Dinitroanthracene 9,10-dinitroanthracene 33685-60-8
    (288-290°)
    (294-296°)
    172 263-270° C. Mdl 74366 [2-(2-dimethylaminoethyl)- 128008-98-0
    2,5,7,8-tetramethylchroman-6-
    yl] acetate hydrochloride
    173 263-264° C. Dibenz(a,h)anthracen-5-ol naphtho[4,3-b]phenanthren- 4002-76-0
    12-ol
    174 263-265° C. Paxillarine A [(4R,8R,10R,13S,17S)-3- 145022-89-5
    (benzoyl-methylamino)-17-(1-
    dimethylaminoethyl)-16-
    hydroxy-10,13-dimethyl-
    2,3,4,5,6,7,8,9,11,12,14,15,16,-
    17-tetradecahydro-1H-
    cyclopenta[a]phenanthren-4-yl]
    acetate
    175 263-267° C. N-Deacetyl-3-demethyl-N- N-(3-hydroxy-1,2,10- 18172-26-4
    formylcolchicine trimethoxy-9-oxo-6,7-dihydro-
    5H-benzo[d]heptalen-7-
    yl)formamide
    176 263-264° C. N-[(2S,4aR,6S,7R,8R,8aS)-8- N-[(2S,4aR,6S,7R,8R,8aS)-8- 13343-63-0
    hydroxy-2-phenyl-6- hydroxy-2-phenyl-6-
    (phenylmethoxy)- (phenylmethoxy)-
    4,4a,6,7,8,8a- 4,4a,6,7,8,8a-
    hexahydropyrano[5,6- hexahydropyrano[5,6-
    d][1,3]dioxin-7-yl]acetamide d][1,3]dioxin-7-yl]acetamide
    177 263° C. 7-Amino-5,8-quinolinedione 7-aminoquinoline-5,8-dione 64636-91-5
    178 263-264° C. 9-Acridinecarboxamide acridine-9-carboxamide 35417-96-0
    179 264° C. Theophylline 1,3-dimethyl-7H-purine- 58-55-9
    (268°) 2,6-dione
    180 264-265° C. Siguazodan 3-cyano-2-methyl-1-[4-(4- 115344-47-3
    methyl-6-oxo-4,5-dihydro-
    1H-pyridazin-3-
    yl)phenyl]guanidine
    181 264° C. 4-nitro-N-(pyridin-2- 4-nitro-N-(pyridin-2- 70421-66-8
    ylmethylideneamino)aniline ylmethylideneamino)aniline
    182 264-266° C. 3-(Hydroxyamino)-1H-isoindol-1- 3-(hydroxyamino)isoindol- 29833-90-7
    one 1-one
    183 264° C. 2,3-Diaminophenazine phenazine-1,2-diamine 655-86-7
    184 264-265° C. Harmine 7-methoxy-1-methyl-9H- 442-51-3
    pyrido[3,4-b]indole
    185 264-265° C. 2-Hydroxyisophenoxazin-3-one 10H-phenoxazine-2,3- 1915-49-7
    dione
    186 264-265° C. 3-Hydroxyestra-1,3,5(10),6- (8R,9S,13S,14S)-3- 2208-12-0
    tetraen-17-one hydroxy-13-methyl-
    9,11,12,14,15,16-
    hexahydro-8H-
    cyclopenta[a]phenanthren-
    17-one
    187 264-268° C. 21-Hydroxyfriedelan-3-one (4R,4aS,6aS,6aS,6bR,8aS,- 59995-80-1
    10R,12aR,14aS,14bS)-
    10-hydroxy-
    4,4a,6a,6b,8a,11,11,14a-
    octamethyl-
    2,4,5,6,6a,7,8,9,10,12,12a,-
    13,14,14b-tetradecahydro-
    1H-picen-3-one
    188 264-266° C. 9-octyl-3H-purine-6-thione 9-octyl-3H-purine-6-thione 60632-18-0
    189 265° C. 3,4,5-tri(phenyl)-1H-pyrazole 3,4,5-tri(phenyl)-1H- 18076-30-7
    pyrazole
    190 265-268° C. Spirobishexahydropyrimidine 4,4,10,10-tetramethyl- 4115-66-6
    1,3,7,9-
    tetrazaspiro[5.5]undecane-
    2,8-dione
    191 265-267° C. 1,2,3,4-tetrahydroacridine-9- 1,2,3,4-tetrahydroacridine- 42878-53-5
    carboxamide 9-carboxamide
    192 265-266° C. 1H-Pyrrolo(2,3-d)pyrimidine- 1,3,7-trimethylpyrrolo[3,2- 39930-51-3
    2,4(3H,7H)-dione,- e]pyrimidine-2,4-dione
    1,3,7-trimethyl-
    193 265° C. 4-(4-carbamoylphenoxy)benzamide 4-(4- 6336-34-1
    carbamoylphenoxy)benzamide
    194 265-266° C. 4,4′-Iminobisbenzonitrile 4-[(4- 36602-05-8
    cyanophenyl)amino]benzonitrile
    195 265-266° C. 1,10-Phenanthroline,- 5,6-dimethyl-1,10- 3002-81-1
    5,6-dimethyl- phenanthroline
    196 265-267° C. 4H-1-Benzopyran-4-one,- 7-hydroxy-2-(4- 487-24-1
    7-hydroxy-2-(4-methoxyphenyl)- methoxyphenyl)chromen-
    4-one
    197 265° C. 1,4,6-triaminopyrimidine-2-thione 1,4,6-triaminopyrimidine-2- 4765-63-3
    thione
    198 265° C. 9,10-Anthracenedione,- 1,8-diaminoanthracene- 129-42-0
    1,8-diamino- 9,10-dione
    199 265° C. 2-hydroxy-1H- 5690-46-0
    benz[de]isoquinoline-
    1,3(2H)N-dione, 9Cl;
    Naphthalhydroxyamic
    acid
    200 265° C. 3-aminoquinoxaline-2-carboxamide 67568-30-3
    Amide derivative
    201 265° C. 6-Nitro-2-quinolinamine 49609-07-6
    202 265° C. 2-aminonaphtho[2,1d] thiazole 54380-14-2
    (N—Ac form)
    203 265° C. hernandonine, deriv 3-methoxy 155944-22-2
    204 265° C. 3-hydroxy-6-methylisoquinoline 51463-11-7
    205 265° C. hexahydro-1,2,4-ethanylylidene- 110243-21-5
    1H-cyclobuta[cd]pentalene-3,5,7-
    trione
    206 265° C. 2,6-anthracenediol,- 13979-53-8
    di-Ac form
    207 265° C. 1H,9H-pyrrolo[3,2- 147345-48-0
    b][1,4]benzoxazin-2(3H)-one
    208 265° C. Histidine phenylalanine anhydride 56586-95-9
    (−)-cis-form
    209 265° C. 2,4,5,6,7-pentamethyl-1H- 69700-34-1
    benzimidazole
    210 265° C. 3-[2-(4-pyridinyl)ethenyl]-1H- 53645-38-8
    indole (E)-form
    211 265° C. 9-aminofluorene (N—Ac form) 5424-77-1
    212 265° C. pyrido[2,3-b]pyrazine-2,3-diol C7H5N3O2/c11-6-7(12)10- 2067-84-7
    (derivative 3-Et ether) 5-4(9-6)2-1-3-8-5/h1-
    3H,(H,9,11)(H,8,10,12)
    213 265° C. diamide derivative 13363-51-4
    (C8H8N2S2)
    214 265° C. 2,4-dinitrophenylhydrazone Not Available
    (derivative of 1-(1H-inden-6-
    yl)ethanone chloride
    215 265° C. Tricarbazyl 6515-02-2
    3-(9-Carbazoly1)-9,9′
    dicarbazole
  • In certain aspects, the one or more organic compounds or chemicals are processed to minimize evaporative loss, enhance crystallinity, and to obtain high purity levels. The one or more organic compounds are processed into compacted shapes, such as pellets or grains, by application of pressure in a die or mold, by way of example. The structural integrity of pellets is desirably sufficient to withstand compressive forces of the HTTCO device, for example to withstand the applied force and bias to the HTTCO springs and encasement in a HTTCO assembly. The unique ability of HTTCO's to maintain physical rigidity and spring compression and therefore maintain electrical continuity at TCO operating temperatures in a high temperature device, yet further having the ability to physically transition and open the circuit at a rated threshold temperature is an important feature of the high-temperature thermal pellet compositions of the present teachings. By way of example, as noted previously, certain HTTCOs are capable of withstanding extended exposure to operating temperatures up to about 5° C. below the threshold or actuation temperature without breaking the electrical continuity of the circuit.
  • The high temperature thermal pellet compositions can be manufactured into any commercially available form suitable for use inside a housing of a TCO, including granules, pellets, spheres and any geometric shape known to those in the art. In addition to the above described organic compounds, the high temperature thermal cutoff pellet compositions of the present disclosure may optionally include one or more components selected from the group consisting of: a binder, a press aid, a release agent, a pigment, or mixtures thereof. The binder component, which generally softens (melts) at a temperature below the melting point of the organic component, is primarily utilized to assist in the production of pellets. While various binders known for pellet formation can be utilized, suitable binders include polyethylene glycol, 1,3-benzenediol, epoxies, polyamides and mixtures thereof. The binder is generally present in amounts up to about 10 wt. % based on the total composition.
  • Additionally, it may be desirable to employ a lubricant or pressing aid to aid in flowing and fill properties when processing the thermal pellets. For example, among the numerous lubricants or press aids which have proven useful are calcium stearate, boron nitride, magnesium silicate and polytetrafluoroethylene (Teflon®), among others. The lubricant is generally present in an amount up to about 5 wt. % based on the total pellet composition. It may also be desirable under certain applications to incorporate coloring agents such as pigments into the thermal cutoff composition to allow for rapid visual inspection of the pellets condition. Virtually any known pigment which is compatible with the aforementioned thermal cutoff composition components may be employed. Pigments, when employed, are typically present in an amount up to about 2 wt. % of the pellet composition.
  • In certain embodiments, the pellet composition may consist essentially of a single organic composition as the primary ingredient to arrive at a transition temperature of greater than or equal to about 240° C., and optionally a binder, optionally a press aid, optionally a release agent, and/or optionally a pigment. Such a pellet composition may comprise minimal amount of diluents or impurities that do not substantially affect the transition temperature of the pellet composition or the performance of the HTTCO at operating temperatures above the threshold temperature.
  • Initially, a first high-temperature thermal pellet sample can be prepared with the objective of obtaining a product having an expected transition temperature (e.g., melting point temperature or melt transition temperature) of about 240° C. The sample is processed to enhance the crystallinity and then prepared by mixing between about 90% to about 100% by weight of chemical either alone or with 10% to about 0.25% by weight of additives such as binders in a hammermill mixer. Added to the aforementioned organic compounds may be 5% to 0.25% by weight of a binders, such as polyamide binder, among others and 1% to 0.05% by weight of an organic azo pigment. The resulting composition exhibits a transition temperature/melting point temperature of about 236° C.
  • Additional samples can be prepared to make a HTTCO product having a melting point temperature of about 257° C. In this regard, the sample is processed to enhance the crystallinity and then prepared by mixing between about 90% to about 100% by weight of chemical either alone or with 10% to about 0.25% by weight of additives, such as binders, in a hammermill mixer. Added to the aforementioned organic compounds may be 5% to 0.25% by weight of binders, such as polyamide binder, among others and 1% to 0.05% by weight of an organic azo pigment. After blending to homogenize the constituent components, the sample may be analyzed using differential scanning calorimetry (DSC). The resulting composition has a transition temperature/melting point temperature of about 257° C.
  • In addition to exhibiting repeatable transition temperatures, the high-temperature thermal cutoff compositions of the present disclosure are also expected to exhibit clean current interrupt properties, decreased material and processing costs, and should have flexibility to permit customized design of predetermined thermal cutoffs to specific customer needs. In certain aspects, high melting point organic compositions can be formulated by use of computer software to calculate melting points of organic compounds for example, such as the computer program sold under the tradename PROMA2000®, manufactured by Daijin Technologies Corp. South Korea.
  • Furthermore, the transition temperatures/melting points of the various compositions to be used in the thermal cutoff composition in the present disclosure can be measured using ThermoGravimetric Analyzers coupled with and without Mass Spectrometer (TGA-MS), differential scanning colorimetry (DSC) and differential thermal analysis (DTA), by way of example. Devices for performing these qualitative and quantitative assays are commercially available, for example, from TA Instruments, New Castle, Del. USA, Model Q2000 (DSC), and Mettler STARe ThermoGravimetric Analyzer, TGA/sDTA851 e, coupled to a Balzers ThermoStar Mass Spectrometer from Mettler-Toledo, Columbus, Ohio. Further, the compositions of the present teachings can be quantitatively analyzed using known techniques such as proton or carbon nuclear magnetic resonance, mass spectroscopy or Fourier transform infrared spectroscopy techniques, by way of non-limiting example.
  • High-Temperature Sealants
  • In various embodiments of the present invention, the high temperature TCO device comprises a high-temperature sealant system that is used over one of more openings in the housing to provide a barrier between the interior of the HTTCO and the external atmosphere. In various aspects, the high temperature sealant system or seal is robust, reliable, and maintains integrity as high operating temperatures of the HTTCO device. The seal is an important aspect of the reliability and longevity of the HTTCO device, in that selection of an appropriate seal material provides a barrier that maintains chemical equilibrium inside the HTTCO, even at the high operating temperatures of the HTTCO and prevents substantial loss of the pellet materials through the seal or barrier.
  • Thus, in various aspects, the seal material system provides a strong sealing mechanism over one or more openings in the housing to prevent undesirable thermal pellet sublimation, and thus, loss of pellet material. In certain aspects, the reliability of the HTTCO sealing system can be related to the lifespan of the HTTCO device, where a predetermined life span is at least 1,000 hours or longer at 235° C. (reflecting the operating temperatures of about 5° C. than the threshold rating temperature of 240° C.).
  • In certain aspects, the high-temperature seal system is an epoxy-based system that is cured to provide a durable, high-temperature, strong sealing mechanism. One particularly suitable high temperature resistant epoxy system is formed from precursors comprising one or more diglycidyl ether of bisphenol A resins, which are combined with a hardener, for example a modified imidazole hardener or epichlorhydrin.
  • In various embodiments, the epoxy systems of the present invention are generally prepared in accordance with the manufacturer's recommendations. In certain embodiments, the epoxy systems are prepared in a modified manner to facilitate curing of the epoxy system in a manner that produces a strong mechanical seal between the HTTCO components (both metal and ceramic), which can withstand temperatures above about 235° C., optionally above about 240° C., optionally above about 245° C., optionally above about 250° C., optionally above about 260° C., optionally above about 265° C., optionally above about 270° C., optionally above about 275° C., optionally above about 280° C., optionally above about 285° C., optionally above about 290° C., and in certain aspects, optionally up to about 300° C., in a manner capable of retaining a stable thermal pellet composition and preventing substantial sublimation of the thermal pellet composition. In some embodiments, the epoxy systems of the present invention are cured to B-stage and/or full advanced or accelerated cure stage at various temperatures and relative humidity suitable to create the desired barrier seal. In certain aspects, the B-stage epoxy cure is a low temperature cure typically performed at less than or equal to about 60° C. at various relative humidities ranging from about 0% to about 85%, optionally at about 0 to about 75%, optionally about 0 to about 50%, optionally about 0 to about 40%, and in certain aspects about 0 to about 35%. A polymer seal is generally considered to be B-stage cured when the seal has a hardness shown by impression of a permanent indent mark at Shore Durometer 75. Thus, in certain aspects, the curing is conducted to achieve a hardness of at least Shore D 75. In certain embodiments, an accelerated or advanced cure is conducted after B-stage curing of the HTTCO device at an elevated temperature, for example from about 150° C. to about 175° C. for 3 to 5 hours, by way of example.
  • Many commercially available epoxy-based systems include at least two to three curable precursors that are mixed together and then cured to form a polymer. In certain embodiments, one suitable high-temperature epoxy-based sealant system to form a seal in the HTTCO comprises precursors comprising a diglycidyl ether bisphenol A resin and a hardener. In certain aspects, such a hardener comprises a modified imidazole compound. In certain embodiments, the hardener comprises a 2-ethyl-4-methyl-1H-imidazole. In certain embodiments, the epoxy-based sealant is formed by combining at least two epoxy precursors, where a first precursor comprises at least one epoxy resin, such as a bisphenol A diglycidyl ether, an elastomer polymer, and neopentyl glycol diglycidyl ether; and a second precursor comprises 2-ethyl-4-methyl-1H-imidazole as the hardener. By way of example, a commercially available diglycidyl ether of bisphenol A and modified imidazole hardener system is commercially available from Henkel Loctite as the following: Loctite® Hysol® 210210 Epoxy Resin Part A (Item No. 36745), Loctite® Hysol® 210211; Epoxy Hardener Part B (Item No. 36746); and Loctite® Hysol® 210209 Epoxy Pigment (Item No. 36745) (this combined epoxy system is referred to as “C5 epoxy”). Loctite® Hysol® 210210 Epoxy Resin Part A contains about 60-100% by weight of a first proprietary epoxy resin, which is believed to be a modified bisphenol A diglycidyl ether epoxy resin 10-30% of a second proprietary epoxy resin, which is also believed to be a modified bisphenol A diglycidyl ether, 10-30% of neopentyl glycol diglycidyl ether (CAS No. 17557-23-2); 5-10% of a proprietary elastomer, 1-5% titanium dioxide pigment, and 1-5% amorphous fumed silica. Loctite® Hysol® 210211 Epoxy Resin Part B contains 60-100% by weight of a proprietary modified imidazole, which is believed to be 2-ethyl-4-methyl-1H-imidazole. Loctite® Hysol® 210209 Epoxy Resin Part C contains 30-60% by weight titanium dioxide, 10-30% of a first proprietary epoxy resin, which is believed to be a modified bisphenol A diglycidyl ether epoxy resin, 10-30% of a second proprietary epoxy resin, which is also believed to be a modified bisphenol A diglycidyl ether, and 1-5% of a third proprietary epoxy resin, which is also believed to be a modified bisphenol A diglycidyl ether epoxy, 1-5% neopentyl glycol diglycidyl ether, 1-5% alkyl glycidyl ether, 1-5% aluminum oxide, 1-5% fumed amorphous silica, and lastly 1-5% of a proprietary elastomeric polymer.
  • In preparing the C5 epoxy, 80-100 parts by weight of the resin Part A is mixed with 0-20 parts by weight for the hardener Part B. Part C is optional and can be added at 0-20 parts by weight to form the final C5 epoxy to be applied to the TCO components for sealing the device containing the thermal pellet composition.
  • In yet another embodiment, an epoxy-based sealant is formed by combining at least two precursors, wherein a first precursor comprises an epoxy resin or bisphenol A diglycidyl ether polymer; a second precursor comprises a hardener or curing agent, such as 1-(2-cyanoethyl)-2-ethyl-4-methyl imidazole; and a third precursor comprises catalysts including benzenetetracarboxylic-1,2,4,5-dianhydride, hexahydrophthalic anhydride, and phthalic anhydride.
  • After the curable epoxy-based material has been applied to seal the TCO components to seal one or more openings (such as shown in FIGS. 1-2), the epoxy-based sealant system is optionally cured. Curing can be conducted by any means known in the art, including by application of heat, actinic radiation, and the like. In certain aspects, the epoxy sealant materials are subjected to a B-stage cure, where the epoxy system is heated to a temperature range of about 45° C. to about 65° C. in a controlled atmosphere having relative humidity ranging from 0% to 80%. Optionally, a full advanced cure can be conducted after B-stage curing. An advanced cure is optionally conducted at a temperature range of about 150° C. to about 200° C. in a controlled atmosphere having relative humidity ranging from 0% to 5%. In certain aspects, the C5 epoxy seal material is cured by placing the HTTCO device in an oven and heating the TCO at 248° C. for about 3 to about 9 hours at 0% relative humidity.
  • In certain other embodiments, the HTTCOs can be sealed with a suitable epoxy-based system commercially available from Emerson & Cuming Corp., Billerica, Mass. USA, which is a bisphenol A diglycidyl ether polymer (Part A); an epichlorohydrin hardener (Part B); and a catalyst (Part C) sold under the trade name Stycast® W 66 epoxy system (herein referred to as the “W66 epoxy system”). Specifically, the W66 epoxy system includes Part A comprising Bisphenol A diglycidyl ether polymer having an average molecular weight of less than 700 at 100 wt. %, Part B comprising 1-(2-cyanoethyle)-2-ethyl-4-methyl Imidazole hardener at greater than 99 wt. % in less than 0.1% acrylonitrile carrier. Part C of the W66 comprises a catalyst of Benzenetetracarboxylic-1,2,4,5-Dianhydride (35-50% by weight), Hexahydrophthalic anhydride (35-50% by weight) and phthalic anhydride (1-5% by weight).
  • In preparing the W66 epoxy, part A in an amount ranging from 50% to about 80% by weight is mixed with part B in an amount ranging from 50% to about 20% by weight and mixed. Once the W66 epoxy system has been applied to seal the HTTCO components, the W66 epoxy is optionally cured to a B-stage and/or advanced cure. By way of non-limiting example, the W66 seal system is applied and cured by placing the device in a controlled atmosphere and heating the TCO at 40° C. for about 48 to about 96 hours at 35% to 85% relative humidity.
  • EXAMPLE 1
  • In accordance with various aspects of the present disclosure, a high temperature TCO device is formed as follows. A pellet is formed by mixing 980 g to 1000 g of triptycene (commercially available from Sigma-Aldrich manufacturer at 95% to 99% purity) with 20 g to 0.5 g of colorants, binders, and or release agents. The homogenized mixture is processed on a standard powder compaction press widely available from pharmaceutical equipment suppliers. The powder is fed through a gated powder flow control system and spread evenly over a rotary die table. The powder fills the dies and punches press the powder in the dies under approximately 1 ton to 4 tons pressure to form a compacted powder pellet having a density of 29 pellets per gram to 50 pellets per gram. The pellet is placed into a high-conductivity metal, closed-end cylinder with an inner diameter approximately the outer diameter of the TCO pellet. The closed end of the cylinder is staked shut with an axial conductive metal lead protruding out of the cylinder. Other components are loaded atop the pellet in a stacked fashion depending on the end-use requirements of the TCO. A sub-assembly comprised of a non-conductive ceramic bushing with an axial bore hole and a conductive metal lead which has been inserted in the open bore and mechanically restrained into a permanent one-piece assembly by deformation of the metal lead is inserted into the open end of the TCO cylinder. The stacked components noted earlier in paragraph 0018 are compressed into the cylinder by the ceramic, isolated lead assembly and the rim of the open end of the cylinder is mechanically rolled over the ceramic bushing to permanently enclose the internal components in the TCO cylinder. The closed TCO is then sealed with a high temperature, epoxy sealant. An epoxy-based sealant is prepared at 25° C. to seal the bushing and isolated lead and rolled over cylinder edge exterior terminal region of the TCO housing by mixing 200 g of LOCTITE® HYSOL® 210210 Epoxy resin Part A (an epoxy resin comprising bisphenol A and diglycidyl ether); 14 g of LOCTITE® HYSOL® 210211 Epoxy hardener Part B (an imidazole hardener); and optionally 13.2 g of LOCTITE® HYSOL® 210209 Epoxy pigment Part C (epoxy resins, neopentyl glycol diglycidyl ether, pigment, . . . ) or an additional 13.2 g of LOCTITE® HYSOL® 210210 Epoxy resin Part A in a sealed paddle mixer at 100 RPM for 10 minutes under vacuum to 30 mmHg to form a uniform epoxy mixture. The reagents are mixed for a total of 1.5 minutes to 5 minutes with a 10 minute no-mix vacuum step at the end of the mechanical mix to form a single component matrix mixture. The epoxy mixture is applied over the bushing and isolated lead to cover down to the rolled over cylinder rim of the TCO device using epoxy dispenser bottles with narrow tips or mechanical application equipment to ensure even coverage.
  • The assembled TCO having the epoxy sealing compound applied is then cured for 9 hours at 48° C. to 60° C. under 0% RH to 85%. The B-staged TCO assemblies are then cured in a controlled over at a temperature of 150° C. optionally up to 235° C. in 0% RH to 35% RH for 3 hours up to 6 hours.
  • The C5 epoxy system is studied to demonstrate the high-temperature performance of the sealant system, as well as the ability to retain polycyclic organic compounds of the pellet of the HTTCO device. Specifically, the high-temperature thermal pellet contained triptycene and a polytetrafluoroethylene release agent, which was retained by the C5 epoxy seal during continuous exposure to 247° C. A thermal pellet formed of a smaller molecule pentaerythritol (CAS No. 115-77-5) having a melting point beginning at 259° C. was not retained in a TCO using the C5 sealing system during continuous exposure to 247° C. The melting points of the two pellet organic compounds, triptycene and pentaerythritol are similar, and, are known to have similar volatile evolution behavior. However, the C5 sealing system is able to retain the triptycene inside the sealed HTTCO housing significantly better than the pentaerythritol.
  • The pellet height of the pentaerythritol at Day 1 goes from an initial pellet height of 101 thousandths of an inch to 0.00 thousandths of an inch. Thus, TCOs having the pentaerythritol open continuity or exhibited resistance greater than 200 kOhm (actuate) almost immediately. The HTTCO having a pellet containing triptycene has an initial pellet height of about 98 thousandths of an inch and retains at least 80 thousandths of an inch pellet height for at least 13 weeks and does not exhibit resistance of greater than 200 kOhm until over 2,100 hours of performance for 9 out of 10 HTTCO samples.
  • Given that the compounds melting points and their volatility onset by TGA are nearly identical, the difference in retention is believed to be attributed to functionality or size of the molecule, or a combination of both. Using a simple computer model, the sizes (radii) of the compounds are calculated. As noted in Table 3, below, triptycene has a radius of 0.46 nm while pentaerythritol has a radius of 0.33 nm. Also, the triptycene molecule is fairly rigid given the steric hindrance of the three benzene rings. When viewed along the end of the molecule, the 3 benzene molecules separate at 120° from each other for maximum spacing. On the other hand, the pentaerythritol has significantly more molecular freedom to twist and reorient itself. The triptycene has little functionality other than the double bonds present in the aromatic ring. However, the aromatic rings have the ability to pi-pi stack with other aromatic rings in the epoxy structure, which could immobilize them in the pores thus blocking the pore. The pentaerythritol has four polar hydroxyl bonds that have hydrogen bond accepting/donating capability.
  • TABLE 3
    Compound triptycene pentaerythritol
    CAS# 477-75-8 115-77-5
    Other Names Triptycene; Methane tetramethylol;
    9,10-o-Benzenoanthracene, 9,10- Pentaerythrital;
    dihydro-; Tetrahydroxymethylmethane;
    Tribenzobicyclo[2.2.2]octatriene; Tetrakis(Hydroxymethyl)methane;
    Tryptycene: Tetramethylolmethane;
    Anthracene, 9,10-dihydro-9,10- 2,2-Bis(hydroxymethyl)-1,3-
    O-benzeno- propanediol;
    Methane,
    tetrakis(hydroxymethyl)-,
    Formula C20H14 C5H12O4
    F.W. 254.33 136.15
    Melting Point 252-256° C. 257-264° C.
    252-254° C. 253-258° C.
    Boiling Point None found 276° C. (at 30 mmHg)
    276° C./30 mmHg(lit.)
    Vapor Pressure None found <1 mmHg (20° C.)
    radius 4.7 Angstroms 3.3 Angstroms
    Structure
    Figure US20100033295A1-20100211-C00003
    Figure US20100033295A1-20100211-C00004
  • A 1-aminoanthraquinone [CAS # 82-45-1] pellet is also examined for its behavior in a C5 epoxy sealing system. The 1-aminoanthraquinone has a melting point in the same range as the pentaerythritol and triptycene, so once again the size and functionality are examined to provide insight into the interaction of the organic compound with the cured epoxy seal material. The 1-aminoanthraquinone molecule lies in a single plane and is a rigid molecule due to the benzene rings and the carbonyl bonds that bond them together—all of which require planar orientation. The radius of the 1-aminoanthraquinone is 0.45 nm, which is similar in size to the triptycene. However, the 1-aminoanthraquinone has the added advantage of having more functionality present with which to interact with the epoxy seal material. The carbonyl bonds can accept hydrogen donation and the amine group can hydrogen donate/accept. Based on its steric similarity to triptycene and its functionality similarity to pentaerythritol, 1-aminoanthraquinone has even greater retention by the epoxy seal that the triptycene or pentaerythritol.
  • Specimens of the C5 system are produced by reacting the components at temperatures and humidities listed below. All specimens are exposed to the same temperature programming for B-staged and advanced cure levels. B-staged specimens are heated at 48° C. for 5 hours and then at 58° C. for 4 hours. The B-staging is performed in two different relative humidity environments (0% and 35% RH) to determine the effect of water on the B-stage curing. Specimens exposed to 35% RH are B-staged in a humidity chamber that maintains the humidity at 35% while following the temperature program. Specimens prepared in 0% RH are B-staged in an oven. To achieve 0% RH, a compressed air source with two water traps is employed to ensure that no water is exposed to the epoxy system during B-staging. Some specimens required advanced curing, which entailed heating the B-staged specimens to 150° C. for 3 hours. The humidity is not monitored during advanced curing, but the specimens are still identified by their B-stage humidity level for labeling purposes.
  • From the surface area data, both cured epoxy seal samples have very low surface areas (approximately 0.09 m2/g), and the shapes of the adsorption plots indicate a very nonporous structure. By dividing the volume of the pores by their area and multiplying by 4, the average pore width is determined. Two different techniques are employed for pore width determination—the BET value and the BJH value. For both techniques, the C5 epoxy sample cured at 35% humidity showed a larger pore width than the C5 epoxy cured with 0% humidity (25.53 as opposed to 0.312 nm with BET, 39.53 as opposed to 27.16 nm with BJH). The inclusion of water during the B-stage curing appears to provide a larger pore structure in the cured epoxy-based polymer. Based on the BET pore widths, a smaller pore width, for example, given by curing in 0% humidity, provides the ability to greatly enhance retention of the larger triptycene molecule.
  • The identification and characterization of the starting material chemistry for the epoxy-based system is included herein, as are the properties of the cured epoxy-based system. For the C5 epoxy, Part A epoxy resin has the six components listed above, including the two proprietary epoxy resins and a proprietary elastomeric polymer; Part B has a single a proprietary imidazole hardener, and Part C is an optional component for colorant and includes nine components, including three proprietary epoxy resins and a proprietary elastomer. Analysis of the materials indicates that the hardener of Part B is 2-ethyl-4-methyl-1H-imidazole. Of the six components listed for the Part A precursor, the silica and titanium dioxide are believed to be relatively inert and do not play a significant role in the cured epoxy chemistry. The neopentyl glycol diglycidyl ether (CAS #17557-23-2) of Part A has two epoxide groups, so it does not reduce the crosslink density and is believed to provide structural flexibility in between the larger, more rigid aromatic epoxy resins. This increased mobility allows the material to desirably flow and increases the pot life. The two proprietary epoxy resins are major constituents of the Part A precursor. The elastomeric polymer is not believed to react with the epoxies during curing, although unsaturated double bonds may participate in some cross-linking. Generally, where the elastomeric polymer does not react, it forms a separate phase within the epoxy which provides more impact resistance and increased mobility. While not limiting the present disclosure to any particular theory, it is likely this elastomeric polymer and the inclusion of the neopentyl glycol diglycidyl ether in the backbone of the epoxy are imparting the high temperature reflow capability of the C5 system. The two remaining Part A epoxy resin precursors are determined to be derivatives of the diglycidyl ether of Bisphenol A.
  • In the manner, the present teachings provide high-temperature thermal cutoff devices and methods of making such devices, by forming high-temperature stable seals and high temperature thermal pellets comprising one or more organic compounds that are substantially retained by the seal barrier. The HTTCOs are highly stable, robust, and are capable of use as switching devices in a variety of high-temperature applications that were previously not possible, such as high-temperature clothing and hair styling irons.

Claims (30)

1. A high temperature thermal cutoff device comprising:
a high-temperature thermal pellet having a transition temperature of greater than or equal to about 240° C. comprising at least one organic compound disposed in a housing;
a high-temperature seal disposed in a portion of at least one opening of said housing to substantially seal said housing up to said transition temperature; and
a current interruption assembly at least partially disposed within said housing that establishes electrical continuity in a first operating condition corresponding to an operating temperature of less than said transition temperature of said pellet, and that discontinues electrical continuity when said operating temperature exceeds said transition temperature.
2. The high temperature thermal cutoff device of claim 1, wherein said at least one organic compound organic compounds has a melting point temperature (mp) of T−5° C.≦mp≦T+2° C., where T represents said transition temperature of said high-temperature thermal pellet.
3. The high temperature thermal cutoff device of claim 1, wherein said at least one organic compound comprises a polycyclic organic compound.
4. The high temperature thermal cutoff device of claim 1, wherein said at least one organic compound comprises triptycene.
5. The high temperature thermal cutoff device of claim 1, wherein said at least one organic compound comprises 1-aminoanthroquinone.
6. The high temperature thermal cutoff device of claim 1, wherein said pellet comprises greater than or equal to about 95 weight % of said at least one organic compound.
7. The high temperature thermal cutoff device of claim 1, wherein said pellet comprises one or more components selected from the group consisting of: a binder, a press aid, a release agent, a pigment, or mixtures thereof.
8. The high temperature thermal cutoff device of claim 1, wherein said high temperature seal comprises an epoxy-based sealant formed from precursors comprising a diglycidyl ether bisphenol A resin and a hardener.
9. The high temperature thermal cutoff device of claim 8, wherein said hardener comprises a modified imidazole compound.
10. The high temperature thermal cutoff device of claim 8, wherein said hardener comprises a 2-ethyl-4-methyl-1H-imidazole.
11. The high temperature thermal cutoff device of claim 8, wherein said epoxy-based sealant is formed by combining at least two epoxy precursors, wherein a first precursor comprises at least one bisphenol A diglycidyl ether, an elastomer, and neopentyl glycol diglycidyl ether; and a second precursor comprises 2-ethyl-4-methyl-1H-imidazole.
12. The high temperature thermal cutoff device of claim 8, wherein said epoxy-based sealant is formed by combining at least two epoxy precursors, wherein a first precursor comprises a bisphenol A diglycidyl ether polymer; a second precursor comprises a 1-(2-cyanoethyl)-2-ethyl-4-methyl imidizole; and a third precursor comprises benzenetetracarboxylic-1,2,4,5-dianhydride, hexahydrophthalic anhydride, and phthalic anhydride.
13. The high temperature thermal cutoff device of claim 1, wherein said transition temperature is greater than or equal to about 240° C. and less than or equal to about 270° C.
14. The high temperature thermal cutoff device of claim 1, wherein said device is capable of operating at greater than or equal to about 1,000 hours at a sustained temperature of about 235° C.
15. A high temperature thermal cutoff device comprising:
a housing having at least one opening;
a high-temperature thermal pellet having a transition temperature of greater than or equal to about 240° C. comprising at least one crystalline organic compound and disposed in said housing;
a high-temperature seal disposed in a portion of said opening to substantially seal said housing to said transition temperature of said high-temperature thermal pellet;
a current interruption assembly comprising: an electric contact in electrical continuity with an external current source to establish an electrical circuit in a first operating condition corresponding to an operating temperature of less than said transition temperature of said pellet, wherein at least a portion of said electric contact is disposed within said housing, a sliding contact member disposed within said housing, and a tensioning mechanism disposed in said housing to bias said sliding contact member against said electric contact in said first operating condition to maintain an electrical circuit and to release and interrupt electrical continuity between said sliding contact member and said electric contact in a second operating condition when said operating temperature is greater than said transition temperature.
16. The high temperature thermal cutoff device of claim 15, wherein said at least one crystalline organic compound comprises a polycyclic organic compound.
17. The high temperature thermal cutoff device of claim 15, wherein said at least one crystalline organic compound comprises triptycene.
18. The high temperature thermal cutoff device of claim 15, wherein said at least one crystalline organic compound comprises 1-aminoanthroquinone.
19. The high temperature thermal cutoff device of claim 15, wherein said pellet comprises greater than or equal to about 95 weight % of said at least one crystalline organic compound.
20. The high temperature thermal cutoff device of claim 15, wherein said pellet comprises one or more components selected from the group consisting of: a binder, a press aid, a release agent, a pigment, or mixtures thereof.
21. The high temperature thermal cutoff device of claim 15, wherein said high temperature seal comprises an epoxy-based sealant formed from precursors comprising a diglycidyl ether bisphenol A resin and a hardener.
22. The high temperature thermal cutoff device of claim 21, wherein said hardener comprises a modified imidazole compound.
23. The high temperature thermal cutoff device of claim 22, wherein said hardener comprises a 2-ethyl-4-methyl-1H-imidazole.
24. The high temperature thermal cutoff device of claim 21, wherein said epoxy-based sealant is formed by combining at least two epoxy precursors, wherein a first precursor comprises at least one bisphenol A diglycidyl ether, an elastomer, and neopentyl glycol diglycidyl ether; and a second precursor comprises 2-ethyl-4-methyl-1H-imidazole.
25. The high temperature thermal cutoff device of claim 21, wherein said epoxy-based sealant is formed by combining at least two epoxy precursors, wherein a first precursor comprises a bisphenol A diglycidyl ether polymer; a second precursor comprises a 1-(2-cyanoethyl)-2-ethyl-4-methyl imidizole; and a third precursor comprises benzenetetracarboxylic-1,2,4,5-dianhydride, hexahydrophthalic anhydride, and phthalic anhydride.
26. The high temperature thermal cutoff device of claim 15, wherein said transition temperature is greater than or equal to about 240° C. and less than or equal to about 270° C.
27. The high temperature thermal cutoff device of claim 15, wherein the device is capable of operating at greater than or equal to about 1,000 hours at a sustained temperature of about 235° C.
28. A high temperature thermal cutoff device comprising:
a housing containing a high-temperature thermal pellet having a transition temperature of greater than or equal to about 240° C. and comprising at least one crystalline organic compound selected from the group consisting of: triptycene and 1-aminoanthroquinone;
a high-temperature epoxy-based seal disposed in a portion of at least one opening of said housing to substantially seal said housing up to said transition temperature; and
a current interruption assembly at least partially disposed within said housing that establishes electrical continuity in a first operating condition corresponding to an operating temperature of less than said transition temperature of said pellet, and that discontinues electrical continuity when said operating temperature exceeds said transition temperature, wherein the high-temperature thermal cut-off device is capable of operating at greater than or equal to about 1,000 hours at a sustained temperature of about 235° C.
29. A method of making a high temperature thermal cutoff device comprising:
disposing a high-temperature thermal pellet in a thermal cutoff device housing, wherein said high-temperature thermal pellet has a transition temperature of greater than or equal to about 240° C. and comprises at least one crystalline organic compound;
disposing a current interruption assembly at least partially in said housing, wherein said current interruption assembly is capable of establishing electrical continuity in a first operating condition corresponding to an operating temperature of less than said transition temperature of said thermal pellet, and discontinuing electrical continuity when said operating temperature exceeds said transition temperature;
sealing at least one opening in the housing with a high-temperature epoxy-based seal to form a sealed housing, wherein the high-temperature thermal cut-off device is capable of operating at greater than or equal to about 1,000 hours at a sustained temperature of about 235° C.
30. The method of claim 29, wherein said sealing further comprises applying a curable epoxy-based mixture over said at least one opening and curing said curable epoxy-based mixture to form a high-temperature seal.
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US13/352,181 US8961832B2 (en) 2008-08-05 2012-01-17 High temperature material compositions for high temperature thermal cutoff devices
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120182116A1 (en) * 2009-07-15 2012-07-19 Vishay Resistors Belgium Bvba Thermal switch
US20120194317A1 (en) * 2011-02-02 2012-08-02 Anthony Vranicar Three-Function Reflowable Circuit Protection Device
US20130200984A1 (en) * 2011-08-12 2013-08-08 Tyco Electronics Corporation Reflowable Circuit Protection Device
EP2674956A1 (en) 2012-06-15 2013-12-18 Therm-O-Disc Incorporated High thermal stability pellet compositions for thermal cutoff devices and methods for making and use thereof
US20140035716A1 (en) * 2012-08-06 2014-02-06 Shelomon Patrick Doblack Reflowable Circuit Protection Device
WO2014099839A3 (en) * 2012-12-18 2014-08-14 Powermag, LLC Power conditioning and saving device
US20150044131A1 (en) * 2012-03-23 2015-02-12 Intelligent Energy Inc. Hydrogen producing fuel cartridge and methods for producing hydrogen
US8961832B2 (en) 2008-08-05 2015-02-24 Therm-O-Disc, Incorporated High temperature material compositions for high temperature thermal cutoff devices
US9276278B2 (en) 2012-03-23 2016-03-01 Intelligent Energy Limited Hydrogen producing fuel cartridge
US9455106B2 (en) 2011-02-02 2016-09-27 Littelfuse, Inc. Three-function reflowable circuit protection device
US9742182B1 (en) * 2016-08-04 2017-08-22 International Business Machines Corporation Acclimation sensing and control of electronic equipment
KR20180021061A (en) * 2015-06-24 2018-02-28 블랙만 게엠베하 코. 카게 Terminal devices for tubular heating devices with integrated fuses
US10276318B1 (en) * 2013-03-15 2019-04-30 Innovative Switchgear IP, LLC Insulated switch
US10566600B2 (en) 2011-10-31 2020-02-18 Powermag, LLC Power conditioning and saving device

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103239140A (en) * 2013-05-27 2013-08-14 江阴市志翔电子科技有限公司 Temperature sensing particle for thermal link for electric rice cooker
US10249460B2 (en) 2014-09-01 2019-04-02 Therm-O-Disc, Incorporated High thermal stability thermal cutoff device pellet composition
US10590352B2 (en) * 2016-03-03 2020-03-17 Exxonmobil Research And Engineering Company Abnormal temperature detection for fixed bed reactors
CN105679603B (en) * 2016-03-18 2018-03-13 厦门赛尔特电子有限公司 A kind of temperature sensitive type change-over switch
DE102017105436B3 (en) * 2017-03-14 2018-06-14 DEHN + SÖHNE GmbH + Co. KG. Thermally triggered, mechanical switching device
CN107633984B (en) * 2017-10-27 2019-12-13 泉州台商投资区镕逸科技有限公司 Temperature fuse structure
CN109187622A (en) * 2018-07-24 2019-01-11 彩虹显示器件股份有限公司 A kind of measurement method that high-resolution display is shunk with electronics glass heat
CN109509678A (en) * 2018-11-22 2019-03-22 漳州雅宝电子有限公司 A kind of high temperature resistant thermo-sensitive material that fusing point is 236 ± 2 DEG C
JP7327289B2 (en) * 2020-06-04 2023-08-16 トヨタ自動車株式会社 Electric heating catalyst device

Citations (93)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3281559A (en) * 1964-05-21 1966-10-25 United Carr Inc Thermal fuse having telescopically received contact members
US3519972A (en) * 1969-03-18 1970-07-07 Micro Devices Corp Temperature responsive electric switch
US3571777A (en) * 1969-07-07 1971-03-23 Cabot Corp Thermally responsive current regulating devices
US3692921A (en) * 1971-04-12 1972-09-19 Joslyn Mfg & Supply Co Cable coupler
US3711428A (en) * 1971-02-01 1973-01-16 Ibm Electrical resistor paste containing a small amount of charcoal
US3727164A (en) * 1972-07-14 1973-04-10 Minnesota Mining & Mfg Temperature-responsive electrical switch
US3745507A (en) * 1972-08-18 1973-07-10 Matsushita Electric Ind Co Ltd Nonflammable composition resistor
US3793716A (en) * 1972-09-08 1974-02-26 Raychem Corp Method of making self limiting heat elements
US3883837A (en) * 1973-11-05 1975-05-13 Robertshaw Controls Co Thermal responsive switch
US3898602A (en) * 1974-01-25 1975-08-05 Itt Enclosed, non-vented expulsion fuse
US3951582A (en) * 1974-05-24 1976-04-20 General Electric Company Switching devices for photoflash unit
US3974105A (en) * 1973-05-30 1976-08-10 Matsushita Electric Industrial Co., Ltd. Overtemperature and overcurrent resistor fuse
US4001754A (en) * 1974-05-21 1977-01-04 Emerson Electric Co. Temperature responsive electrical switch construction and method of making the same
US4006443A (en) * 1975-09-11 1977-02-01 Allen-Bradley Company Composition resistor with an integral thermal fuse
US4023072A (en) * 1973-01-08 1977-05-10 Emerson Electric Co. Electrical protection means and method
US4031497A (en) * 1975-09-23 1977-06-21 Juichiro Ozawa Fusible resistor
US4068204A (en) * 1975-12-26 1978-01-10 New Nippon Electric Company, Ltd. Thermal fuse employing a slidable resilient contact member in a conductive housing
US4075596A (en) * 1976-08-23 1978-02-21 Emerson Electric Co. Sealed casing for a thermally actuable electrical switch
US4084147A (en) * 1977-05-31 1978-04-11 Emerson Electric Co. Normally open, thermal sensitive electrical switching device
US4142418A (en) * 1977-04-05 1979-03-06 Gunnar Lagher Temperature sensitive member
US4184139A (en) * 1977-08-29 1980-01-15 Illinois Tool Works Inc. Thermal cut-off fuse
US4186366A (en) * 1978-10-20 1980-01-29 Illinois Tool Works Inc. Radial lead thermal cut-off device
US4189697A (en) * 1977-09-09 1980-02-19 Nifco Inc. Thermal cut-off fuse
US4249154A (en) * 1979-02-12 1981-02-03 Emerson Electric Co. Temperature responsive electrical switching device and method of calibrating
US4259656A (en) * 1979-05-11 1981-03-31 Illinois Tool Works Inc. Thermal cut-off device with an activating spring that is held in a prestressed condition by a thermally fusible pellet
US4276532A (en) * 1978-07-08 1981-06-30 Murata Manufacturing Co., Ltd. Thermal fuse
US4276531A (en) * 1979-04-20 1981-06-30 Davis Merwyn C Nonresetable thermally actuated switch
US4281309A (en) * 1978-03-28 1981-07-28 Olson Harry W Thermally actuated cut-off link or switch and method of making the same
US4281308A (en) * 1979-12-26 1981-07-28 Illinois Tool Works Inc. Thermal switch with split ring construction
US4310469A (en) * 1978-12-29 1982-01-12 General Electric Company Diaryliodonium salts
US4322705A (en) * 1979-09-26 1982-03-30 Nifco Inc. Thermal cutout fuse
US4344061A (en) * 1979-09-11 1982-08-10 Showa Electric Wire & Cable Co., Ltd. Temperature-sensitive fuse
US4373556A (en) * 1981-12-02 1983-02-15 Canadian General Electric Company Limited Cut-out fuse tube
US4384267A (en) * 1980-07-07 1983-05-17 Murata Manufacturing Co., Ltd. Thermosensitive fuse
US4480247A (en) * 1981-10-06 1984-10-30 Nifco Inc. Thermal cutout fuse
US4514718A (en) * 1983-12-02 1985-04-30 Emerson Electric Co. Thermal cutoff construction, member therefor and methods of making the same
US4675641A (en) * 1986-06-20 1987-06-23 General Electric Company Rating plug for molded case circuit breakers
US4757423A (en) * 1986-02-15 1988-07-12 Stc Plc Fuse for electronic component
US4763228A (en) * 1987-11-20 1988-08-09 Union Carbide Corporation Fuse assembly for solid electrolytic capacitor
US4763099A (en) * 1985-12-04 1988-08-09 Thorn Emi Plc Temperature sensitive device
US4808965A (en) * 1987-11-06 1989-02-28 Therm-O-Disc, Incorporated Thermal protector
US4821010A (en) * 1987-12-30 1989-04-11 Therm-O-Disc, Incorporated Thermal cutoff heater
US4841273A (en) * 1987-12-18 1989-06-20 Therm-O-Disc, Incorporated High temperature sensing apparatus
US4873604A (en) * 1983-04-21 1989-10-10 Hoechst Celanese Corp. Fuses having suppressed voltage transients
US4873506A (en) * 1988-03-09 1989-10-10 Cooper Industries, Inc. Metallo-organic film fractional ampere fuses and method of making
US4933658A (en) * 1989-05-10 1990-06-12 Ingersoll-Rand Company High temperature fluid sensor
US5003283A (en) * 1990-01-22 1991-03-26 Therm-O-Disc, Incorporated Thermal cutoff with lead indicia
US5015514A (en) * 1987-08-18 1991-05-14 A. B. Chance Company Pultruded or filament wound synthetic resin fuse tube
US5027101A (en) * 1987-01-22 1991-06-25 Morrill Jr Vaughan Sub-miniature fuse
US5106540A (en) * 1986-01-14 1992-04-21 Raychem Corporation Conductive polymer composition
US5106538A (en) * 1987-07-21 1992-04-21 Raychem Corporation Conductive polymer composition
US5212261A (en) * 1990-12-17 1993-05-18 Henkel Research Corporation Latent, heat-curable epoxy resin compositions containing metal carboxylate curing systems
US5215636A (en) * 1991-09-27 1993-06-01 American International Technologies, Inc. Pulsed discharge surface treatment apparatus and process
US5530417A (en) * 1994-06-06 1996-06-25 Therm-O-Disc, Incorporated Thermal cutoff with floating contact member
US5545679A (en) * 1993-11-29 1996-08-13 Eaton Corporation Positive temperature coefficient conductive polymer made from thermosetting polyester resin and conductive fillers
US5601924A (en) * 1991-07-17 1997-02-11 Materials Innovation Inc. Manufacturing particles and articles having engineered properties
US5663702A (en) * 1995-06-07 1997-09-02 Littelfuse, Inc. PTC electrical device having fuse link in series and metallized ceramic electrodes
US5712610A (en) * 1994-08-19 1998-01-27 Sony Chemicals Corp. Protective device
US5750277A (en) * 1996-04-10 1998-05-12 Texas Instruments Incorporated Current interrupter for electrochemical cells
US5772949A (en) * 1996-02-23 1998-06-30 Hoechst Celanese Corp. Thermally expandable, viscosity modified wax compositions and method of use in actuators
US5777540A (en) * 1996-01-29 1998-07-07 Cts Corporation Encapsulated fuse having a conductive polymer and non-cured deoxidant
US5808538A (en) * 1996-06-19 1998-09-15 Littelfuse, Inc. Electrical apparatus for overcurrent protection of electrical circuits
US5856773A (en) * 1996-11-04 1999-01-05 Raychem Corporation Circuit protection device
US5914649A (en) * 1997-03-28 1999-06-22 Hitachi Chemical Company, Ltd. Chip fuse and process for production thereof
US5929741A (en) * 1994-11-30 1999-07-27 Hitachi Chemical Company, Ltd. Current protector
US5939968A (en) * 1996-06-19 1999-08-17 Littelfuse, Inc. Electrical apparatus for overcurrent protection of electrical circuits
US6059997A (en) * 1995-09-29 2000-05-09 Littlelfuse, Inc. Polymeric PTC compositions
US6282074B1 (en) * 1999-01-28 2001-08-28 X2Y Attenuators, L.L.C. Polymer fuse and filter apparatus
US6359544B1 (en) * 2000-10-10 2002-03-19 Therm-O-Disc Incorporated Conductive polymer compositions containing surface treated kaolin clay and devices
US6375867B1 (en) * 1993-11-29 2002-04-23 Eaton Corporation Process for making a positive temperature coefficient conductive polymer from a thermosetting epoxy resin and conductive fillers
US6388553B1 (en) * 2000-03-02 2002-05-14 Eaton Corproation Conductive polymer current-limiting fuse
US6396384B1 (en) * 2000-10-10 2002-05-28 Therm-O-Disc, Incorporated Conductive polymer compositions containing perhydrotriphenylene
US6403935B2 (en) * 1999-05-11 2002-06-11 Thermosoft International Corporation Soft heating element and method of its electrical termination
US6452138B1 (en) * 1998-09-25 2002-09-17 Thermosoft International Corporation Multi-conductor soft heating element
US6515570B2 (en) * 1999-12-08 2003-02-04 Abb Research Ltd Fuse with overstoichiometric amount of oxidant
US6563094B2 (en) * 1999-05-11 2003-05-13 Thermosoft International Corporation Soft electrical heater with continuous temperature sensing
US20030112117A1 (en) * 2001-07-18 2003-06-19 Ikuhiro Miyashita Thermal fuse
US6673257B1 (en) * 2000-09-12 2004-01-06 Therm-O-Disc, Incorporated Thermal cutoff construction compositions
US6713733B2 (en) * 1999-05-11 2004-03-30 Thermosoft International Corporation Textile heater with continuous temperature sensing and hot spot detection
US20040070484A1 (en) * 2001-10-29 2004-04-15 Krause John A. Arrester housing support bracket
US20040191556A1 (en) * 2000-02-29 2004-09-30 Jardine Peter A. Shape memory device having two-way cyclical shape memory effect due to compositional gradient and method of manufacture
US6878782B2 (en) * 1999-12-01 2005-04-12 General Electric Thermoset composition, method, and article
US20050088272A1 (en) * 2003-10-28 2005-04-28 Nec Schott Components Corporation Thermal pellet incorporated thermal fuse and method of producing thermal pellet
US6922131B2 (en) * 2000-01-11 2005-07-26 Tyco Electronics Corporation Electrical device
US20050179516A1 (en) * 2002-04-24 2005-08-18 Tokihiro Yoshikawa Temperature sensing material type thermal use
US6981319B2 (en) * 2003-02-13 2006-01-03 Shrier Karen P Method of manufacturing devices to protect election components
US20060208845A1 (en) * 2005-03-17 2006-09-21 Nec Schott Components Corporation Thermal fuse employing thermosensitive pellet
US7205035B2 (en) * 2002-04-09 2007-04-17 General Electric Company Thermoset composition, method, and article
US7235192B2 (en) * 1999-12-01 2007-06-26 General Electric Company Capped poly(arylene ether) composition and method
US7250477B2 (en) * 2002-12-20 2007-07-31 General Electric Company Thermoset composite composition, method, and article
US7362208B2 (en) * 2004-09-17 2008-04-22 Nec Schott Components Corporation Thermal pellet type thermal fuse
US7532101B2 (en) * 2002-04-25 2009-05-12 Tyco Electronics Raychem K.K. Temperature protection device
US7785732B2 (en) * 2005-05-03 2010-08-31 Samsung Sdi Co., Ltd. Lithium rechargeable battery having functional center pin

Family Cites Families (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE186526C (en) 1904-02-22
US3781737A (en) 1973-02-20 1973-12-25 Essex International Inc Thermal circuit protector
US3924218A (en) * 1974-05-22 1975-12-02 Micro Devices Corp Thermal limiter construction
DE2431409C2 (en) 1974-06-29 1982-10-21 Bayer Ag, 5090 Leverkusen Process for the preparation of 1-aminoanthraquinone
US3930215A (en) * 1974-11-29 1975-12-30 Texas Instruments Inc Nonresettable thermally actuated switch
US4197634A (en) * 1976-08-23 1980-04-15 Emerson Electric Co. Method of making a thermally actuatable electrical switch construction
US4065741A (en) 1977-03-29 1977-12-27 New Nippon Electric Co., Ltd. Thermal fuse with a fusible temperature sensitive pellet
JPS58150545A (en) 1982-03-03 1983-09-07 Sumitomo Chem Co Ltd Purification method of 1-aminoanthraquinone
US4786438A (en) 1983-03-08 1988-11-22 Georgia-Pacific Corporation Lignosulfonate/urea binder for particulate composites
DE3422528A1 (en) 1984-06-16 1985-12-19 Philips Patentverwaltung Gmbh, 2000 Hamburg ELECTRICAL MELTFUSE
US4878038A (en) 1987-12-07 1989-10-31 Tsai James T Circuit protection device
JP2710160B2 (en) 1988-06-08 1998-02-10 王子製紙株式会社 Thermal recording medium
US4881055A (en) 1988-11-10 1989-11-14 Ingersoll-Rand Company High-temperature-fluid sensor
JP2733076B2 (en) 1988-11-28 1998-03-30 大東通信機株式会社 PTC composition
JPH0814372B2 (en) 1989-12-28 1996-02-14 信越ポリマー株式会社 Electric cigarette lighter
US4968962A (en) 1990-01-12 1990-11-06 Therm-O-Disc, Incorporated Thermal cutoff and resistor assembly
US5153553A (en) 1991-11-08 1992-10-06 Illinois Tool Works, Inc. Fuse structure
US5473303A (en) 1994-05-31 1995-12-05 Therm-O-Disc, Incorporated Electrical lead
US5816493A (en) 1996-04-08 1998-10-06 Texan Corporation Thermally expansible compositions methods for preparation and devices using same
US6133547A (en) 1996-09-05 2000-10-17 Medtronic, Inc. Distributed activator for a two-dimensional shape memory alloy
US5825277A (en) 1996-09-27 1998-10-20 Therm-O-Disc, Incorporated Thermal pellet cutoff switch
US5837164A (en) 1996-10-08 1998-11-17 Therm-O-Disc, Incorporated High temperature PTC device comprising a conductive polymer composition
US5985182A (en) 1996-10-08 1999-11-16 Therm-O-Disc, Incorporated High temperature PTC device and conductive polymer composition
JP3272252B2 (en) * 1996-12-18 2002-04-08 秀夫 伊藤 Thermal fuse
FR2761204B1 (en) 1997-03-24 1999-05-14 Siemens Automotive Sa DEVICE FOR DISTRIBUTING ELECTRICAL ENERGY IN MULTIPLE PARALLEL-POWERED CIRCUITS, AND METHOD FOR MANUFACTURING THE DEVICE
US5993698A (en) 1997-11-06 1999-11-30 Acheson Industries, Inc. Electrical device containing positive temperature coefficient resistor composition and method of manufacturing the device
US6150051A (en) 1998-02-27 2000-11-21 Telcordia Technologies, Inc. Thermal switch for use in plastic batteries
FR2779582B1 (en) 1998-06-04 2000-07-13 Alsthom Cge Alcatel INTEGRATED CUT LINE PROTECTION DEVICE
US5963121A (en) 1998-11-11 1999-10-05 Ferro Corporation Resettable fuse
CN2385431Y (en) * 1999-07-15 2000-06-28 中山市升平热保护器实业公司 Heat fuse
US6300859B1 (en) 1999-08-24 2001-10-09 Tyco Electronics Corporation Circuit protection devices
US6812276B2 (en) 1999-12-01 2004-11-02 General Electric Company Poly(arylene ether)-containing thermoset composition, method for the preparation thereof, and articles derived therefrom
US6489879B1 (en) 1999-12-10 2002-12-03 National Semiconductor Corporation PTC fuse including external heat source
US6896554B2 (en) 2000-10-13 2005-05-24 Lasko Holdings, Inc. Safety device for electrical apparatus or appliances
US20020196592A1 (en) 2001-06-20 2002-12-26 Chen William W. Positive temperature coefficient resistivity protected power transformer
WO2003005118A1 (en) * 2001-07-02 2003-01-16 Loctite Corporation Epoxy-based composition
CN100367432C (en) 2002-09-10 2008-02-06 株式会社克拉比 Code-shaped temperature fuse and sheet-shaped temperature fuse
DE102004013525B4 (en) * 2003-04-10 2006-02-02 Forschungszentrum Karlsruhe Gmbh Light-conducting material and optical fibers
US7154369B2 (en) 2004-06-10 2006-12-26 Raytheon Company Passive thermal switch
JP4583228B2 (en) 2005-04-18 2010-11-17 エヌイーシー ショット コンポーネンツ株式会社 Thermal pellet type thermal fuse
CN101321799B (en) * 2005-12-08 2011-06-15 日立化成工业株式会社 Liquid resin composition for electronic element and electronic element device
US20080006795A1 (en) 2006-07-10 2008-01-10 General Electric Company Article and associated device
US20100033295A1 (en) 2008-08-05 2010-02-11 Therm-O-Disc, Incorporated High temperature thermal cutoff device
CN103515041B (en) * 2012-06-15 2018-11-27 热敏碟公司 High thermal stability pellet composition and its preparation method and application for hot stopper

Patent Citations (100)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3281559A (en) * 1964-05-21 1966-10-25 United Carr Inc Thermal fuse having telescopically received contact members
US3519972A (en) * 1969-03-18 1970-07-07 Micro Devices Corp Temperature responsive electric switch
US3571777A (en) * 1969-07-07 1971-03-23 Cabot Corp Thermally responsive current regulating devices
US3711428A (en) * 1971-02-01 1973-01-16 Ibm Electrical resistor paste containing a small amount of charcoal
US3692921A (en) * 1971-04-12 1972-09-19 Joslyn Mfg & Supply Co Cable coupler
US3727164A (en) * 1972-07-14 1973-04-10 Minnesota Mining & Mfg Temperature-responsive electrical switch
US3745507A (en) * 1972-08-18 1973-07-10 Matsushita Electric Ind Co Ltd Nonflammable composition resistor
US3793716A (en) * 1972-09-08 1974-02-26 Raychem Corp Method of making self limiting heat elements
US4023072A (en) * 1973-01-08 1977-05-10 Emerson Electric Co. Electrical protection means and method
US3974105A (en) * 1973-05-30 1976-08-10 Matsushita Electric Industrial Co., Ltd. Overtemperature and overcurrent resistor fuse
US3883837A (en) * 1973-11-05 1975-05-13 Robertshaw Controls Co Thermal responsive switch
US3898602A (en) * 1974-01-25 1975-08-05 Itt Enclosed, non-vented expulsion fuse
US4001754A (en) * 1974-05-21 1977-01-04 Emerson Electric Co. Temperature responsive electrical switch construction and method of making the same
US4075595A (en) * 1974-05-21 1978-02-21 Emerson Electric Co. Temperature responsive electrical switch construction and method of making the same
US3951582A (en) * 1974-05-24 1976-04-20 General Electric Company Switching devices for photoflash unit
US4006443A (en) * 1975-09-11 1977-02-01 Allen-Bradley Company Composition resistor with an integral thermal fuse
US4031497A (en) * 1975-09-23 1977-06-21 Juichiro Ozawa Fusible resistor
US4068204A (en) * 1975-12-26 1978-01-10 New Nippon Electric Company, Ltd. Thermal fuse employing a slidable resilient contact member in a conductive housing
US4075596A (en) * 1976-08-23 1978-02-21 Emerson Electric Co. Sealed casing for a thermally actuable electrical switch
US4142418A (en) * 1977-04-05 1979-03-06 Gunnar Lagher Temperature sensitive member
US4084147A (en) * 1977-05-31 1978-04-11 Emerson Electric Co. Normally open, thermal sensitive electrical switching device
US4184139A (en) * 1977-08-29 1980-01-15 Illinois Tool Works Inc. Thermal cut-off fuse
US4189697A (en) * 1977-09-09 1980-02-19 Nifco Inc. Thermal cut-off fuse
US4281309A (en) * 1978-03-28 1981-07-28 Olson Harry W Thermally actuated cut-off link or switch and method of making the same
US4276532A (en) * 1978-07-08 1981-06-30 Murata Manufacturing Co., Ltd. Thermal fuse
US4186366A (en) * 1978-10-20 1980-01-29 Illinois Tool Works Inc. Radial lead thermal cut-off device
US4310469A (en) * 1978-12-29 1982-01-12 General Electric Company Diaryliodonium salts
US4249154A (en) * 1979-02-12 1981-02-03 Emerson Electric Co. Temperature responsive electrical switching device and method of calibrating
US4276531A (en) * 1979-04-20 1981-06-30 Davis Merwyn C Nonresetable thermally actuated switch
US4259656A (en) * 1979-05-11 1981-03-31 Illinois Tool Works Inc. Thermal cut-off device with an activating spring that is held in a prestressed condition by a thermally fusible pellet
US4344061A (en) * 1979-09-11 1982-08-10 Showa Electric Wire & Cable Co., Ltd. Temperature-sensitive fuse
US4322705A (en) * 1979-09-26 1982-03-30 Nifco Inc. Thermal cutout fuse
US4281308A (en) * 1979-12-26 1981-07-28 Illinois Tool Works Inc. Thermal switch with split ring construction
US4384267A (en) * 1980-07-07 1983-05-17 Murata Manufacturing Co., Ltd. Thermosensitive fuse
US4480247A (en) * 1981-10-06 1984-10-30 Nifco Inc. Thermal cutout fuse
US4529957A (en) * 1981-10-06 1985-07-16 Nifco Inc. Thermal cutout fuse
US4373556A (en) * 1981-12-02 1983-02-15 Canadian General Electric Company Limited Cut-out fuse tube
US4873604A (en) * 1983-04-21 1989-10-10 Hoechst Celanese Corp. Fuses having suppressed voltage transients
US4514718A (en) * 1983-12-02 1985-04-30 Emerson Electric Co. Thermal cutoff construction, member therefor and methods of making the same
US4763099A (en) * 1985-12-04 1988-08-09 Thorn Emi Plc Temperature sensitive device
US4763099B1 (en) * 1985-12-04 1991-08-27 Emi Plc Thorn
US5106540A (en) * 1986-01-14 1992-04-21 Raychem Corporation Conductive polymer composition
US4757423A (en) * 1986-02-15 1988-07-12 Stc Plc Fuse for electronic component
US4675641A (en) * 1986-06-20 1987-06-23 General Electric Company Rating plug for molded case circuit breakers
US5027101A (en) * 1987-01-22 1991-06-25 Morrill Jr Vaughan Sub-miniature fuse
US5106538A (en) * 1987-07-21 1992-04-21 Raychem Corporation Conductive polymer composition
US5015514A (en) * 1987-08-18 1991-05-14 A. B. Chance Company Pultruded or filament wound synthetic resin fuse tube
US4808965A (en) * 1987-11-06 1989-02-28 Therm-O-Disc, Incorporated Thermal protector
US4763228A (en) * 1987-11-20 1988-08-09 Union Carbide Corporation Fuse assembly for solid electrolytic capacitor
US4841273A (en) * 1987-12-18 1989-06-20 Therm-O-Disc, Incorporated High temperature sensing apparatus
US4821010A (en) * 1987-12-30 1989-04-11 Therm-O-Disc, Incorporated Thermal cutoff heater
US4873506A (en) * 1988-03-09 1989-10-10 Cooper Industries, Inc. Metallo-organic film fractional ampere fuses and method of making
US4933658A (en) * 1989-05-10 1990-06-12 Ingersoll-Rand Company High temperature fluid sensor
US5003283A (en) * 1990-01-22 1991-03-26 Therm-O-Disc, Incorporated Thermal cutoff with lead indicia
US5212261A (en) * 1990-12-17 1993-05-18 Henkel Research Corporation Latent, heat-curable epoxy resin compositions containing metal carboxylate curing systems
US5601924A (en) * 1991-07-17 1997-02-11 Materials Innovation Inc. Manufacturing particles and articles having engineered properties
US5215636A (en) * 1991-09-27 1993-06-01 American International Technologies, Inc. Pulsed discharge surface treatment apparatus and process
US5545679A (en) * 1993-11-29 1996-08-13 Eaton Corporation Positive temperature coefficient conductive polymer made from thermosetting polyester resin and conductive fillers
US6375867B1 (en) * 1993-11-29 2002-04-23 Eaton Corporation Process for making a positive temperature coefficient conductive polymer from a thermosetting epoxy resin and conductive fillers
US5530417A (en) * 1994-06-06 1996-06-25 Therm-O-Disc, Incorporated Thermal cutoff with floating contact member
US5712610C1 (en) * 1994-08-19 2002-06-25 Sony Chemicals Corp Protective device
US5712610A (en) * 1994-08-19 1998-01-27 Sony Chemicals Corp. Protective device
US5929741A (en) * 1994-11-30 1999-07-27 Hitachi Chemical Company, Ltd. Current protector
US5663702A (en) * 1995-06-07 1997-09-02 Littelfuse, Inc. PTC electrical device having fuse link in series and metallized ceramic electrodes
US6059997A (en) * 1995-09-29 2000-05-09 Littlelfuse, Inc. Polymeric PTC compositions
US5777540A (en) * 1996-01-29 1998-07-07 Cts Corporation Encapsulated fuse having a conductive polymer and non-cured deoxidant
US5772949A (en) * 1996-02-23 1998-06-30 Hoechst Celanese Corp. Thermally expandable, viscosity modified wax compositions and method of use in actuators
US5750277A (en) * 1996-04-10 1998-05-12 Texas Instruments Incorporated Current interrupter for electrochemical cells
US5808538A (en) * 1996-06-19 1998-09-15 Littelfuse, Inc. Electrical apparatus for overcurrent protection of electrical circuits
US5939968A (en) * 1996-06-19 1999-08-17 Littelfuse, Inc. Electrical apparatus for overcurrent protection of electrical circuits
US5856773A (en) * 1996-11-04 1999-01-05 Raychem Corporation Circuit protection device
US5914649A (en) * 1997-03-28 1999-06-22 Hitachi Chemical Company, Ltd. Chip fuse and process for production thereof
US6452138B1 (en) * 1998-09-25 2002-09-17 Thermosoft International Corporation Multi-conductor soft heating element
US6282074B1 (en) * 1999-01-28 2001-08-28 X2Y Attenuators, L.L.C. Polymer fuse and filter apparatus
US6388856B1 (en) * 1999-01-28 2002-05-14 X2Y Attenuators, Llc Polymer fuse and filter apparatus
US6563094B2 (en) * 1999-05-11 2003-05-13 Thermosoft International Corporation Soft electrical heater with continuous temperature sensing
US6403935B2 (en) * 1999-05-11 2002-06-11 Thermosoft International Corporation Soft heating element and method of its electrical termination
US6713733B2 (en) * 1999-05-11 2004-03-30 Thermosoft International Corporation Textile heater with continuous temperature sensing and hot spot detection
US6878782B2 (en) * 1999-12-01 2005-04-12 General Electric Thermoset composition, method, and article
US7235192B2 (en) * 1999-12-01 2007-06-26 General Electric Company Capped poly(arylene ether) composition and method
US6515570B2 (en) * 1999-12-08 2003-02-04 Abb Research Ltd Fuse with overstoichiometric amount of oxidant
US6922131B2 (en) * 2000-01-11 2005-07-26 Tyco Electronics Corporation Electrical device
US20040191556A1 (en) * 2000-02-29 2004-09-30 Jardine Peter A. Shape memory device having two-way cyclical shape memory effect due to compositional gradient and method of manufacture
US6388553B1 (en) * 2000-03-02 2002-05-14 Eaton Corproation Conductive polymer current-limiting fuse
US6673257B1 (en) * 2000-09-12 2004-01-06 Therm-O-Disc, Incorporated Thermal cutoff construction compositions
US6359544B1 (en) * 2000-10-10 2002-03-19 Therm-O-Disc Incorporated Conductive polymer compositions containing surface treated kaolin clay and devices
US6396384B1 (en) * 2000-10-10 2002-05-28 Therm-O-Disc, Incorporated Conductive polymer compositions containing perhydrotriphenylene
US20030112117A1 (en) * 2001-07-18 2003-06-19 Ikuhiro Miyashita Thermal fuse
US20040070484A1 (en) * 2001-10-29 2004-04-15 Krause John A. Arrester housing support bracket
US7205035B2 (en) * 2002-04-09 2007-04-17 General Electric Company Thermoset composition, method, and article
US20050179516A1 (en) * 2002-04-24 2005-08-18 Tokihiro Yoshikawa Temperature sensing material type thermal use
US7532101B2 (en) * 2002-04-25 2009-05-12 Tyco Electronics Raychem K.K. Temperature protection device
US7250477B2 (en) * 2002-12-20 2007-07-31 General Electric Company Thermoset composite composition, method, and article
US6981319B2 (en) * 2003-02-13 2006-01-03 Shrier Karen P Method of manufacturing devices to protect election components
US20050088272A1 (en) * 2003-10-28 2005-04-28 Nec Schott Components Corporation Thermal pellet incorporated thermal fuse and method of producing thermal pellet
US7323966B2 (en) * 2003-10-28 2008-01-29 Nec Schott Components Corporation Thermal pellet incorporated thermal fuse and method of producing thermal pellet
US7362208B2 (en) * 2004-09-17 2008-04-22 Nec Schott Components Corporation Thermal pellet type thermal fuse
US20060208845A1 (en) * 2005-03-17 2006-09-21 Nec Schott Components Corporation Thermal fuse employing thermosensitive pellet
US7330098B2 (en) * 2005-03-17 2008-02-12 Nec Schott Components Corporation Thermal fuse employing a thermosensitive pellet
US7785732B2 (en) * 2005-05-03 2010-08-31 Samsung Sdi Co., Ltd. Lithium rechargeable battery having functional center pin

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8961832B2 (en) 2008-08-05 2015-02-24 Therm-O-Disc, Incorporated High temperature material compositions for high temperature thermal cutoff devices
US9779901B2 (en) 2008-08-05 2017-10-03 Therm-O-Disc, Incorporated High temperature material compositions for high temperature thermal cutoff devices
US20120182116A1 (en) * 2009-07-15 2012-07-19 Vishay Resistors Belgium Bvba Thermal switch
US9058949B2 (en) * 2009-07-15 2015-06-16 Vishay Resistors Belgium Bvba Thermal switch
US20120194317A1 (en) * 2011-02-02 2012-08-02 Anthony Vranicar Three-Function Reflowable Circuit Protection Device
US9455106B2 (en) 2011-02-02 2016-09-27 Littelfuse, Inc. Three-function reflowable circuit protection device
US8941461B2 (en) * 2011-02-02 2015-01-27 Tyco Electronics Corporation Three-function reflowable circuit protection device
US20130200984A1 (en) * 2011-08-12 2013-08-08 Tyco Electronics Corporation Reflowable Circuit Protection Device
US9620318B2 (en) * 2011-08-12 2017-04-11 Littlefuse, Inc. Reflowable circuit protection device
US10566600B2 (en) 2011-10-31 2020-02-18 Powermag, LLC Power conditioning and saving device
US9825316B2 (en) 2012-03-23 2017-11-21 Intelligent Energy Limited Hydrogen producing fuel cartridge and methods for producing hydrogen
US20150044131A1 (en) * 2012-03-23 2015-02-12 Intelligent Energy Inc. Hydrogen producing fuel cartridge and methods for producing hydrogen
US9276278B2 (en) 2012-03-23 2016-03-01 Intelligent Energy Limited Hydrogen producing fuel cartridge
US9266728B2 (en) * 2012-03-23 2016-02-23 Intelligent Energy Limited Hydrogen producing fuel cartridge and methods for producing hydrogen
KR20130141393A (en) * 2012-06-15 2013-12-26 써엄-오-디스크 인코포레이티드 High thermal stability pellet compositions for thermal cutoff devices and methods for making and use thereof
US9171654B2 (en) * 2012-06-15 2015-10-27 Therm-O-Disc, Incorporated High thermal stability pellet compositions for thermal cutoff devices and methods for making and use thereof
KR102024388B1 (en) 2012-06-15 2019-09-23 써엄-오-디스크 인코포레이티드 High thermal stability pellet compositions for thermal cutoff devices and methods for making and use thereof
US20130334471A1 (en) * 2012-06-15 2013-12-19 Therm-O-Disc, Incorporated High thermal stability pellet compositions for thermal cutoff devices and methods for making and use thereof
EP2674956A1 (en) 2012-06-15 2013-12-18 Therm-O-Disc Incorporated High thermal stability pellet compositions for thermal cutoff devices and methods for making and use thereof
US9431203B2 (en) * 2012-08-06 2016-08-30 Littelfuse, Inc. Reflowable circuit protection device
US20140035716A1 (en) * 2012-08-06 2014-02-06 Shelomon Patrick Doblack Reflowable Circuit Protection Device
WO2014099839A3 (en) * 2012-12-18 2014-08-14 Powermag, LLC Power conditioning and saving device
US10276318B1 (en) * 2013-03-15 2019-04-30 Innovative Switchgear IP, LLC Insulated switch
US10290437B1 (en) 2013-03-15 2019-05-14 Innovative Switchgear IP, LLC Interrupter spring guide assembly
US10290436B1 (en) 2013-03-15 2019-05-14 Innovative Switchgear IP, LLC Insulated interrupter
US10978256B1 (en) 2013-03-15 2021-04-13 Innovative Switchgear IP, LLC Electrical switching device
US20180266725A1 (en) * 2015-06-24 2018-09-20 Bleckmann Gmbh & Co. Kg Terminal device for a tubular heating device with integrated fuse
KR20180021061A (en) * 2015-06-24 2018-02-28 블랙만 게엠베하 코. 카게 Terminal devices for tubular heating devices with integrated fuses
US11204186B2 (en) * 2015-06-24 2021-12-21 Bleckmann Gmbh & Co. Kg Terminal device for a tubular heating device with integrated fuse
KR102521458B1 (en) * 2015-06-24 2023-04-13 블랙만 게엠베하 코. 카게 Terminal devices for tubular heaters with integral fuses
US9742182B1 (en) * 2016-08-04 2017-08-22 International Business Machines Corporation Acclimation sensing and control of electronic equipment

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