US 20140327513A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0327513 A1 Yang et al. (43) Pub. Date: Nov. 6, 2014

(54) MACROMOLECULE-BASED CONDUCTIVE Publication Classification COMPOSITE MATERAL AND PTC ELEMENT (51) Int. Cl. CSK 3/38 (2006.01) HOIC 7700 (2006.01) (71) Applicant: Shanghai Changyuan Wayon Circuit C08K 3/4 (2006.01) Protection Co., Ltd., Shanghai (CN) (52) U.S. Cl. CPC. C08K 3/38 (2013.01); C08K 3/14 (2013.01); (72) Inventors: Quanquan Yang, Shanghai (CN); HOIC 77008 (2013.01) Zhengping Liu, Shanghai (CN); Yong USPC ...... 338/22 R; 252/519.21 Fang, Shanghai (CN); Yutang Liu, Shanghai (CN): Lifeng Liu, Shanghai (57) ABSTRACT (CN); Wei Wang, Shanghai (CN); A macromolecule-based conductive composite material and Daohua Gao, Shanghai (CN); Xuan a PTC element. The macromolecule-based conductive com Gong, Shanghai (CN); Jun Wang, posite material comprises: a macromolecule base material, Shanghai (CN) having a Volume fraction of the macromolecule base material of 20%-75%; a conductive filler with a core-shell granule structure and dispersed in the macromolecule base material, (21) Appl. No.: 14/369,919 having a Volume fraction of 25%-80%; and a coupling agent, being a titanate coupling agent and accounting for 0%-5% of (22) PCT Fled: Dec. 24, 2012 the volume of the conductive filler. The PTC element pre pared by using the macromolecule-based conductive com (86) PCT NO.: PCT/CN2O12/087264 posite material comprises at least two metal electrode plates (12, 12"), a macromolecule-based conductive composite S371 (c)(1), material (11) being closely combined with the metal elec (2), (4) Date: Jun. 30, 2014 trode plates (12, 12). The PTC element prepared from the macromolecule-based conductive composite material has the (30) Foreign Application Priority Data advantages of low room-temperature resistivity, outstanding Weather durability, good Voltage resistance and good resistor Dec. 31, 2011 (CN) ...... 2011 104588OO.4 repeatability.

Patent Application Publication Nov. 6, 2014 US 2014/0327513 A1

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MACROMOLECULE-BASED CONDUCTIVE 0006. The invention also needs to solve another technical COMPOSITE MATERAL AND PTC problem that is offering the PTC components that are pro ELEMENT duced by the Macromolecule Based Conductive Composite Material mentioned above. This kind of PTC components TECHNOLOGY FIELD needs to have low room-temperature resistivity, outstanding 0001. The invention refers to a kind of Macromolecule weather durability, good Voltage resistance and resistor Based Conductive Composite Material and the PTC compo repeatability. nents be made from it, which with low room-temperature 0007. The mentioned technical problem can be solved resistivity, outstanding weather durability, good Voltage resis through the below technical scheme: a kind of Macromol tance and resistor repeatability. ecule Based Conductive Composite Material includes Mac romolecule Based Material, conductive filler and coupling TECHNOLOGY BACKGROUND agent. Among it: 0002 Macromolecule Based Conductive Composite 0008 (a) The mentioned Macromolecule Based Materials Material is sensitive to the change of temperature, and can are one kind of and the mixture of polythene, polypropylene, keep a low resistance at normal temperature, which means the PVDF, Polyolefin elastomer, epoxy resin, ethylene-vinyl resistance can rise to a very high point to break the circuit acetate copolymer, polymethylmethacrylate and ethylene when over current or over Voltage happens So that the elec acrylic acid copolymer. It accounts for 20%-75% of volume tronic components can be protected. Thus the Macromolecule fraction in the Macromolecule Based Conductive Composite Based Conductive Composite Material can be connected to Material. As to the percentage, 25%-70% is preferred, the circuit as the current sensor material. This kind of material 30%-65% is better; has been widely used in the circuit protection components. 0009 (b) Conductive filler with particles structure of core 0003 Macromolecule Based Conductive Composite shell type, which accounts for 25%-80% of volume fraction Material generally is the composition of polymer and con of the Macromolecule Based Conductive Composite Mate ductive filler. Conductive filler is macro evenly distributed in rial. Its particle diameter is 0.1 um-20 um, but 0.05 um-50 the mentioned Macromolecule Based Materials. Polymer um is preferred, 0.1-20um is better. What's more, the volume generally is polyolefin and its copolymer likes polythene or resistivity is under 0.03 S.2m, but 0.02 C2m is preferred, 0.01 copolymer of ethylene and vinyl acetate, but conductive filler S.2m is better. The mentioned conductive filler is distributed in is usually black, metal powder or conducting ceramic the Macromolecule Based Materials; powder. Regarding the carbon black as conductive filler, (0010) (c) Coupling agent accounts for 0.05%-5% of the because its special structure of aggregates and the polar volume of conductive filler. As to the percentage, 0.1%-5% is group on the Surface can make a good adhesive properties, so preferred, 0.5%-3% is better. The mentioned coupling agent the kind of composite material has a good stability in resis is titanate, its structural formula as below: tance. But carbon black with a limited conductive ability, so it cannot meet the requirement of low resistance. Regarding the (RO), Ti-(OX—R Y), Macromolecule Based Conductive Composite Material with I0011. In the structural formula, R group is one of ethyl, conductive filler of mental power, it has a low resistance, but propyl, butyl, amyl or their isomeride; X group is one of the mental powder is easy to oxidize, so the conductive com carboxyl, Sulfo, Sulfuryl, phosphate based, phosphite based; posite material needs to be packed to protect from the increas R2 group is one of hexyl, heptyl, octyl or their isomeride; Y ing of resistance during the oxidation. However, the size of group is one of acyloxy and amidogen; n is functionality of packed PTC components can’t meet the demand of miniatur titanate. During the formula, 1sms4, 1sns3, mand in both are ization. For reaching a low resistance and overcoming the integer. The mentioned coupling agent is the mixture of one or defaults of oxidation, in the industry, metal carbide, metal Some of titanate coupling agent of mono-alkoxy type, mono nitride, metal silicate or metal boride ceramic powder (such alkoxy pyrophosphate type, chelate type, coordination type as titanium carbide) are tend to be used as the conductive filler and quaternary ammonium salt type. of low resistance Macromolecule Based Conductive Com posite Material, what’s more, this kind of materials have been 0012 Concretely, the structures of coupling agent can be great developed. But the proportion of metal carbide, metal divided into 6 different functional areas: nitride, metal silicate or metal boride ceramic powder is rela 0013 III III IV V VI tively big in the Macromolecule Based Conductive Compos (RO), Ti-(OX—R Y), ite Material, so the hard processing and poor distribution in polymer led to the resistance can’t be further reduced. 0014 Functional area I is for coupling inorganic matter 0004 Besides, the thickness of PTC components are made and titanium; functional area II is for transesterification and by metal carbide, metal nitride, metal silicate or metal boride crosslinking; functional area III is for connecting the group ceramic powder is limited (like below 1.0 mm, 0.8 mm, 0.6 that in the center of titanium; functional area IV is the long mm etc.), and the requirements of electrical conductivity chain entanglement group of thermoplastic polymer, func can't be met when size be smaller (like 1210,1206,0805,0603 tional area V is the reactive group of thermosetting polymer; etc.). Thus developing the conductive filler with lower resis functional area VI is the functionality of titanate. tivity and better oxidation resistibility is necessary. 0015 The Macromolecule Based Conductive Composite Materials can contain other components, such as antioxygen, CONTENTS OF INVENTION radiation crosslinking agent (often called radiation promoter, 0005. The invention aims to solve a technical problem that crosslinking agent or cross linking promoter, like TAIC), is offering a Macromolecule Based Conductive Composite coupling agent, dispersing agent, stabilizer, non-conductive Material with good conductivity and dispersion of process filler (like magnesium hydroxide, calcium carbonate), com ing. bustion improver, arc inhibitor, etc. Those components gen US 2014/0327513 A1 Nov. 6, 2014

erally account for 15% of the volume in the Macromolecule hafnium disilicide, tungsten disilicide, trichromium silicide Based Conductive Composite Material, like 5% of the vol (Cr-Si) or chromium disilicide. le. 0028. The described Macromolecule Based Conductive 0016 Base on the scheme described above, the mentioned Composite Material can contain other promoter, Such as anti particles structure of core-shell type consists of core, shell oxidant, radiation cross-linking agent (usually be called irra and interlayer: diation accelerator, cross-linking agent or cross-linking 0017. The core consists of one of tantalum, zirconium, accelerator, like Triallyl isocyanurate), coupling agent, dis titanium, , molybdenum, hafnium, tungsten, chro persant, stabilizer, non-conductivity filler (like magnesium mium or beryllium; the shell is made up of one of boride, hydroxide and calcium carbonate), flame retardant, arc light nitride or silicide of core matter; the interlayer consists of one inhibitor or other compositions. Those compositions are gen of boride, nitride or silicide of core matter. The molecular erally less than 15% of the volume in Macromolecule Based structure is different between the boride, nitride or silicide Conductive Composite Material, such as 10% of the volume. that makes up interlayer and the one that makes up shell. 0029. The invention also will show the PTC components 0.018. The invention also offers a kind of Macromolecule that produced by the Macromolecule Based Conductive Based Conductive Composite Material, which include: Composite Material that mentioned above. The Macromol 0.019 Macromolecule Based Material that is one kind of ecule Based Conductive Composite Material plates are com or the mixture of polythene, polypropylene, PVDF, Polyole pounded tightly with the two metal electrode slices to form finelastomer, epoxy resin, ethylene-vinyl acetate copolymer, the polymer conductive composite material sheets. The metal polymethylmethacrylate and ethylene-acrylic acid copoly electrode slices include one of nickel, copper, aluminum or mer. Among them, polythenes include High-density polyeth Zinc and their compounds, such as copper foil, nickel foil, ylene, low-density polyethylene, linear low density polyeth nickel and copper single plated foil, nickel and copper double ylene and ultrahigh molecular weight polyethylene, etc., plated foil. The thickness of Macromolecule Based Conduc which accounts for 20%-75% of the volume in the Macro tive Composite Material plate is 0.01-3.0 mm, 0.05-2.0 mm molecule Based Conductive Composite Material. As to the is preferred. What's more, for processing easier, the plate is percentage, 25%-70% is preferred, 30%-65% is better. cut into single component with plane shape. The mentioned 0020 Regarding the diameter of conductive filler with single component has two Surfaces perpendicularing to the particles structure of core-shell type, 0.05um-50 um is pre direction of electric. The thickness of metal electrode slices is ferred, 0.1 um-20 um is better; the volume resistivity is under less than 0.3 mm, less than 0.2 mm is preferred, less than 0.1 0.03 S.2m, but 0.02 .2m is preferred, 0.01 S.2m is better. The mm is better, likes 0.035 mm. mentioned conductive filler with particle structure of core 0030. At the temperature of 25°C., the PTC component is shell type consists of core, shell and interlayer, which with a volume resistivity lower than 0.1 S2 cm, lower than accounts for 25%-80% of volume in the Macromolecule 0.05 G.2-cm is preferred, lower than 0.02 C2 cm is better, and it Based Conductive Composite Material, but 30%-75% is pre is also with outstanding weather durability, good Voltage ferred, 35%-70% is better. The conductive filler distributed in resistance, resistor repeatability and PTC strength. So, the the Macromolecule Based Material, among it: PTC components produced with the composite material can 0021. The core consists of one of tantalum, zirconium, get a very low resistance at the temperature of 25°C. Such as titanium, niobium, molybdenum, hafnium, tungsten, chro 1.0 mS2-10 mS2. mium or beryllium; 0031. The single component mentioned above is laminate 0022. The shell is made up of one of boride, nitride or structure of square, triangle, round, rectangle, annulus, poly silicide of core matter; gon or other irregular shape. 0023 The interlayer consists of one of boride, nitride or silicide of core matter. The molecular structure is different 0032. The steps of producing the PTC components by the between the boride, nitride or silicide that makes up interlayer mentioned Macromolecule Based Conductive Composite and the one that makes up shell. Material are as below: 0024. According to the scheme, the boride is one of tan 0033 1) Putting the polymer material, conductive filler talum boride, tantalum diboride, Vanadium boride, Vanadium and additive (if have) into the mixing equipment like torque diboride, , , niobium rheometer, internal mixer, open mill, single-screw extruder or boride, niobium diboride, molybdenum boride (MoB), double-screw extruder, stc. to mix and melt under the tem molybdenum pentaboride((MoBs), , tung perature that above polymer melting temperature. Then, sten boride, ditungsten boride, chromium boride, dichro through extrusion molding, compression molding or calen mium boride(CrB), chromium diboride or chromium tri daring, the mixed polymer will be processed into Macromol boride(CrsB). ecule Based Conductive Composite Material sheet with 0025. The mentioned nitride is one of tantalum nitride, thickness 0.01-3.0 mm, thickness 0.05-2.0 mm is preferred, Vanadium nitride, Zirconium nitride, titanium nitride, nio 0.1-1.0 mm is better for processing easier; bium nitride or hafnium nitride. 0034 2) Compounding metal electrode slice on the two 0026. The mentioned carbide is one of tantalum carbide, sides of polymer conductive composite material sheet. The Vanadium carbide, Zirconium carbide, titanium carbide, nio way is to tightly press the electrode slice on the two sides of bium carbide, molybdenum carbide(MoC), hafnium car sheet by roller when the Macromolecule Based Conductive bide, tungsten monocarbide, ditungsten carbide or trichro Composite Material sheet still in melting. The composite mium dicarbide(CrCl). sheet can be processed into the surface mounted PTC devices 0027. The mentioned silicide is one of tantalum disilicide, by etching, laminating, drilling, copper deposition, tin plat tantalum silicide (TasSis), trivanadium silicide, Vanadium ing, scribing and other series of PTC processing way. It also disilicide, Zirconium disilicide, titanium disilicae, titanium can be cut into single components and then connect it with silicide(TiSi.), niobium disilicide, molybdenum disilicide, other metal parts to process into strips of PTC components; US 2014/0327513 A1 Nov. 6, 2014

0035. 3) The way of cutting composite sheet into single NO. EXPLANATION IN THE DRAWING components including any method that can isolate single components from composite products, such as punching, 0044) 11—Macromolecule Based Conductive Composite etching, scribing and laser cutting. The mentioned single Materials; component with plane shape means that it has two Surfaces 0045 12, 12 metal electrode slices: that perpendicular to the direction of current. What's more the 0046) 13, 13 metal conductive components. distance between two surfaces is very close, its at most 3.0 mm, if at most 2.0 mm will be preferred, at most 1.0 mm will Concrete Implementing Ways be better, such as 0.4 mm. 0047 Implementation No. 1-6 is the material mentioned 0036, 4) The way of cross linking and heat treating to the in the invention with coupling agent mentioned PTC components can improve its stability. Cross linking can be chemical cross linking or radiation cross Implementation No. 1 linking, for example, it can be realized with cross-linking promoter and the way of electron beam irradiation or Co60 0048. The conductive composite materials for producing radiation. The needed radiation dosages of PTC components PTC parts include: are generally under 100Mrad, and 1-50Mrad is preferred, 0049 (a) Macromolecule Based Material is High-density 1-20Mrad is better; heat treating can be annealing, heat cycle polyethylene, and the melting temperature is 134°C., density or high-low temperature cycle. Such as the high-low tempera is 0.953 g/cm, volume fraction is 40%; ture cycle under +85°C./-40°C. The mentioned temperature 0050 (b) The conductive filer is with the core-shell par environment of annealing can be any temperature that below ticles structure, and consists of the core, shell and interlayer. the decomposition temperatures of polymer materials, like The shell is W2B, the interlayer is WB, and the core is metal the high temperature annealing with the temperature higher tungsten. It’s grain size is 2.0 um, and the Volume fraction is than the melting temperature of composite materials and the 60%. low temperature annealing with the temperature lower than 0051 (c) Coupling agent is single alcoxyl based isopropyl the melting temperature of composite materials. di-oleic acid acyloxy titanate, the Volume fraction accounts for the 0.5% of the volume in conductive filler, and the density 0037. In the mentioned PTC components, the two mental is 0.976 g/cm. electrode slices are tandem connected into the protective cir 0.052 Setting the internal mixer temperature at 180°C., cuit by conductive components. The conductive parts, also be speed at 30 rotation per minute, putting the polymer in it for called other mental parts can be connected on the electrode mixing 3 minutes, and then adding the conductive filler to go slices through electroplating, electroless plating, printing, on mixing 15 minutes, finally the Macromolecule Based Con dipping, spot welding, reflow soldering or conductive adhe ductive Composite Material will be finished. The melted and sive so that to connect the PTC into circuit. The “mental mixed Macromolecule Based Conductive Composite Mate components' includes any structural components that can rial was flattened by mill, and the Macromolecule Based conduct with mental electrode slices. It can be any shape, Conductive Composite Material 11 with the thickness 0.2-0. Such as dot, line, band, sheet, column and other combined 25 mm is done. body. The mentioned base material of “mental components’ 0053. The production process of PTC components is as can be any conductive metals and their alloy, like nicke, below: copper, aluminum, Zinc and their alloy. 0054 PIs refer to the drawing 1 (sketch of the PTC com 0038. The mentioned PTC components as thermistor ponents mentioned in the invention), let's put the Macromol components or over protection components have low room ecule Based Conductive Composite Material 11 in the middle temperature resistivity, outstanding weather durability, good of the two symmetric metal electrode slices 12 and 12, then Voltage resistance and resistor repeatability. Its strength is the metal electrode slices 12 and 12 will be tightly connected very high. Under 25°C., the resistivity of PTC components with the Macromolecule Based Conductive Composite Mate will be lower than 0.02 S2-cm. rial through thermo compression bonding. The temperature 0039. The advantage of the Macromolecule Based Con of thermo compression bonding will be set at 180°C., at first ductive Composite Material lies in the fact that it has good to warm up 5 minutes, and next to hot press the materials 3 conductivity and processing dispersion. What's more, the minutes with the press 5 MPa, then cold press it 8 minutes in PTC components that be made from the Macromolecule the cold press machine, after that punching it into single Based Conductive Composite Material are with a low room component with 34mm boy mould, at last jointing the two temperature resistivity, and still have outstanding weather metal pins 13 and 13" on the surface of metal electrode slices durability, good Voltage resistance and resistor repeatability 12 and 12", the PTC components are produced. at the same time. 0055. The electrical property of the PTC components in 0040. The further detailed explanations to the invention the implementation is as the attached chart No. 1. with the attached drawing areas below. Implementation No. 2 ILLUSTRATION 0056. The steps of producing Macromolecule Based Con ductive Composite Material and PTC components are the 0041 Drawing NO. 1 is the structure schematic of the same with the implementation No. 1, but the proportion of the invented PTC components. Volume fraction of the coupling agent that in the conductive 0042 Drawing NO. 2 is the structure schematic of the composite material is changed from 0.5% of the volume in the invented PTC components implementations. conductive filler to 1.0%. 0043. Drawing NO. 3 is the resistance-temperature graph 0057 The electrical property of the PTC components in of the thermistor components of the implementation NO. 6. the implementation is as the attached chart No. 1. US 2014/0327513 A1 Nov. 6, 2014

Implementation No. 3 Comparison No. 1 0066. The steps of producing Macromolecule Based Con 0058. The steps of producing Macromolecule Based Con ductive Composite Material and PTC components are the ductive Composite Material and PTC components are the same with the implementation No. 3, but the Macromolecule same with the implementation No. 1, but the proportion of the Based Conductive Composite Material is without any cou Volume fraction of the coupling agent that in the conductive pling agent. composite material is changed from 0.5% of the volume in the 0067. The electrical property of the PTC components in conductive filler to 1.5%. the implementation is as the attached chart No. 1. 0059. The electrical property of the PTC components in 0068. The R in the table 1 means the resistance after the implementation is as the attached chart No. 1. soldering two metal pins 13 and 13 on the surface of the two metal electrode slices 12 and 12", which is the minimum Implementation No. 4 resistance of 10 pcs. PTC components; 0060. The steps of producing Macromolecule Based Con I0069. R, means the resistance after soldering two ductive Composite Material and PTC components are the metal pins 13 and 13 on the surface of the two metal electrode same with the implementation No. 1, but the proportion of the slices 12 and 12", which is the average value of 10 pcs. PTC Volume fraction of the coupling agent that in the conductive components; composite material is changed from 0.5% of the volume in the 0070 R means the resistance after soldering two metal conductive filler to 2.0%. pins 13 and 13" on the surface of the two metal electrode slices 0061 The electrical property of the PTC components in 12 and 12", which is the max value of 10 pcs. PTC components. the implementation is as the attached chart No. 1. (0071 STDEV means the standard deviation of 10 pcs. PTC components, which reflected the discreteness of resistance. Implementation No. 5 0072 R1 means the resistance that is tested on the condi tion that PTC components are electrified (6V750A) 6 seconds 0062. The steps of producing Macromolecule Based Con and then be placed at the temperature 25°C. for an hour. ductive Composite Material and PTC components are the 0073 Roo means the resistance that is tested on the con same with the implementation No. 1, but the proportion of the dition that PTC components be electrified (6V750 A) 6 sec Volume fraction of the coupling agent that in the conductive onds, then be cut off the power 60 seconds, keeping the cycle composite material is changed from 0.5% of the volume in the 100 times, finally be placed at the temperature 25°C. for an conductive filler to 2.5%. hour. 0063. The electrical property of the PTC components in I0074 Roo, means the resistance that is tested on the the implementation is as the attached chart No. 1. condition that PTC components are put at the temperature of +85°C. for 30 minutes, and then be put at the temperature of Implementation No. 6 -40°C. for 30 minutes, keeping the cycle 100 times, finally be placed at the temperature of 25°C. for an hour. 0064. The steps of producing Macromolecule Based Con 0075 Riso , means the resistance that is tested on the ductive Composite Material and PTC components are the condition that the PTC components withstand voltage for 2 same with the implementation No. 2, but the used coupling hours under 6V, 50A, then be placed at the temperature 25°C. agent is single alkoxy style isopropyl tri-oleic acid acyloxy for an hour. titanate, and the additive amount accounts for 1.0% of the 0076 Riso, means the resistance that is tested on the volume in conductive filler, density is 1.01 g/cm. condition that the PTC components withstand voltage for 2 0065. The electrical property of the PTC components in hours under 12V, 50A, then be placed at the temperature 25° the implementation is as the attached chart No. 1. C. for an hour. TABLE 1.

Implementation Implement- Implement Implement- Implement- Implement- Implement- Comparison Comparison ation 1 ation 2 ation 3 ation 4 ation 5 ation 6 1

Concentrition R, 5.4 S.6 5.5 6.1 6.6 6.8 7.2 of resistance (mohm) average 6.6 6.5 6.O 6.7 7.0 7.6 8.4 (mohm) Rmax 7.2 7.0 6.6 7.4 8.0 8.3 9.7 (mohm) STDEV O.S O.S 0.4 0.4 O.S 0.7 O.9 Current R 7.6 7.8 7.2 7.6 7.9 8.8 9.6 resistance R100 18.3 18.6 16.7 19.5 20.4 22.3 27.8 Weatherability Heat cycle 8.5 8.4 8.0 8.2 9.1 9.6 10.7 R100 cycles (mohm) Pressure R677504 16.0 15.6 14.6 17.2 17.8 18.5 20.4 resistance (mohm) Rp v7504 18.6 19.0 18.8 20.1 22.4 24.1 Breakdown (mohm) US 2014/0327513 A1 Nov. 6, 2014

TABLE 1-continued Implementation Implement- Implement- Implement- Implement- Implement- Implement- Comparison Comparison ation 1 ation 2 ation 3 ation 4 ation 5 ation 6 1 Processability Torque 45.3 42.5 40.4 42.6 44.1 46.2 44.8 (N. m)

0077. From the table 1 we can see that the implementation I0082. The thermistor components mentioned in the inven 1-6 has the same volume fraction of crystalline polymer and tion are as drawing 1. Let's put the Macromolecule Based conductive filler with the comparison, but the implementation Conductive Composite Material 11 in the middle of the two 1-6 is added coupling agent, and the resistance of finished symmetric metal electrode slices 12 and 12", then the metal products is lower than the one without it. What's more the electrode slices 12 and 12" will be tightly connected with the added one is with a lower discreteness, which means the Macromolecule Based Conductive Composite Material coupling agent can help the conductive material to disperse in through thermo compression bonding. The temperature of the polymer matrix. In the implementation 3, when its with thermo compression bonding will be set at 180°C., at first to the same volume fraction of conductive filler, and the volume warm up 5 minutes, and next to hot press the materials 3 fraction of coupling agent comes to 1.5%, the PTC compo minutes with the press 5 MPa, then cold press it 8 minutes in nents are with the lowest resistance. The PTC components in the cold press machine, after that punching it into single Implementation 1-6 and in comparison 1 both can withstand component with 34mm boy mould, at last jointing the two the voltage of 6V, but the PTC components in implementation metal pins 13 and 13" on the surface of metal electrode slices 1-6 can withstand the Voltage of 12V, the one in the compari 12 and 12", the PTC components are produced. son can't, which means coupling agent can increase the pres I0083 Table 3 is the resistance-temperature graph of ther sure resistance of PTC components. The torque at the time of mistor components in the implement. The resistance of ther processing the Macromolecule Based Conductive Composite mistor components will be very low when its at the tempera Materials showed us that the implementation 1-6 with a ture of 25°C., and the resistance will be higheran higher with certain of coupling agent has a lower torque proportion than the increasing oftemperature. When temperature increases to those without coupling agent, which means coupling agent 130° C. or so, the resistance of thermistor components will can improve the shaping and processing ability of Macromol change suddenly, and increases about 10 order of magnitude. ecule Based Conductive Composite Material. At this time, the thermistor components will change from 0078. In the implement 1-6, the conductive composite conductor to insulator so that the circuit will be turn off to material that used by the PTC parts added the coupling agent protect the circuit components. that can improve the disperse state of conductive filler and can Implement No. 8 strengthen the conductive network of the composite material, I0084. The composition of Macromolecule Based Conduc thus the PTC parts have higher concentration of resistance. tive Composite Material for producing thermistor compo What's more, the conductive filler with core-shell structure is nents is the same with implement 7, and the formula of not easy to be oxidized, and needn't to protect the Macromol Macromolecule Based Conductive Composite Material and ecule Based Conductive Composite Material by packing, thus the electrical specification of thermistor components are as the small size PTC components with the thickness 0.2 table 2, but the steps for producing Macromolecule Based mm-2.0 mm and the current carrying area 1210, 1206,0805, Conductive Composite Material sheet and thermistor compo 0603 can be produced. nents are different. The steps are as below: 007.9 The below implements are without coupling agent, I0085. After flouring the polymer, put the flour into mixer formula and performance will be showed in table 2. to dry mix with conductive filler for 30 minutes, and then add the mixture into twin-screw extruder, after melting and mix Implement No. 7 ing at the temperature of 180°C.-220°C., the mixture will be 0080. The formula of Macromolecule Based Conductive Squeezed out and be granulated, then the granules of Macro Composite Material that for producing thermistor compo molecule Based Conductive Composite Material are formed. nents is showed as table 2. In it, polymer 1 is high density The granules will be added into another twin-screw extruder, polyethylene, its melting temperature is at 134°C., density is at the temperature of 180°C.-220°C., it will be squeezed out by extruder die head and turn into fused Macromolecule 0.953 g/cm; conductive filler 1 is titanium carbide, its Fisher Based Conductive Composite Material sheet11. The sheet 11 particle size is 2.0 um, density id 1.93 g cm; conductive filler will be tightly connected with the upper and lower two sym 2 is with core-shell structure, its size is 2.0 um, the shell is metric metal electrode slices 12 and 12' through hot pressing W2B, the interlayer is WB, and the core is metal tungsten. by hot press roller. After that, the sheet will be cut into the core 0081. The productive processes of thermistor components material with size 110200 mm, and then the core material are as below: Setting the internal mixer temperature at 180° will be punched into single components with size 3*4 mm by C., speed at 30 rotation per minute, putting the polymer in it modules, at last the two metal pins 14 and 15 will be soldered for mixing 3 minutes, and then adding the conductive filler to on the surface of upper and lower metal electrode slices 12 go on mixing 15 minutes, finally the Macromolecule Based and 12' by reflow soldering to form the thermstor compo Conductive Composite Material will be finished. The melted nentS. and mixed Macromolecule Based Conductive Composite Material was flattened by mill, and the Macromolecule Based Implement No. 9 Conductive Composite Material 11 with the thickness 0.2-0. I0086. The composition of Macromolecule Based Conduc 25 mm is done. tive Composite Material for producing thermistor compo US 2014/0327513 A1 Nov. 6, 2014 6 nents is the same with implement 7, and the formula of conductive filler will be changed from 60% to 52%. In it, the Macromolecule Based Conductive Composite Material and resistance of thermistor components is measured by four the electrical specification of thermistor components are as probe method. table 2, but the volume fraction of polymer 1 will be changed 0091 Results analysis: the resistance data in the table 2 are from 34% to 38%, and the volumefraction of conductive filler tested on the condition that the thermistor components that is 2 will be changed from 60% to 56%. made from the Macromolecule Based Conductive Composite Material mentioned in the invention are placed at the tem Implementation No. 10 perature of 25°C. for an hour after triggering in the condition 0087. The composition of Macromolecule Based Conduc- of 6V750 A. tive Composite Material for producing thermistor compo- 0092. The R in the table 2 means the resistance of ther nents is the same with implement 7, and the formula of mistor components two metal electrode slices 12 and 12 Macromolecule Based Conductive Composite Material and before being soldered the two metal pins 13 and 13" on their the electrical specification of thermistor components are as surfaces; R means the resistance of thermistor components table 2, but the Volume fraction of polymer 1 will be changed two metal electrode slices 12 and 12" after being soldered the from 34% to 38%, the volume fraction of polymer 2 will be two metal pins 13 and 13 on their surfaces; R means the changed from 6% to 10%, and the volume fraction of con- resistance that is tested on the condition that PTC components ductive filler 2 will be changed from 60% to 56%. are electrified (6V750 A) 6 seconds and then be placed at the temperature of 25°C. for an hour. Ras means the resistance Comparison 2 that is tested on the condition that PTC components be elec 0088. The formula of Macromolecule Based Conductive trified (6V750 A) 6 Seconds, then be cut off the power 60 Composite Material and the electrical specification of ther- seconds, and keep the cycle 25 times, finally be placed at the mistor components areas table 2, and the steps on producing temperature 25°C. for an hour Rso means the resistance that Macromolecule Based Conductive Composite Material and is tested on the condition that PTC components be electrified over current protection components are the same with the (6V750 A) 6 seconds, then be cut off the power 60 seconds, implementation 1, but the conductive filler 2 will turned to and keep the cycle 50 times, finally be placed at the tempera conductive filler 1. ture 25°C. for an hour. Roo means the resistance that is tested on the condition that PTC components be electrified (6V750 Comparison 3 A) 6 seconds, then be cut off the power 60 seconds, and keep O Composite1989 the Material formula and of Marpmoleculethe electrical specification Based conductive of ther theERR, condition that PTC"RE, components are put at the temperature mistor components are as table 2. and the steps on producing of +85°C. for 30 minutes, and then be put at the temperature Macromolecule Based Conductive Composite Material and of -40° C. for 30 minutes, and keep the cycle 100 times, over current protection components are the same with the finally be placed at the temperature of 25°C. for an hour. implementation 1, but the conductive filler 2 will turned tO (High temperature and humidity) Rooo, means the resistance conductive filler 1, the volume fraction of polymer 1 will be that is tested on the condition that PTC components are put in changed from 34% to 38%, and the volume fraction of con- the environment of 85°C., 85% RH for 1000 hours and then ductive filler will be changed from 60% to 56%. be placed at the temperature of 25° C. for an hour. (High Comparison 4 humidity) Roo, means the resistance that is tested on the condition that PTC components are put in the environment of 0090 the formula of Macromolecule Based Conductive 60° C., 95% RH for 1000 hours and then be placed at the Composite Material and the electrical specification of ther- temperature of 25°C. for an hour. Regarding the press resis mistor components are as table 2, and the steps on producing tance, 6V750 A2H means the thermistor components with Macromolecule Based Conductive Composite Material and stand voltage for 2 hours in the condition of 6V, 50 A; 12V750 over current protection components are the same with the A/2H means the thermistor components withstand voltage for implementation 1, but the conductive filler 2 will turned to 2 hours in the condition of 12V, 50 A; Pressure resistance is conductive filler 1, the volume fraction of polymer 1 will be OK means the over current protection components do not changed from 34% to 38%, the volume fraction of polymer 2 burn and crack, NG means thermistor components burn or will be increased from 6% to 10%, and the volumefraction of crack. TABLE 2

Implementation Implement- Implement- Implement- Implement- Comparison Comparison Comparison Comparison ation 7 ation 8 ation 9 ation 10 2 3 4

Composition (Volume percent) (%)

Polymer 1 34 34 38 38 34 38 38 Polymer 2 6 6 10 6 6 10 Conductivity 60 56 52 filler 1 Conductivity 60 60 56 52 filler 2 US 2014/0327513 A1 Nov. 6, 2014

TABLE 2-continued mplementation Implement- Implement- Implement- Implement Comparison Comparison Comparison Comparison ation 7 ation 8 ation 9 ation 10 2 3 4 Electrical characteristic

R (mohm) 1.O O.8 1.1 1.5 1.6 2.1 2.5 Ro (mohm) S.O 4.5 5.4 5.7 6.2 6.7 7.5 R (mohm) 5.9 4.8 6.0 6.5 8.7 9.1 9.7 R2s (mohm) 9.5 6.8 9.8 10.4 12.5 13.6 14.8 Rso (mohm) 12.8 9.7 13.2 14.5 17.6 17.8 18.9 Roo (mohm) 17.5 13.1 18.6 20.1 24.3 27.7 31.3 Weather durability

heat cycle 8.5 6.O 12.0 12.8 18.7 20.6 24.7 R100 cycles (mohm) High temperature 7.8 6.6 8.6 9.2 9.4 7.3 8.5 and humidity Rooo, (mohm) High humidity 7.2 6.O 7.9 8.6 7.8 8.2 8.6 Rooo, (mohm) Pressure resistance

6 WSOA2 OK OK OK OK OK OK OK 2WSOA2 OK OK OK OK NG NG NG

0093. From table 2 we can see: implementation 7-8 and maybe will more than the contents that are mentioned in the comparison 2; implementation 9 and comparison 3; imple paper. Thus the invention’s protective range will not be lim mentation 10 and comparison 4, each of the group has the ited in the contents of the implementation part, but should same volume fraction of conductive filler, but the conductive includes the combination of all the contents that showed in filler used in the implementation 7-10 is with the core-shell different part, and the various of replacement and embellish granule structure, the resistance of finished products that are ment that accord with the invention, which is covered by made from this kind of filler is lower than the resistance of claims of the invention. products with the conductive filler that is not core-shell gran ule structure but titanium carbide used in the implementation 1. A kind of Macromolecule Based Conductive Composite 2-4. The resistance tested in the implementation 7-10 is Material includes Macromolecule Based Material, conduc lower than the resistance tested in the implementation 2-4 tive filler and coupling agent. Its characteristics areas below: after the thermistor components being punch 100 times by the (a) The mentioned Macromolecule Based Materials are current of 6V750 A, which showed the good resistor repeat one kind of and the mixture of polythene, polypropy ability. lene, PVDF, Polyolefin elastomer, epoxy resin, ethyl 0094. The thermistor components in Implementation ene-vinyl acetate copolymer, polymethylmethacrylate 7-10 and in comparison 2-4 all can withstand the voltage of and ethylene-acrylic acid copolymer. It accounts for 6V, but the thermistor components in implementation 7-10 20%-75% of volume fraction in the Macromolecule can withstand the Voltage of 12V, the one in the comparison Based Conductive Composite Material. 2-4 can't, which means that the thermistor components pro (b) Conductive filler with particles structure of core-shell duced by the conductive filler with core-shell structure has type, which accounts for 25%-80% of volume fraction good pressure resistance. From table 3 we can see that the of the Macromolecule Based Conductive Composite thermistor components produced by the conductive filler with Material. Its particle diameter is 0.1 um-20 um, and core-shell structure has good PTC strength (the mentioned volume resistivity is under 10 S2 m. The mentioned PTC strength is the logarithm values of the max resistivity of conductive filler is dispersed in the Macromolecule samples in the resistivity-temperature graph and the resistiv Based material. ity of samples at the room temperature). (c) Coupling agent accounts for 0.05%-5% of the volume 0095. The thermistore components mentioned in the of conductive filler. The mentioned coupling agent is one implementation 7-10 has low room-temperature resistivity, or more mixture of titanate coupling agent, single type outstanding weather durability, good Voltage resistance, alkoxy titanate coupling agent, single alkoxypyrophos excellent resistor repeatability and PTC strength, because it phate titanate coupling agent, chelate type titanate cou used the Macromolecule Based Conductive Composite Mate pling agent, coordination type titanate coupling agent rial that contained the core-shell structural conductive filler and quaternary ammonium salt type titanate coupling with low resistivity. What's more, the conductive filler with agent. core-shell structure is hard to be oxidized, and needn't to 2. According to the Macromolecule Based Materials that protect the Macromolecule Based Conductive Composite mentioned in the claims 1, the characters are as below: the Material by packing, thus the small size PTC components mentioned particles structure of core-shell type consists of with the thickness 0.2 mm-2.0 mm and the current carrying core, shell and interlayer. The core consists of one of tanta area 1210, 1206,0805,0603 can be produced. lum, Zirconium, titanium, niobium, molybdenum, hafnium, 0096. The invention’s characteristics and contents are tungsten, chromium or beryllium; the shell is made up of one explained as above, but the explanation is still limited or just of boride, nitride or silicide of core matter; the interlayer refers to some particular part, the invention's characteristic consists of one of boride, nitride or silicide of core matter. The US 2014/0327513 A1 Nov. 6, 2014

molecular structure is different between the boride, nitride or diboride, molybdenum boride (MoB), molybdenum pent silicide that makes up interlayer and the one that makes up aboride((MoBs), hafnium diboride, tungstenboride, ditung shell. sten boride, chromium boride, dichromium boride(CrB), 3. According to the Macromolecule Based Materials that chromium diboride or chromium triboride(CrsB). mentioned in the claims 2, the characters are as below: the 9. According to the Macromolecule Based Conductive described boride is one oftantalumboride, tantalum diboride, Composite Material that described in the claims 7, its char vanadium boride, Vanadium diboride, zirconium diboride, acter is that the described nitride is one of tantalum nitride, titanium diboride, niobium boride, niobium diboride, molyb Vanadium nitride, Zirconium nitride, titanium nitride, nio denum boride (MoB), molybdenum pentaboride((MoBs), bium nitride or hafnium nitride. hafnium diboride, tungsten boride, ditungsten boride, chro 10. According to the Macromolecule Based Conductive mium boride, dichromium boride(CrB), chromium diboride Composite Material that described in the claims 7, its char or chromium triboride(CrsB). acter is that the described carbide is one of tantalum carbide, 4. According to the Macromolecule Based Materials that Vanadium carbide, Zirconium carbide, titanium carbide, nio mentioned in the claims 2, the characters are as below: the bium carbide, molybdenum carbide(MoC), hafnium car described nitride is one of tantalum nitride, Vanadium nitride, bide, tungsten monocarbide, ditungsten carbide or trichro Zirconium nitride, titanium nitride, or mium dicarbide(CrCl). hafnium nitride. 11. According to the Macromolecule Based Conductive 5. According to the Macromolecule Based Materials that Composite Material that described in the claims 7, its char mentioned in the claims 2, the characters are as below: the acter is that the described silicide is one of tantalum disilicide, described carbide is one of tantalum carbide, Vanadium car tantalum silicide (TasSi), trivanadium silicide, Vanadium bide, zirconium carbide, titanium carbide, , disilicide, Zirconium disilicide, titanium disilicae, titanium molybdenum carbide(MoC), hafnium carbide, tungsten silicide(TiSi.), niobium disilicide, molybdenum disilicide, monocarbide, ditungsten carbide or trichromium dicarbide hafnium disilicide, tungsten disilicide, trichromium silicide (CrCl). (Cr,Si) or chromium disilicide. 6. According to the Macromolecule Based Materials that 12. According to the claims 1-11, the mentioned PTC mentioned in the claims 2, the characters are as below: the components that be made from the Macromolecule Based described silicide is one of tantalum disilicide, tantalum sili Conductive Composite Material is two metal electrode slices cide (TasSis), trivanadium silicide, Vanadium disilicide, Zir with the Macromolecule Based Conductive Composite Mate conium disilicide, titanium disilicae, titanium silicide rial plate in the middle. The Macromolecule Based Conduc (Ti Si.), niobium disilicide, molybdenum disilicide, hafnium tive Composite Material plate with thickness 0.01-3.0 mm is disilicide, tungsten disilicide, trichromium silicide(CrSi) or cut into single component with plane shape. The mentioned chromium disilicide. single component has two Surfaces perpendicularing to the 7. A kind of Macromolecule Based Conductive Composite direction of electric. The thickness of metal electrode slices is Material includes Macromolecule Based Material and con less than 0.3 mm, and, at the temperature of 25°C., the PTC ductive filler, the characters are as below: component is with a volume resistivity lower than 0.02 C2 cm. The mentioned polymer Based Materials are one kind of 13. According to the claims 12, the character of PTC com and the mixture of polythene, polypropylene, PVDF, ponents that be made from the Macromolecule Based Con Polyolefin elastomer, epoxy resin, ethylene-vinyl ductive Composite Material is that the single component acetate copolymer, polymethylmethacrylate and ethyl mentioned above is with the laminate structure of square, ene-acrylic acid copolymer. It accounts for 20%-75% of triangle, round, rectangle, annulus, polygon or other irregular Volume fraction in the Macromolecule Based Conduc shape. tive Composite Material. 14. According to the claims 12 or 12, the production way of The mentioned Conductive filler is with particles structure PTC components are as below: of core-shell type, and its particle diameter is 0.1 1) Putting the polymer material and conductive filler into um-20 um, volume resistivity is under 0.03 G2m. The the mixing equipment to mix and melt under the tem mentioned Conductive filler with particles structure of perature that above polymer melting temperature. Then, core-shell type consists of core, shell and interlayer, and through extrusion molding, compression molding or accounts for 25%-80% of volume fraction of the Mac calendaring, the mixed polymer will be processed into romolecule Based Conductive Composite Material. Macromolecule Based Conductive Composite Material Among it: sheet with thickness 0.01-3.0 mm. The core consists of one of tantalum, Zirconium, titanium, 2) The composite plate will be produced through tightly niobium, molybdenum, hafnium, tungsten, chromium pressing the electrode slice on each two sides of sheet by or beryllium; roller when the Macromolecule Based Conductive The shell is made up of one of boride, nitride or silicide of Composite Material sheet still in melting. core matter, 3) The composite plate will be cut into single component The interlayer consists of one of boride, nitride or silicide by punching, etching, scribing or laser cutting, and then of core matter. The compound of boride, nitride or sili the PTC component is done. The mentioned single com cide that makes up interlayer is different from the one ponent with plane shape means that it has two Surfaces that makes up shell. that perpendicular to the direction of current. What's 8. According to the Macromolecule Based Conductive more the distance between two Surfaces is very close, Composite Material that described in the claims 7, its char which is at most 3.0 mm. acter is that the described boride is one of tantalum boride, 4) Processing the PTC components by cross linking and/or tantalum diboride, Vanadium boride, vanadium diboride, Zir heat treating. conium diboride, titanium diboride, niobium boride, niobium