CN106576398B - 电阻碳复合材料 - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- 239000006229 carbon black Substances 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- 229920005596 polymer binder Polymers 0.000 claims abstract description 8
- 239000002491 polymer binding agent Substances 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 4
- 238000004870 electrical engineering Methods 0.000 abstract description 2
- 238000009472 formulation Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004972 Polyurethane varnish Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000011158 industrial composite Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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Abstract
本发明涉及电气工程，特别涉及电阻碳复合材料。它可用于制备高导电性浆料和能够提供可靠电接触的粘合剂，以及制造工业和家用加热器。电阻碳复合材料包括基于高导电等级炭黑的导电相，与高导电胶体等级的石墨和耐热等级的聚合物粘合剂的组合。与此同时，提供高导电性的炭黑具有至少300至600m2/g的比表面积，10至50nm的粒径；胶体石墨制剂具有小于4微米的石墨颗粒尺寸。要求保护的本发明声称的技术结果是通过优化粘合剂的含量和有效导电组分的选择来提高导电性和降低电阻。
Description
技术领域
本发明涉及电气工程，特别是电阻碳复合材料，并且可用于制备能够提供可靠电接触的高导电性浆料和粘合剂，以及用于工业和家用加热器的制造。
相关技术
导电粘合剂和浆料以及工业和家用加热器的生产需要柔性的和耐热的，耐热温度高达150℃的电阻复合材料，根据计算，所述电阻复合材料需具有在5-200欧姆/平方范围内的表面电阻。具体值取决于加热器类型和加热元件的拓扑。
碳材料是公知的并且在各种复合材料中用作导电相。
已知一种复合电阻材料(Pugachev GA导电混凝土，新西伯利亚(Novosibirsk)，“科学(science)”，1993，p.225)由比特尔(betel)的混合物组成，其由含有11.43％的作为导电相的炭黑П-80Э，45.72％的波特兰水泥M-400，和42.85％的作为矿物添加剂的石英砂。
该材料具有许多缺点，例如：长期加热到约90℃或更高的温度是不可能的，混凝土基体的导电性能是不稳定的，导电性低等。
由高导电性炭黑和聚合物粘合剂溶液组成的材料广泛用于制造具有低加热温度(地板下加热等)的膜加热器。
目前已知的材料的缺点是最高加热温度为70℃，并且，不能使用于需要约10瓦每平方分米的比功率的任何加热器。
用于导电涂层的组合物(RU2460750C1，C09D133/04,21.04.2011)是已知的。它含有成膜共聚物，有机溶剂，导电石墨基粉末与羰基铁的混合物，其特征在于将碳黑粉末(烟灰)加入到混合物中。
已知的技术解决方案的缺点是由于石墨组分(太大的颗粒)的次优使用和使用不正确类型的炭黑而导致低的电导率(比本发明低几乎两个数量级)。由于显著的表面电阻和氧化表面的倾向，羰基铁不提供高的导电性。
最接近要求保护的技术决定是复合电阻材料(RU2364967C1，H01S7/00,09.01.2008)，该复合电阻材料包含通过槽法获得的作为导电相的工业碳(所述的工业碳具有高度发达的，400-500m2/g的表面积，粒径为15至25nm)，和聚氨酯清漆，其具有以下比例的组分：18-22wt％工业碳，余量为聚氨酯清漆。在25至110℃的温度范围内，散热覆盖区域的最小加热温度偏差在±0.4℃之内，根据专利，最低电阻率为0.349欧姆*厘米(3.49*10-3欧姆*米)。
已知的解决方案的缺点是，填充有炭黑的材料的这种电阻率导致厚度为0.1mm的电阻层的表面电阻率等于34.9欧姆/平方。此表面电阻率对于加热器的一些实施例以及对于高导电性浆料和粘合剂来说太大了。用分散的碳组分高度填充的材料由于缺乏粘合剂而通常具有较差的机械性能。
发明内容
本发明的目的是获得比在相关技术中要求的具有至少一个数量级，即10-15倍或更高的高导电性的复合电阻碳材料。
使用所提出的发明的技术结果是通过优化粘合剂的含量和选择根据渗透理论有效导电且同时保持导电复合材料的柔性和耐久性的导电材料而增加导电性和降低电阻。电导率显著超过所述的最大的模拟值，数量级，并且溶剂含量的变化允许在宽范围内调节胶体分散体的粘度。
结果通过电阻碳复合材料的含量实现：根据本发明，该电阻碳复合材料包括基于炭黑的导电相和包含基于高导电等级炭黑的导电相的聚合物粘合剂，并且与导电胶体等级的石墨和溶液形式的耐热聚合物粘合剂结合。同时，提供高导电性的炭黑具有至少300至600m2/g的比表面积，10至50nm的粒度，胶体石墨制剂颗粒具有小于4微米的尺寸。为了制备胶体悬浮液，使用耐热聚合物粘合剂溶液作为介质。此外，基于对苯二甲酸或癸二酸或己二酸或乙二醇或二甘醇，或所述组分的部分的聚酯，如TP-60树脂以溶液的形式以如下比例用作耐热聚合物粘合剂，wt％：
具体实施方式
复合电阻材料的制备在其使用实例中示出。
为了产生所意图的工业复合材料的导电性，使用胶体石墨制剂C-0和/或C-1以及磨碎的天然石墨铅笔作为高质量和高导电性的材料。使用在本国生产的一些等级的高导电性炭黑，例如OMCARBTM CH210和/或OMCARBTM CH220，和/或OMCARBTM CH230和OMCARBTMCH600。
为了获得复合材料所需的特性，在耐热树脂TF-60的溶液中制备一些基于胶体石墨-炭黑的悬浮液。根据GOST R 50563.4-93在珠磨机中制备悬浮体系。分散体粒径不超过4微米。
然后通过注射器选择获得的胶体悬浮液的样品并沉积在偶数层的方形基底上。在形成层液体并蒸发溶剂之后，产生电阻复合材料的样品。一些结果如下所示：
表1
粘合剂含量的增加明显增加了电阻性直到完全绝缘。
改变溶剂含量可以在宽范围内调节悬浮液的粘度。使用氯仿或二氯甲烷，或二氯乙烷作为溶剂。
电导率显著地，数量级地超过了在先前专利中声称的弹性的最大值，是。同时，所述的复合材料仍保持强度和导电性。
在本发明中实现的复合碳电阻材料的电导率水平为约5*103S/m，其比现有技术中所述的电导率高出至少一个数量级，即10-15倍或更多。
所提供的材料在工业上适用。可以通过实现相同的技术结果来重复实施。
本发明的技术效果是材料的制造和使用的简单性，以及低生产成本。
Claims (5)
1.一种柔性电阻碳复合材料，其包含基于炭黑的导电相和石墨以及耐热聚合物粘合剂，所述耐热聚合物粘合剂为对苯二甲酸和乙二醇的聚酯与癸二酸和乙二醇的聚酯的共聚物或对苯二甲酸和乙二醇的聚酯与己二酸和乙二醇的聚酯的共聚物的形式。
2.如权利要求1所述的柔性电阻碳复合材料，其中炭黑选自OMCARBTMCH210和/或OMCARBTMCH220和/或OMCARBTMCH230和OMCARBTMCH600。
3.如权利要求1所述的柔性电阻碳复合材料，其中所述石墨是胶体石墨。
4.如权利要求3所述的柔性电阻碳复合材料，其中所述胶体石墨是天然石墨。
5.如权利要求1所述的柔性电阻碳复合材料，由包含以下的悬浮液制得：碳黑、石墨、形式为对苯二甲酸和乙二醇的聚酯与癸二酸和乙二醇的聚酯的共聚物或对苯二甲酸和乙二醇的聚酯与己二酸和乙二醇的聚酯的共聚物的耐热聚合物粘合剂、以及选自氯仿、二氯甲烷和二氯乙烷中的至少一种溶剂，其中包含以下组分，wt.％：
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| Application Number | Priority Date | Filing Date | Title |
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| RU2014132728/07A RU2573594C1 (ru) | 2014-08-07 | 2014-08-07 | Резистивный углеродный композиционный материал |
| RU2014132728 | 2014-08-07 | ||
| PCT/RU2015/000490 WO2016022048A1 (ru) | 2014-08-07 | 2015-08-06 | Резистивный углеродный композиционный материал |
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| CN106576398A CN106576398A (zh) | 2017-04-19 |
| CN106576398B true CN106576398B (zh) | 2021-05-25 |
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| EP (1) | EP3179825B1 (zh) |
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| EP3179827A4 (en) * | 2014-08-07 | 2018-04-18 | Obshhestvo S Ogranichennoj Otvetstvennost'ju "Inzhiniriingovaja Kompanija "Teplofon" | Flexible resistive heating element |
| US10468164B2 (en) * | 2016-06-22 | 2019-11-05 | Thueringisches Institut Fuer Textil-Und Kunststoff-Forschung E.V. | Electrically conductive shaped body with a positive temperature coefficient |
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| US4464421A (en) * | 1982-02-04 | 1984-08-07 | Corning Glass Works | Glass frits containing WO3 or MoO3 in RuO2 -based resistors |
| US4600602A (en) * | 1984-07-18 | 1986-07-15 | Rohm And Haas Company | Low resistance resistor compositions |
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| RU2074519C1 (ru) * | 1994-05-31 | 1997-02-27 | Борис Арсентьевич Мурашов | Способ изготовления полимерного электронагревателя |
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| US6673864B2 (en) | 2000-11-30 | 2004-01-06 | General Electric Company | Conductive polyester/polycarbonate blends, methods for preparation thereof, and articles derived therefrom |
| US8999200B2 (en) * | 2002-07-23 | 2015-04-07 | Sabic Global Technologies B.V. | Conductive thermoplastic composites and methods of making |
| US20060041050A1 (en) * | 2002-12-25 | 2006-02-23 | Chikara Manane | Liquid mixture, structure, and method of forming structure |
| CN1253504C (zh) * | 2003-01-10 | 2006-04-26 | 侯毅 | 聚四氟乙烯电热材料的制备方法 |
| EP1858694A4 (en) * | 2005-02-25 | 2012-04-04 | Superior Graphite Co | GRAPHITE COATING OF PARTICLE MATERIALS |
| KR101256792B1 (ko) | 2005-07-20 | 2013-04-19 | 에이전시 포 사이언스, 테크놀로지 앤드 리서치 | 전기 전도성 경화성 수지 |
| CN101919005A (zh) * | 2007-09-13 | 2010-12-15 | 汉高股份两合公司 | 导电组合物 |
| RU2364967C1 (ru) * | 2008-01-09 | 2009-08-20 | Государственное образовательное учреждение высшего профессионального образования "Томский государственный архитектурно-строительный университет" (ГОУВПО "ТГАСУ") | Композиционный резистивный материал |
| RU2387105C2 (ru) * | 2008-04-07 | 2010-04-20 | Владимир Евгеньевич Волошин | Способ изготовления резистивного материала |
| RU2460750C1 (ru) * | 2011-04-21 | 2012-09-10 | Общество с ограниченной ответственностью "МЕДКОМПЛЕКТ" | Состав для электропроводящих покрытий и способ изготовления твердых электропроводящих покрытий |
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2014
- 2014-08-07 RU RU2014132728/07A patent/RU2573594C1/ru active
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2015
- 2015-08-06 WO PCT/RU2015/000490 patent/WO2016022048A1/ru active Application Filing
- 2015-08-06 EP EP15829105.4A patent/EP3179825B1/en active Active
- 2015-08-06 CN CN201580042538.1A patent/CN106576398B/zh active Active
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| JPH05114468A (ja) * | 1991-10-24 | 1993-05-07 | Mitsubishi Plastics Ind Ltd | 通電発熱体 |
| CN1898753A (zh) * | 2003-09-30 | 2007-01-17 | 通用电气公司 | 导电组合物、其制造方法以及由此种组合物衍生的制品 |
| CN1597502A (zh) * | 2004-09-13 | 2005-03-23 | 东北师范大学 | 纳米碳与石墨碳混合材料及其在锂离子电池中的应用 |
| WO2008091003A2 (en) * | 2007-01-22 | 2008-07-31 | Panasonic Corporation | Ptc resistor |
Also Published As
| Publication number | Publication date |
|---|---|
| US10098182B2 (en) | 2018-10-09 |
| RU2573594C1 (ru) | 2016-01-20 |
| EP3179825B1 (en) | 2021-01-13 |
| US20170171917A1 (en) | 2017-06-15 |
| CN106576398A (zh) | 2017-04-19 |
| EP3179825A4 (en) | 2018-04-18 |
| EP3179825A1 (en) | 2017-06-14 |
| WO2016022048A1 (ru) | 2016-02-11 |
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