WO2017198233A1 - Ptc inorganic composite material, and manufacturing method and application thereof - Google Patents

Ptc inorganic composite material, and manufacturing method and application thereof Download PDF

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Publication number
WO2017198233A1
WO2017198233A1 PCT/CN2017/085396 CN2017085396W WO2017198233A1 WO 2017198233 A1 WO2017198233 A1 WO 2017198233A1 CN 2017085396 W CN2017085396 W CN 2017085396W WO 2017198233 A1 WO2017198233 A1 WO 2017198233A1
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ptc
inorganic composite
composite material
carbon
graphite
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PCT/CN2017/085396
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French (fr)
Chinese (zh)
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张金柱
栾峰
张明
刘顶
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济南圣泉集团股份有限公司
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Publication of WO2017198233A1 publication Critical patent/WO2017198233A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5001—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with carbon or carbonisable materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/021—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient formed as one or more layers or coatings
    • 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—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater 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—Heater 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

Definitions

  • the invention relates to the field of composite material preparation with PTC properties, in particular to a PTC inorganic composite material and a preparation method and application thereof.
  • Carbon crystal heating plate is an emerging heating product. After nearly ten years of development, the technology is becoming more mature. Its characteristics are: 1. Subverting the heating tradition, saving energy and reducing emissions, adapting to the new requirements of the state and society; 2. No troubles with water seepage and water leakage, no troubles for collecting uniform heating costs. It is easy to install and use, that is, it is hot immediately; 3. It has the function of health care; the wavelength is 8-18 microns, and people in this environment for a long time are beneficial to the health of the body. 4. Relying on far-infrared heating and air convection, quiet, no noise, high sense of comfort; 5. Do not dry, release far infrared rays, do not take away the moisture in the air.
  • the solutions are as follows: (1) Develop a PTC material, that is, a material with a positive temperature coefficient. When a certain temperature is exceeded, the resistance value of the material increases with temperature. When the resistance is increased, the current and power are decreased, and the repetition can cause the temperature to fluctuate up and down around the target temperature without overheating. (2) Installing the thermostat, using the thermostat to monitor each board greatly increases the cost. On the other hand, in the case of a malfunction of the thermostat, local high heat may occur, and in a serious case, a fire may occur.
  • patent CN101407628A discloses a method for producing a water-soluble PTC functional conductive carbon paste, and a polymer-containing carbon containing oxide is disclosed in CN104371329A.
  • a method for preparing a slurry and a heating material having a PTC effect, a PTC carbon slurry constant temperature electric heating film is disclosed in the CN202652568U patent, and a PTC effect far infrared radiation heating cloth and a preparation method and use thereof are disclosed in the CN105415830A patent, but these
  • the PTC materials used in the technology are polymer materials or composites of carbon paste and silver paste, including polyethylene, polyurethane, stearic acid, monoglyceride, glycerin, ethylene glycol butyl ether acetate, isothiocyanate. Ester, silver paste, etc. Such materials are not stable.
  • PTC ceramic materials exist in the prior art, they are directly used as electronic devices after sintering.
  • CN104311004A discloses a PTC ceramic material and a method for improving the temperature stability of the PTC ceramic material below the Curie point.
  • CN102173786A discloses a novel PTC ceramic material composition comprising a ceramic phase and a glass phase, characterized in that the ceramic phase is a conventional PTC ceramic material and the glass phase is a PbO-BN material.
  • the content of the PbO-BN material is 1-10% by weight, and the content of the PTC ceramic material is 90-99% by weight.
  • This product uses PbO-BN glass phase to reduce the sintering temperature of PTC ceramic materials, and has high-performance PTC characteristics and a wide range of applications. It can be seen that inorganic ceramic PTC materials are used independently as electronic devices and both require high temperature sintering.
  • a first object of the present invention is to provide a PTC inorganic composite material by combining a nano ceramic material such as an inorganic material with a graphite-based carbon material coating agent, and using a carbon material to encapsulate the inorganic material itself, thereby realizing the carbon material.
  • Conductive, internal insulation effect the material can be applied to electric heating materials, for example, for carbon crystal heating plates, the performance is more stable, there will be no problems such as aging, flatulence, etc., which will bring subversive properties to the performance of the carbon crystal plate itself.
  • the ground lift greatly prolongs the service life and brings considerable economic benefits.
  • a second object of the present invention is to provide a method for preparing the above PTC inorganic composite material, which has the advantages of being able to completely retain the active ingredient of the raw material, and has the advantages of simple and easy operation, mild operating conditions, and no need for a high-temperature carbonization step.
  • a third object of the present invention is to provide the above-mentioned application of the PTC inorganic composite material, which can effectively solve the problem of overheating of the carbon crystal plate and increase of power runaway, and the carbon crystal plate has a frequency conversion function.
  • the increase in resistance causes the power to be appropriately attenuated to adjust to the appropriate power to control the temperature, thereby being more energy efficient than conventional carbon crystal plates.
  • the embodiment of the invention provides a PTC inorganic composite material, which is mainly prepared from the following raw materials: Percentage of mass, nano-ceramic material 75-95%, graphite-based carbon material coating agent 1-20%, dispersing agent 0.5-5%.
  • the present invention provides an inorganic composite material having PTC properties by combining a nano ceramic material with a graphite-based carbon material coating agent.
  • the addition of the PTC inorganic composite material of the invention to the carbon slurry can effectively solve the problem of overheating of the carbon crystal plate and an increase in power runaway.
  • the PTC material allows the carbon crystal plate to have a frequency conversion function. When the temperature gradually reaches the set temperature, the increase in resistance causes the power to be appropriately weakened to adjust to a suitable power to control the temperature, thereby greatly saving energy compared to the conventional carbon crystal plate.
  • Nano-ceramic materials Compared with other materials with PTC properties, this inorganic type of material can effectively prevent the failure of PTC materials caused by decomposition, gas release and aging.
  • the graphite-based carbon material coating agent is coated on the outer surface of the ceramic material, the outer surface has good electrical conductivity, the inner surface has good insulation, and when used as an electric heating material, the far-infrared radiation effect can be improved, and mixed with other carbon materials. Improve the dispersion effect.
  • the graphite-based carbon material coating agent is a nano-sheet carbon material, and the nano-sheet carbon material has a thickness of 100 nm or less, preferably 50 nm or less, more preferably 30 nm or less, including nano-scale graphite, graphene oxide, and graphene. One or several mixtures, preferably graphene.
  • graphene itself has high electrical and thermal conductivity, and has the advantages of light weight, good flexibility, large-area use, and low oxidation resistance. It has far-infrared radiation performance more prominent than other carbon materials.
  • the heating element has the characteristics of high somatosensory temperature and good thermal comfort, so it has the characteristics of excellent electrothermal material.
  • the sheet structure of graphene is also more favorable for completing the coating of the nano ceramic inorganic material particles, and further improving the dispersibility of the inorganic material and the carbon material.
  • the structure of graphene itself includes a single-layer graphene structure and a multi-layer graphene structure, and may be a six-membered ring-shaped honeycomb layer structure of 1-10 layers of carbon, and may also be a single layer, a double layer or a 3-10 layer.
  • any combination of any one or more of the structures it is the graphene having such a lamellar structure that is composite coated with the nanoceramic inorganic material, so that the performance of the ceramic inorganic material is more excellent, and when used in subsequent use Longer life, and the use of graphene to increase the far-infrared ability in subsequent applications, so that heating comfort is further improved, and heating efficiency is improved to indirectly save energy.
  • the invention fully utilizes the advantages of the nano ceramic material and the graphite carbon material coating agent respectively, and the PTC inorganic composite material prepared by using the specific raw material of the invention improves the compatibility of the powder and the carbon slurry on the one hand, It helps to disperse the powder; on the other hand, it makes the surface of such insulator particles have certain conductivity.
  • the inventor has also optimized the optimal addition amount of each raw material through a large number of practices.
  • the amount of nano ceramic material is generally 75-95% (in terms of mass percentage), and may be 80-91%, more preferably 85.
  • the main components include one or more of metal oxides, non-metal oxides, and metal borides, including Ti, Si, Ba, Sn, Cu, Fe, Ag, B, One or several of the O and C elements, of course, if the conditions permit, the nano ceramic material can be prepared by itself.
  • the state of the nano ceramic material is powdery, because the powder shape is favorable for the subsequent uniform formation of the graphene composite.
  • the substance preferably has a particle size of between 0.1 and 10 ⁇ m, and may also be 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m or the like.
  • the nano ceramic material used in the present invention is different from the ordinary ceramic material, and the powder is ultra-fineized by nano-crystallization, so that the surface electronic structure and crystal structure of the ceramic material are changed, and a bulk material is produced.
  • the amount of the graphite-based carbon material coating agent is 1-20% (in terms of mass percentage), and may be 5-16%, more preferably 13%, or 2%, 3%, 4%, 6%. 7%, 8%, 9%, etc., the mass ratio of the nano-ceramic material to the graphite-based carbon material coating agent is controlled to be optimal between (5-9):1, and the compounding ratio is obtained under such a ratio.
  • PTC inorganic composite materials have superior performance in all aspects.
  • a dispersing agent is added to the raw material to stabilize the dispersed medium, improve the surface properties of the powder, and adjust the powder.
  • the kinetic action enables the graphite-based carbon material coating agent to effectively coat the inorganic material, and the conventional addition amount is 0.5-5% (in terms of mass percentage), and may also be 1-4%, more preferably 2%.
  • the addition amount may also be 0.7%, 0.9%, 1.2%, 1.4%, 2%, 3%, 4.5%, etc.
  • the amount of the dispersant added as an additive should not be too large (generally not more than 5%), so The range of quantities also needs to be strictly controlled.
  • the type of dispersing agent includes one or more of polyvinyl alcohol, polyethylene glycol, and polypropylene glycol.
  • the preferred choice of polyvinyl alcohol, the dispersing agent of the alcohol can substantially meet the dispersion requirement in the solution of the present invention, and does not need to be used.
  • Other dispersants such as silanes, these types of dispersants are not environmentally friendly, so they are not recommended.
  • the present invention also provides a preferred preparation method of the above composite material, which specifically includes the following steps:
  • Ethanol acts as a solvent to dissolve and disperse, and is not the main raw material.
  • the formula of Ming is not reflected, and there is no certain requirement for the addition amount.
  • the subsequent heat treatment is performed to remove the volatile components in the composite material, and the heat treatment is performed.
  • the temperature is controlled below 200 ° C, the better heat treatment temperature is controlled between 80-150 ° C, and the heat treatment time is 40-80 min, mainly to achieve the evaporation of the added solvent and dispersant.
  • the method of mixing uniformity includes one of ultrasonic, ball milling and agitation.
  • the operating conditions of the ball mill are: the ball milling time is controlled at 2-3 h, the rotation speed is controlled at 400-500 rpm, and the stirring operation condition is: the stirring time is controlled at 30. -40min, the speed is controlled at 700-800rpm, the operating conditions of the ultrasonic are: the ultrasonic power is controlled at 700-900W, and the ultrasonic time is controlled at 60-70min.
  • These three operation modes can be freely selected according to actual operating conditions, as long as they can be realized.
  • the method of mixing the raw materials uniformly can be used.
  • the PTC inorganic composite material of the invention has a good application in the carbon crystal heating plate, and the specific method is to uniformly mix the PTC inorganic composite material and the carbon slurry, and more preferably, the PTC inorganic composite material is added in the amount described above. 2 to 5 wt% of the mass of the carbon paste, in such a manner, a carbon slurry having enhanced PTC properties and far-infrared properties can be obtained.
  • the amount of addition of the PTC inorganic composite material is limited, and is not unlimitedly added.
  • the control is 2-5 wt% of the mass of the carbon paste, and may also be 3 wt% and 4 wt%.
  • the performance of the carbon crystal heating plate is optimal, and the service life is also the longest, if the taste is increased.
  • the addition of PTC inorganic composite material will not continue to enhance the performance of the carbon slurry, but will also have the opposite effect, so the addition amount is best controlled.
  • the present invention develops a novel PTC inorganic composite material, which is obtained by compounding an inorganic material such as a nano ceramic material with a graphite-based carbon material coating agent, and encapsulating the inorganic material itself by using a carbon material.
  • the material can be electrically conductive and has internal insulation effect.
  • the material can be applied to electric heating materials, for example, for carbon crystal heating plates, the performance is more stable, and there is no aging, flatulence, etc. The problem is to subvert the performance of the carbon crystal plate itself, greatly extending the service life, and at the same time bringing considerable economic benefits;
  • the preparation method of the PTC inorganic composite material of the present invention has the advantages of being able to completely retain the active ingredient of the raw material, and has the advantages of simple and easy operation, mild operating conditions, high temperature carbonization step, and the like, and can realize graphene and nano ceramics.
  • the two materials of the material are well compounded and have good performance when applied in the subsequent addition of carbon slurry;
  • the PTC inorganic composite material of the invention is added to the carbon slurry, which can effectively solve the problem of overheating of the carbon crystal plate and an increase in power runaway.
  • the PTC material allows the carbon crystal plate to have a frequency conversion function.
  • the increase in resistance causes the power to be appropriately weakened to adjust to a suitable power to control the temperature, thereby greatly saving energy compared to the conventional carbon crystal plate.
  • Example 1 is a graph showing changes in temperature of a carbon slurry having PTC properties prepared according to Example 3 of the present invention as a function of time.
  • the molar ratio of each element Ti is 5-15%, Si is 20-50%, Fe is 1-5%, B 5-10%, O 50-70%;
  • the obtained product is heat-treated to remove the polyvinyl alcohol, the heat treatment temperature is 200 ° C, the temperature is kept for 30 min, and the whole process is vacuum N 2 protection;
  • the heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 2 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
  • the molar ratio of each element Ba is 10-20%, Ti is 5-30%, Si is 5-10%, Ag is 5-10 %, O is 50-75%;
  • the obtained product is heat-treated to remove the polyethylene glycol, the heat treatment temperature is 150 ° C, the temperature is kept for 40 min, and the whole process is vacuum N 2 protection;
  • the heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 5 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
  • the molar ratio of each element Ti is 10-30%, Fe is 5-10%, Si is 10-20%, Cu 5-10%, Sn is 1-5%, O is 50-70%;
  • the obtained product is heat-treated to remove the polyethylene glycol, the heat treatment temperature is 150 ° C, the temperature is maintained for 80 min, and the whole process is vacuum N 2 protection;
  • the heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 4 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
  • the molar ratio of each element Ti is 10-30%, Fe is 5-10%, Si is 10-20%, Cu 5-10%, Sn is 1-5%, O is 50-70%;
  • the obtained product is heat-treated to remove the polyethylene glycol, the heat treatment temperature is 80 ° C, the heat preservation is 60 min, and the whole process is vacuum N 2 protection;
  • the heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 3 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
  • the molar ratio of each element Ti is 10-30%, Fe is 5-10%, Si is 10-20%, Cu 5-10%, Sn is 1-5%, O is 50-70%;
  • the obtained product is heat-treated to remove the polyethylene glycol, the heat treatment temperature is 150 ° C, the heat preservation is 60 min, and the whole process is vacuum N 2 protection;
  • the heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 3 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
  • the molar ratio of each element Ti is 10-30%, Fe is 5-10%, Si is 10-20%, Cu 5-10%, Sn is 1-5%, O is 50-70%;
  • the obtained product is heat-treated to remove the polyethylene glycol, the heat treatment temperature is 150 ° C, the heat is kept for 60 min, and the whole process is vacuum N 2 protection;
  • the heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 3 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
  • a water-soluble PTC functional conductive carbon paste prepared by the method of Example 1 of the CN101407628A patent.
  • the carbon paste prepared in Example 3 and Comparative Example 1 was subjected to temperature change with time.
  • the specific results can be seen in the accompanying drawings of FIG. 1.
  • the carbon paste resistance of the organic material PTC material added in Comparative Example 1 is The response of the temperature has a certain delay, and the resistance is gradually increased to lower the temperature after the residence time is longer in the high temperature phase.
  • the inorganic PTC material of Embodiment 3 of the present invention reaches the temperature warning point, the resistance increases immediately and the temperature is quickly lowered, and the subsequent process is stable overall, precisely because of the present invention.
  • the material has sufficient smoothness in temperature, which greatly extends the life of the material itself in subsequent use.

Abstract

A PTC inorganic composite material manufactured using the following primary raw materials, in weight percentage: 75-95% of a nanoceramic, 1-20% of a graphite carbon coating agent, and 0.5-5% of a dispersant. The manufacturing method comprises: uniformly mixing the nanoceramic and the graphite carbon coating agent, then adding the dispersant and a suitable amount of ethanol to obtain a homogenized solution, and performing heat processing with an inert gas protection and a maximum temperature of 200°C. The method combines the nanoceramic with the graphite carbon coating agent. A carbon material is used to coat an inorganic particle, achieving electrical conductivity by means of the carbon material and insulation provided by an interior material. The composite material can be applied in an electroheating material, such as a carbon crystal heating panel.

Description

一种PTC无机复合材料及其制备方法、应用PTC inorganic composite material, preparation method and application thereof
相关申请的交叉引用Cross-reference to related applications
本申请要求于2016年05月20日提交中国专利局的申请号为201610343555.5、名称为“一种PTC无机复合材料及其制备方法、应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。The present application claims priority to Chinese Patent Application No. 201610343555.5, entitled "A PTC Inorganic Composite Material and Its Preparation Method, Application", filed on May 20, 2016, the entire contents of which are incorporated by reference. In this application.
技术领域Technical field
本发明涉及具有PTC性质的复合材料制备领域，具体而言，涉及一种PTC无机复合材料及其制备方法、应用。The invention relates to the field of composite material preparation with PTC properties, in particular to a PTC inorganic composite material and a preparation method and application thereof.
背景技术Background technique
碳晶发热板是一种新兴的采暖产品，经过近十年的发展，技术日趋成熟。其特点有：1.颠覆采暖传统，节能环保减排，适应国家和社会的新要求；2.无渗水漏水烦恼、无统一采暖费用收取的烦恼。安装使用方便，即开即热；3.具有保健理疗作用；波长在8-18微米，人长期在此环境中，有利于身体的健康。4.依靠远红外发热和空气对流，安静、无噪音，体感舒适度较高；5.不干燥，释放的是远红外线，不带走空气中的水分。Carbon crystal heating plate is an emerging heating product. After nearly ten years of development, the technology is becoming more mature. Its characteristics are: 1. Subverting the heating tradition, saving energy and reducing emissions, adapting to the new requirements of the state and society; 2. No troubles with water seepage and water leakage, no troubles for collecting uniform heating costs. It is easy to install and use, that is, it is hot immediately; 3. It has the function of health care; the wavelength is 8-18 microns, and people in this environment for a long time are beneficial to the health of the body. 4. Relying on far-infrared heating and air convection, quiet, no noise, high sense of comfort; 5. Do not dry, release far infrared rays, do not take away the moisture in the air.
然而碳晶板也有着自身的缺点，其中最主要的是温度叠加问题。权威部门近年来不敢力推电热地暖主要原因，很大程度上是现有技术中存在的因控制***失灵或局部复盖物过厚所产生的过热现象，如不消除不安全隐患，易导致火灾事故的发生。该隐患的主要原因是目前大多数材料都为负温度系数材料，即随着温度升高或长期反复加热，材料的电阻会减小，从而导致电流 和功率增大。特别是在表面有覆盖物的情况下，功率和电流的增大会进一步使温度提高导致恶性循环而引发安全隐患。However, carbon crystal plates also have their own shortcomings, the most important of which is the temperature superposition problem. In recent years, the authoritative department has not dared to push the main cause of electric heating, which is largely due to the overheating phenomenon caused by the failure of the control system or the excessive coverage of the local covering in the prior art. If the unsafe hidden danger is not eliminated, it is easy to cause The occurrence of a fire accident. The main cause of this hidden danger is that most materials are currently negative temperature coefficient materials, that is, as the temperature rises or the heating is repeated for a long time, the resistance of the material decreases, resulting in current. And power increases. Especially in the case of a covering on the surface, an increase in power and current will further increase the temperature, causing a vicious cycle and causing a safety hazard.
针对此难题，解决方法有：(1)开发PTC材料，即正温度系数材料，当超过一定温度时，该种材料的电阻值会随着温度升高而增高。电阻增高则电流和功率下降，如此反复可以使温度在目标温度附近上下波动而不至于过热。(2)安装温控器，使用温控器对每一块板都进行监测一方面大大提高了成本，另一方面在温控器故障的情况下会导致局部高热现象，严重时可能发生火灾。To solve this problem, the solutions are as follows: (1) Develop a PTC material, that is, a material with a positive temperature coefficient. When a certain temperature is exceeded, the resistance value of the material increases with temperature. When the resistance is increased, the current and power are decreased, and the repetition can cause the temperature to fluctuate up and down around the target temperature without overheating. (2) Installing the thermostat, using the thermostat to monitor each board greatly increases the cost. On the other hand, in the case of a malfunction of the thermostat, local high heat may occur, and in a serious case, a fire may occur.
现有技术中对于用在碳晶板上的PTC材料的研发层出不穷，比如专利CN101407628A公开了一种水溶性PTC功能导电碳浆的制造方法，CN104371329A专利中公开了一种含有氧化物的高分子碳浆及具有PTC效应的加热材料的制备方法，CN202652568U专利中公开了一种PTC碳浆恒温电热膜，CN105415830A专利中公开了一种具有PTC效应远红外辐射发热布及其制备方法和用途，但是这些技术中所采用的PTC材料均为高分子材料或碳浆与银浆的复合物，包括聚乙烯、聚氨酯、硬脂酸、单甘酯、甘油、乙二醇丁醚醋酸酯、异硫氰酸酯、银浆等。此类材料并不稳定，在反复加热的过程中，高分子材料或银会局部发生分解、释放气体、老化、氧化(银)等一系列问题，造成导电性不均、胀气、电阻逐渐降低从而失去了PTC材料的作用，严重影响材料本身的使用寿命。In the prior art, the development of PTC materials for use on carbon crystal plates is endless. For example, patent CN101407628A discloses a method for producing a water-soluble PTC functional conductive carbon paste, and a polymer-containing carbon containing oxide is disclosed in CN104371329A. A method for preparing a slurry and a heating material having a PTC effect, a PTC carbon slurry constant temperature electric heating film is disclosed in the CN202652568U patent, and a PTC effect far infrared radiation heating cloth and a preparation method and use thereof are disclosed in the CN105415830A patent, but these The PTC materials used in the technology are polymer materials or composites of carbon paste and silver paste, including polyethylene, polyurethane, stearic acid, monoglyceride, glycerin, ethylene glycol butyl ether acetate, isothiocyanate. Ester, silver paste, etc. Such materials are not stable. In the process of repeated heating, polymer materials or silver will locally decompose, release gases, aging, oxidation (silver) and other problems, resulting in uneven conductivity, flatulence, and electrical resistance. Loss of the role of PTC materials, seriously affecting the life of the material itself.
另外，虽然现有技术中已存在PTC陶瓷材料，但都是通过烧结后作为电子器件直接使用，例如CN104311004A公开了一种PTC陶瓷材料及提高PTC陶瓷材料居里点以下电阻温度稳定性的方法，所述PTC陶瓷材料组成的化学式为Ba1-x-yCaxYyTi1.01O3-aAl2O3-bSiO2-cMnCO3，其中，x＝0.04～0.06，y＝0.004-0.007，a＝0.02～0.04，b＝0.2～0.3，c＝0.05-0.07。再例如，CN102173786A 公开了一种新型PTC陶瓷材料组成物，该组成物包括陶瓷相和玻璃相，其特征在于：所述陶瓷相为常规PTC陶瓷材料，所述玻璃相为PbO-BN材料，所述PbO-BN材料的含量为1-10wt％，PTC陶瓷材料的含量为90-99wt％。本产品采用PbO-BN玻璃相作降低PTC陶瓷材料烧结温度，同时具有高性能PTC特性，使用范围广。可以看出，无机陶瓷PTC材料都是作为电子器件独立使用，并且都需要经过高温烧结。In addition, although PTC ceramic materials exist in the prior art, they are directly used as electronic devices after sintering. For example, CN104311004A discloses a PTC ceramic material and a method for improving the temperature stability of the PTC ceramic material below the Curie point. The chemical formula of the PTC ceramic material is Ba1-x-yCaxYyTi1.01O 3 -aAl 2 O 3 -bSiO 2 -cMnCO 3 , wherein x=0.04-0.06, y=0.004-0.007, a=0.02-0.04, b = 0.2 to 0.3, c = 0.05 to 0.07. For another example, CN102173786A discloses a novel PTC ceramic material composition comprising a ceramic phase and a glass phase, characterized in that the ceramic phase is a conventional PTC ceramic material and the glass phase is a PbO-BN material. The content of the PbO-BN material is 1-10% by weight, and the content of the PTC ceramic material is 90-99% by weight. This product uses PbO-BN glass phase to reduce the sintering temperature of PTC ceramic materials, and has high-performance PTC characteristics and a wide range of applications. It can be seen that inorganic ceramic PTC materials are used independently as electronic devices and both require high temperature sintering.
有鉴于此，特提出本发明。In view of this, the present invention has been specifically proposed.
发明内容Summary of the invention
本发明的第一目的在于提供一种PTC无机复合材料通过将纳米陶瓷材料这种无机材料与石墨类碳材料包覆剂进行复合，并利用碳材料对无机材料本身颗粒的包裹，实现碳材料可导电，内部绝缘的效果，该材料可应用于电加热材料上，例如用于碳晶发热板上，性能更加稳定，不会出现老化、胀气等问题，给碳晶板本身的性能带来颠覆性地提升，大大延长了使用寿命，并同时带来了可观的经济效益。A first object of the present invention is to provide a PTC inorganic composite material by combining a nano ceramic material such as an inorganic material with a graphite-based carbon material coating agent, and using a carbon material to encapsulate the inorganic material itself, thereby realizing the carbon material. Conductive, internal insulation effect, the material can be applied to electric heating materials, for example, for carbon crystal heating plates, the performance is more stable, there will be no problems such as aging, flatulence, etc., which will bring subversive properties to the performance of the carbon crystal plate itself. The ground lift greatly prolongs the service life and brings considerable economic benefits.
本发明的第二目的在于提供上述PTC无机复合材料的制备方法，制备方法具有能完整保留原料的有效成份的优点，而且具有方法简单易于操作，操作条件温和，无需高温碳化步骤等优点。A second object of the present invention is to provide a method for preparing the above PTC inorganic composite material, which has the advantages of being able to completely retain the active ingredient of the raw material, and has the advantages of simple and easy operation, mild operating conditions, and no need for a high-temperature carbonization step.
本发明的第三目的在于提供上述PTC无机复合材料的应用，可有效解决碳晶板过热和功率失控增大问题，使碳晶板具有变频功能。在温度渐渐达到设定温度时，电阻增大使得功率适当减弱从而调整至适宜功率来控制温度，从而比传统碳晶板更为节能。A third object of the present invention is to provide the above-mentioned application of the PTC inorganic composite material, which can effectively solve the problem of overheating of the carbon crystal plate and increase of power runaway, and the carbon crystal plate has a frequency conversion function. As the temperature gradually reaches the set temperature, the increase in resistance causes the power to be appropriately attenuated to adjust to the appropriate power to control the temperature, thereby being more energy efficient than conventional carbon crystal plates.
为了实现本发明的上述目的，特采用以下技术方案：In order to achieve the above object of the present invention, the following technical solutions are adopted:
本发明实施例提供了一种PTC无机复合材料，主要由以下原料制得：以 质量百分比计，纳米陶瓷材料75-95％，石墨类碳材料包覆剂1-20％，分散剂0.5-5％。The embodiment of the invention provides a PTC inorganic composite material, which is mainly prepared from the following raw materials: Percentage of mass, nano-ceramic material 75-95%, graphite-based carbon material coating agent 1-20%, dispersing agent 0.5-5%.
现有技术中一般会采用高分子材料为原料来制备具有PTC性质的复合材料，但是高分子材料本身容易老化、胀气，这样当其与炭浆混合应用于碳晶发热板上，会因为高分子材料本身的性能问题限制其进一步的应用，大大降低碳晶发热板本身的使用寿命。本发明为了解决以上出现的技术问题，提供了一种将纳米陶瓷材料与石墨类碳材料包覆剂复合制备具有PTC性质的无机复合材料。将本发明这种PTC无机复合材料添加到碳浆中，可有效解决碳晶板过热和功率失控增大问题。PTC材料可使碳晶板具有变频功能。在温度渐渐达到设定温度时，电阻增大使得功率适当减弱从而调整至适宜功率来控制温度，从而比传统碳晶板大大节能。In the prior art, a polymer material is generally used as a raw material to prepare a composite material having PTC properties, but the polymer material itself is prone to aging and flatulence, so that when it is mixed with a carbon slurry for use on a carbon crystal heating plate, it is because of a polymer. The performance problems of the material itself limit its further application and greatly reduce the service life of the carbon crystal heating plate itself. In order to solve the above-mentioned technical problems, the present invention provides an inorganic composite material having PTC properties by combining a nano ceramic material with a graphite-based carbon material coating agent. The addition of the PTC inorganic composite material of the invention to the carbon slurry can effectively solve the problem of overheating of the carbon crystal plate and an increase in power runaway. The PTC material allows the carbon crystal plate to have a frequency conversion function. When the temperature gradually reaches the set temperature, the increase in resistance causes the power to be appropriately weakened to adjust to a suitable power to control the temperature, thereby greatly saving energy compared to the conventional carbon crystal plate.
纳米陶瓷材料与其他具有PTC性质的材料相比，这种无机类型的材料可有效防止分解、释放气体、老化而带来的PTC材料的失效问题。Nano-ceramic materials Compared with other materials with PTC properties, this inorganic type of material can effectively prevent the failure of PTC materials caused by decomposition, gas release and aging.
石墨类碳材料包覆剂包覆到陶瓷材料外表面，外表面具有良好的导电性，内部具有良好的绝缘性，并且当用作电加热材料是能够提高远红外辐射效果，与其他碳材料混合时提高分散效果。The graphite-based carbon material coating agent is coated on the outer surface of the ceramic material, the outer surface has good electrical conductivity, the inner surface has good insulation, and when used as an electric heating material, the far-infrared radiation effect can be improved, and mixed with other carbon materials. Improve the dispersion effect.
石墨类碳材料包覆剂为纳米片层碳材料，所述纳米片层碳材料的厚度在100nm以下，优选在50nm以下，更优选30nm以下，包括纳米级石墨，氧化石墨烯，石墨烯中的一种或几种的混合，优选石墨烯。石墨烯本身作为新兴的碳材料，具有高导电导热性能的同时，具有轻便、柔韧性好、可大面积使用、不易氧化等优点，具有比其它碳材料更加突出的远红外辐射性能，制成的加热元器件具有体感温度高、热舒适性好的特点，因此具备优异电热材料的特点。 The graphite-based carbon material coating agent is a nano-sheet carbon material, and the nano-sheet carbon material has a thickness of 100 nm or less, preferably 50 nm or less, more preferably 30 nm or less, including nano-scale graphite, graphene oxide, and graphene. One or several mixtures, preferably graphene. As an emerging carbon material, graphene itself has high electrical and thermal conductivity, and has the advantages of light weight, good flexibility, large-area use, and low oxidation resistance. It has far-infrared radiation performance more prominent than other carbon materials. The heating element has the characteristics of high somatosensory temperature and good thermal comfort, so it has the characteristics of excellent electrothermal material.
另外，石墨烯的片层结构也更有利于完成对纳米陶瓷无机材料颗粒的包覆，进一步提高无机材料与碳材料的分散性。石墨烯本身的结构既包含单层石墨烯结构又包含多层石墨烯结构，可以为1-10层碳的六元环蜂窝状片层结构，还可以为单层、双层或3-10层结构的中的任意一种或多种的组合，正是拥有这样片层结构的石墨烯对纳米陶瓷无机材料进行复合包覆后，才可以使得陶瓷无机材料的性能上更为优异，后续使用时寿命更长，并利用石墨烯增加后续应用时的远红外能力，使采暖舒适度进一步提高，提高了加热效率从而间接节能。In addition, the sheet structure of graphene is also more favorable for completing the coating of the nano ceramic inorganic material particles, and further improving the dispersibility of the inorganic material and the carbon material. The structure of graphene itself includes a single-layer graphene structure and a multi-layer graphene structure, and may be a six-membered ring-shaped honeycomb layer structure of 1-10 layers of carbon, and may also be a single layer, a double layer or a 3-10 layer. Any combination of any one or more of the structures, it is the graphene having such a lamellar structure that is composite coated with the nanoceramic inorganic material, so that the performance of the ceramic inorganic material is more excellent, and when used in subsequent use Longer life, and the use of graphene to increase the far-infrared ability in subsequent applications, so that heating comfort is further improved, and heating efficiency is improved to indirectly save energy.
本发明正是充分利用了纳米陶瓷材料与石墨类碳材料包覆剂各自的优点，采用本发明这种特定的原料制备出的PTC无机复合材料一方面提高了粉体与碳浆的兼容性，有助于粉体分散；另一方面使此类绝缘物颗粒表面具有一定的导电性。发明人也是经过大量的实践优化出了各原料的较优添加量，纳米陶瓷材料加量比较大一般为75-95％(以质量百分比计)，还可以为80-91％，更优为85％，除此之外还可以选择76％、77％、78％、79％以及85％等，所谓的纳米陶瓷材料可以直接通过市面上购买，市售的这种材料属于半成品，后续用于制备陶瓷之用，主要的成分包括金属氧化物、非金属氧化物、金属硼化物中的一种或几种组成，所含的元素包括Ti、Si、Ba、Sn、Cu、Fe、Ag、B、O、C元素中的一种或几种，当然如果条件允许也可自行制备纳米陶瓷材料，这种纳米陶瓷材料的状态呈粉体状，因为粉状有利于后续与石墨烯复合均匀形成均一的物质，粒度最好控制在0.1-10μm之间，还可以为1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm等。另外需要注意的是本发明采用的纳米陶瓷材料区别于普通的陶瓷材料，其通过纳米化将粉体超细化，使得陶瓷材料的表面电子结构和晶体结构发生变化，产生了块状材料所 不具有的特殊的效应，比如可以显著降低材料的烧结温度、节能能源，使陶瓷材料的组成结构致密化、均匀化，改善陶瓷材料的性能，提高其使用可靠性，可见发明人在挑选每一种原料时也是有具体要求的，并不是随意选择就可以得到的。The invention fully utilizes the advantages of the nano ceramic material and the graphite carbon material coating agent respectively, and the PTC inorganic composite material prepared by using the specific raw material of the invention improves the compatibility of the powder and the carbon slurry on the one hand, It helps to disperse the powder; on the other hand, it makes the surface of such insulator particles have certain conductivity. The inventor has also optimized the optimal addition amount of each raw material through a large number of practices. The amount of nano ceramic material is generally 75-95% (in terms of mass percentage), and may be 80-91%, more preferably 85. %, in addition to 76%, 77%, 78%, 79% and 85%, so-called nano-ceramic materials can be directly purchased through the market, the commercially available materials are semi-finished products, and subsequently used for preparation. For ceramics, the main components include one or more of metal oxides, non-metal oxides, and metal borides, including Ti, Si, Ba, Sn, Cu, Fe, Ag, B, One or several of the O and C elements, of course, if the conditions permit, the nano ceramic material can be prepared by itself. The state of the nano ceramic material is powdery, because the powder shape is favorable for the subsequent uniform formation of the graphene composite. The substance preferably has a particle size of between 0.1 and 10 μm, and may also be 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or the like. In addition, it should be noted that the nano ceramic material used in the present invention is different from the ordinary ceramic material, and the powder is ultra-fineized by nano-crystallization, so that the surface electronic structure and crystal structure of the ceramic material are changed, and a bulk material is produced. The special effects that are not available, such as significantly reducing the sintering temperature of the material, energy-saving energy, densifying and homogenizing the composition of the ceramic material, improving the performance of the ceramic material, and improving the reliability of its use, it can be seen that the inventors are selecting each There are also specific requirements for the raw materials, which are not available at will.
石墨类碳材料包覆剂的添加量为1-20％(以质量百分比计)，还可以为5-16％，更优为13％，还可以选择2％、3％、4％、6％、7％、8％、9％等，将纳米陶瓷材料与石墨类碳材料包覆剂的质量比控制在(5-9):1之间为最佳，这样的配比条件下复合得到的PTC无机复合材料各方面性能均较优。The amount of the graphite-based carbon material coating agent is 1-20% (in terms of mass percentage), and may be 5-16%, more preferably 13%, or 2%, 3%, 4%, 6%. 7%, 8%, 9%, etc., the mass ratio of the nano-ceramic material to the graphite-based carbon material coating agent is controlled to be optimal between (5-9):1, and the compounding ratio is obtained under such a ratio. PTC inorganic composite materials have superior performance in all aspects.
当然为了提高分散性能，除了纳米陶瓷材料、石墨类碳材料包覆剂这两种主料，原料中还添加了分散剂，以起到稳定所分散的介质，改善粉体表面性质，调整粉体的运动性的作用，使石墨类碳材料包覆剂有效的包覆无机材料，其常规添加量为0.5-5％(以质量百分比计)，还可以为1-4％，更优为2％，例如添加量还可以为0.7％、0.9％、1.2％、1.4％、2％、3％、4.5％等，分散剂作为一种添加剂添加量不宜过大(一般不超过5％)，因此加量范围也需要严格控制。分散剂的种类包括聚乙烯醇、聚乙二醇、聚丙二醇中的一种或几种，较优的选择聚乙烯醇，醇类的分散剂基本可以满足本发明方案中的分散要求，无需采用其他比如硅烷类等分散剂，这些种类的分散剂本身不绿色环保，所以也不建议应用。Of course, in order to improve the dispersion performance, in addition to the two main materials of nano ceramic material and graphite carbon material coating agent, a dispersing agent is added to the raw material to stabilize the dispersed medium, improve the surface properties of the powder, and adjust the powder. The kinetic action enables the graphite-based carbon material coating agent to effectively coat the inorganic material, and the conventional addition amount is 0.5-5% (in terms of mass percentage), and may also be 1-4%, more preferably 2%. For example, the addition amount may also be 0.7%, 0.9%, 1.2%, 1.4%, 2%, 3%, 4.5%, etc., and the amount of the dispersant added as an additive should not be too large (generally not more than 5%), so The range of quantities also needs to be strictly controlled. The type of dispersing agent includes one or more of polyvinyl alcohol, polyethylene glycol, and polypropylene glycol. The preferred choice of polyvinyl alcohol, the dispersing agent of the alcohol can substantially meet the dispersion requirement in the solution of the present invention, and does not need to be used. Other dispersants such as silanes, these types of dispersants are not environmentally friendly, so they are not recommended.
本发明除了提供一种PTC无机复合材料，还提供了上述复合材料的一种较优的制备方法，具体包括如下步骤：In addition to providing a PTC inorganic composite material, the present invention also provides a preferred preparation method of the above composite material, which specifically includes the following steps:
将纳米陶瓷材料与石墨类碳材料包覆剂混合后，加入分散剂及适量乙醇混合均匀得到均一溶液，惰性气体保护条件下不高于200℃进行热处理，即可。After mixing the nano ceramic material with the graphite carbon material coating agent, adding a dispersing agent and an appropriate amount of ethanol to uniformly obtain a uniform solution, and heat treatment under an inert gas protection condition of not higher than 200 ° C.
乙醇作为一种溶剂起到溶解分散的作用，并不是主要原料，因此在本发 明的配方中并没有体现，添加量也没有确定的要求，只要能实现将各原料很好的融合为均一的物质即可，混合均匀后，后续热处理以去除复合材料中的挥发性成分，热处理的温度控制在200℃以下，更优的热处理温度控制在80-150℃之间，热处理时间为40-80min，主要是为了实现将添加进去的溶剂和分散剂挥发干净。Ethanol acts as a solvent to dissolve and disperse, and is not the main raw material. The formula of Ming is not reflected, and there is no certain requirement for the addition amount. As long as the raw materials can be well integrated into a uniform substance, after the mixing is uniform, the subsequent heat treatment is performed to remove the volatile components in the composite material, and the heat treatment is performed. The temperature is controlled below 200 ° C, the better heat treatment temperature is controlled between 80-150 ° C, and the heat treatment time is 40-80 min, mainly to achieve the evaporation of the added solvent and dispersant.
混合均匀的方式包括超声、球磨以及搅拌中的其中一种，球磨的操作条件为：球磨的时间控制在2-3h，转速控制在400-500rpm，搅拌的操作条件为：搅拌的时间控制在30-40min，转速控制在700-800rpm，超声的操作条件为：超声的功率控制在700-900W，超声的时间控制在60-70min，这三种操作方式可根据实际操作条件自由选择，只要能实现原料之间混合均匀的方式均可。The method of mixing uniformity includes one of ultrasonic, ball milling and agitation. The operating conditions of the ball mill are: the ball milling time is controlled at 2-3 h, the rotation speed is controlled at 400-500 rpm, and the stirring operation condition is: the stirring time is controlled at 30. -40min, the speed is controlled at 700-800rpm, the operating conditions of the ultrasonic are: the ultrasonic power is controlled at 700-900W, and the ultrasonic time is controlled at 60-70min. These three operation modes can be freely selected according to actual operating conditions, as long as they can be realized. The method of mixing the raw materials uniformly can be used.
本发明的PTC无机复合材料在碳晶发热板方面具有很好的应用，具体方法为将PTC无机复合材料与碳浆均匀混合，更优的为，所述PTC无机复合材料的添加量为所述碳浆质量的2-5wt％，通过这样的方式可获得具有PTC性质和远红外性能增强的碳浆，当然PTC无机复合材料的添加量是有一定的限度的，并不是无限制的添加的，控制为所述碳浆质量的2-5wt％，还可以为3wt％、4wt％，在这样的用量范围内碳晶发热板的各方面性能最优，使用寿命也达到最长，如果一味的增加PTC无机复合材料的添加量不但不会继续增强碳浆的性能，还会起到适得其反的效果，因此加量最好控制适宜。The PTC inorganic composite material of the invention has a good application in the carbon crystal heating plate, and the specific method is to uniformly mix the PTC inorganic composite material and the carbon slurry, and more preferably, the PTC inorganic composite material is added in the amount described above. 2 to 5 wt% of the mass of the carbon paste, in such a manner, a carbon slurry having enhanced PTC properties and far-infrared properties can be obtained. Of course, the amount of addition of the PTC inorganic composite material is limited, and is not unlimitedly added. The control is 2-5 wt% of the mass of the carbon paste, and may also be 3 wt% and 4 wt%. In such a range, the performance of the carbon crystal heating plate is optimal, and the service life is also the longest, if the taste is increased. The addition of PTC inorganic composite material will not continue to enhance the performance of the carbon slurry, but will also have the opposite effect, so the addition amount is best controlled.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
(1)本发明开发了一种新型的PTC无机复合材料，通过将纳米陶瓷材料这种无机材料与石墨类碳材料包覆剂进行复合，并利用碳材料对无机材料本身颗粒的包裹，实现碳材料可导电，内部绝缘的效果，该材料可应用于电加热材料上，例如用于碳晶发热板上，性能更加稳定，不会出现老化、胀气等 问题，给碳晶板本身的性能带来颠覆性地提升，大大延长了使用寿命，并同时带来了可观的经济效益；(1) The present invention develops a novel PTC inorganic composite material, which is obtained by compounding an inorganic material such as a nano ceramic material with a graphite-based carbon material coating agent, and encapsulating the inorganic material itself by using a carbon material. The material can be electrically conductive and has internal insulation effect. The material can be applied to electric heating materials, for example, for carbon crystal heating plates, the performance is more stable, and there is no aging, flatulence, etc. The problem is to subvert the performance of the carbon crystal plate itself, greatly extending the service life, and at the same time bringing considerable economic benefits;
(2)本发明的PTC无机复合材料的制备方法本身具有能完整保留原料的有效成份的优点，而且具有方法简单易于操作，操作条件温和，无需高温碳化步骤等优点，能够实现石墨烯、纳米陶瓷材料这两种原料很好的复合，并在后续加入碳浆中应用时，具有很好的性能；(2) The preparation method of the PTC inorganic composite material of the present invention has the advantages of being able to completely retain the active ingredient of the raw material, and has the advantages of simple and easy operation, mild operating conditions, high temperature carbonization step, and the like, and can realize graphene and nano ceramics. The two materials of the material are well compounded and have good performance when applied in the subsequent addition of carbon slurry;
(3)本发明的PTC无机复合材料添加到碳浆中，可有效解决碳晶板过热和功率失控增大问题。PTC材料可使碳晶板具有变频功能。在温度渐渐达到设定温度时，电阻增大使得功率适当减弱从而调整至适宜功率来控制温度，从而比传统碳晶板大大节能。(3) The PTC inorganic composite material of the invention is added to the carbon slurry, which can effectively solve the problem of overheating of the carbon crystal plate and an increase in power runaway. The PTC material allows the carbon crystal plate to have a frequency conversion function. When the temperature gradually reaches the set temperature, the increase in resistance causes the power to be appropriately weakened to adjust to a suitable power to control the temperature, thereby greatly saving energy compared to the conventional carbon crystal plate.
附图说明DRAWINGS
为了更清楚地说明本发明实施例或现有技术中的技术方案，以下将对实施例或现有技术描述中所需要使用的附图作简单地介绍。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art description will be briefly described below.
图1为本发明实施例三制备得到的具有PTC性质的碳浆的温度随时间变化的曲线图。1 is a graph showing changes in temperature of a carbon slurry having PTC properties prepared according to Example 3 of the present invention as a function of time.
具体实施方式detailed description
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。The embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but the present invention is to be construed as illustrative only. Those who do not specify the specific conditions in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are conventional products that can be obtained by commercially available purchase.
实施例1Example 1
1)采用由金属氧化物、非金属氧化物、金属硼化物组成的纳米陶瓷材料中，各元素摩尔比，Ti为5-15％，Si为20-50％，Fe为1-5％，B为5-10％，O 为50-70％；1) In the nano ceramic material composed of metal oxide, non-metal oxide and metal boride, the molar ratio of each element, Ti is 5-15%, Si is 20-50%, Fe is 1-5%, B 5-10%, O 50-70%;
2)将上述纳米陶瓷材料75kg，厚度在100nm以下的纳米级石墨20kg，随后加入0.5kg的聚乙烯醇和适量乙醇至溶液状态，使用细胞粉碎机进行混合粉碎30min，转速控制在800rpm；2) 75 kg of the above nano ceramic material, 20 kg of nano-scale graphite having a thickness of 100 nm or less, followed by adding 0.5 kg of polyvinyl alcohol and an appropriate amount of ethanol to a solution state, mixing and pulverizing using a cell pulverizer for 30 minutes, and controlling the rotation speed at 800 rpm;
3)将乙醇蒸干后，对获得物进行热处理以去除聚乙烯醇，热处理温度为200℃，保温30min，全程真空N2保护；3) After evaporating the ethanol, the obtained product is heat-treated to remove the polyvinyl alcohol, the heat treatment temperature is 200 ° C, the temperature is kept for 30 min, and the whole process is vacuum N 2 protection;
4)热处理产物研末过筛后与碳浆进行均匀复合，添加比例为2wt％，即获得具有PTC性质和远红外性能增强的碳浆。4) The heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 2 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
实施例2Example 2
1)采用由金属氧化物、非金属氧化物组成的纳米陶瓷材料中，各元素摩尔比，Ba为10-20％，Ti为5-30％，Si为5-10％，Ag为5-10％，O为50-75％；1) In the nano ceramic material composed of metal oxide and non-metal oxide, the molar ratio of each element, Ba is 10-20%, Ti is 5-30%, Si is 5-10%, Ag is 5-10 %, O is 50-75%;
2)将上述纳米陶瓷材料95kg，厚度在50nm以下的氧化石墨烯10kg，随后加入5kg的聚乙二醇和适量乙醇至溶液状态，使用真空球磨机进行球磨2h，转速为500rpm；2) 95 kg of the above nano ceramic material, 10 kg of graphene oxide having a thickness of 50 nm or less, followed by adding 5 kg of polyethylene glycol and an appropriate amount of ethanol to a solution state, ball milling for 2 h using a vacuum ball mill, and rotating at 500 rpm;
3)将乙醇蒸干后，对获得物进行热处理以去除聚乙二醇，热处理温度为150℃，保温40min，全程真空N2保护；3) After evaporating the ethanol, the obtained product is heat-treated to remove the polyethylene glycol, the heat treatment temperature is 150 ° C, the temperature is kept for 40 min, and the whole process is vacuum N 2 protection;
4)热处理产物研末过筛后与碳浆进行均匀复合，添加比例为5wt％，即获得具有PTC性质和远红外性能增强的碳浆。4) The heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 5 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
实施例3Example 3
1)采用由金属氧化物、非金属氧化物、金属硼化物组成的纳米陶瓷材料中，各元素摩尔比，Ti为10-30％，Fe为5-10％，Si为10-20％，Cu为5-10％，Sn为1-5％，O为50-70％；1) In the nano ceramic material composed of metal oxide, non-metal oxide and metal boride, the molar ratio of each element, Ti is 10-30%, Fe is 5-10%, Si is 10-20%, Cu 5-10%, Sn is 1-5%, O is 50-70%;
2)将上述纳米陶瓷材料80kg，厚度在30nm以下的石墨烯1kg，随后加 入1kg的聚乙二醇和适量乙醇至溶液状态，700W超声60min；2) 80 kg of the above-mentioned nano ceramic material, 1 kg of graphene having a thickness of 30 nm or less, and then added Add 1kg of polyethylene glycol and appropriate amount of ethanol to the solution state, 700W ultrasonic for 60min;
3)将乙醇蒸干后，对获得物进行热处理以去除聚乙二醇，热处理温度为150℃，保温80min，全程真空N2保护；3) After evaporating the ethanol, the obtained product is heat-treated to remove the polyethylene glycol, the heat treatment temperature is 150 ° C, the temperature is maintained for 80 min, and the whole process is vacuum N 2 protection;
4)热处理产物研末过筛后与碳浆进行均匀复合，添加比例为4wt％，即获得具有PTC性质和远红外性能增强的碳浆。4) The heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 4 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
实施例4Example 4
1)采用由金属氧化物、非金属氧化物、金属硼化物组成的纳米陶瓷材料中，各元素摩尔比，Ti为10-30％，Fe为5-10％，Si为10-20％，Cu为5-10％，Sn为1-5％，O为50-70％；1) In the nano ceramic material composed of metal oxide, non-metal oxide and metal boride, the molar ratio of each element, Ti is 10-30%, Fe is 5-10%, Si is 10-20%, Cu 5-10%, Sn is 1-5%, O is 50-70%;
2)将上述纳米陶瓷材料91kg，石墨烯16kg，随后加入4kg的聚乙二醇和适量乙醇至溶液状态，900W超声70min；2) 91kg of the above nano ceramic material, 16kg of graphene, followed by adding 4kg of polyethylene glycol and an appropriate amount of ethanol to the solution state, 900W ultrasonic 70min;
3)将乙醇蒸干后，对获得物进行热处理以去除聚乙二醇，热处理温度为80℃，保温60min，全程真空N2保护；3) After evaporating the ethanol, the obtained product is heat-treated to remove the polyethylene glycol, the heat treatment temperature is 80 ° C, the heat preservation is 60 min, and the whole process is vacuum N 2 protection;
4)热处理产物研末过筛后与碳浆进行均匀复合，添加比例为3wt％，即获得具有PTC性质和远红外性能增强的碳浆。4) The heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 3 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
实施例5Example 5
1)采用由金属氧化物、非金属氧化物、金属硼化物组成的纳米陶瓷材料中，各元素摩尔比，Ti为10-30％，Fe为5-10％，Si为10-20％，Cu为5-10％，Sn为1-5％，O为50-70％；1) In the nano ceramic material composed of metal oxide, non-metal oxide and metal boride, the molar ratio of each element, Ti is 10-30%, Fe is 5-10%, Si is 10-20%, Cu 5-10%, Sn is 1-5%, O is 50-70%;
2)将上述纳米陶瓷材料85kg，石墨烯与纳米级石墨的混合物5kg，随后加入2kg的聚乙二醇和适量乙醇至溶液状态，使用真空球磨机进行球磨3h，转速为400rpm；2) 85kg of the above nano ceramic material, a mixture of graphene and nano-scale graphite, followed by adding 2kg of polyethylene glycol and an appropriate amount of ethanol to a solution state, ball milling using a vacuum ball mill for 3h, the rotation speed is 400rpm;
3)将乙醇蒸干后，对获得物进行热处理以去除聚乙二醇，热处理温度为 150℃，保温60min，全程真空N2保护；3) After evaporating the ethanol, the obtained product is heat-treated to remove the polyethylene glycol, the heat treatment temperature is 150 ° C, the heat preservation is 60 min, and the whole process is vacuum N 2 protection;
4)热处理产物研末过筛后与碳浆进行均匀复合，添加比例为3wt％，即获得具有PTC性质和远红外性能增强的碳浆。4) The heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 3 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
实施例6Example 6
1)采用由金属氧化物、非金属氧化物、金属硼化物组成的纳米陶瓷材料中，各元素摩尔比，Ti为10-30％，Fe为5-10％，Si为10-20％，Cu为5-10％，Sn为1-5％，O为50-70％；1) In the nano ceramic material composed of metal oxide, non-metal oxide and metal boride, the molar ratio of each element, Ti is 10-30%, Fe is 5-10%, Si is 10-20%, Cu 5-10%, Sn is 1-5%, O is 50-70%;
2)将上述纳米陶瓷材料85kg，石墨烯13kg，随后加入2kg的聚乙二醇和适量乙醇至溶液状态，使用细胞粉碎机进行混合粉碎40min，转速控制在700rpm；2) 85 kg of the above-mentioned nano ceramic material, 13 kg of graphene, followed by adding 2 kg of polyethylene glycol and an appropriate amount of ethanol to a solution state, using a cell pulverizer for mixing and pulverizing for 40 min, the rotation speed is controlled at 700 rpm;
3)将乙醇蒸干后，对获得物进行热处理以去除聚乙二醇，热处理温度为150℃，保温60min，全程真空N2保护；3) After evaporating the ethanol, the obtained product is heat-treated to remove the polyethylene glycol, the heat treatment temperature is 150 ° C, the heat is kept for 60 min, and the whole process is vacuum N 2 protection;
4)热处理产物研末过筛后与碳浆进行均匀复合，添加比例为3wt％，即获得具有PTC性质和远红外性能增强的碳浆。4) The heat-treated product is sieved and uniformly compounded with the carbon slurry, and the addition ratio is 3 wt%, that is, a carbon slurry having PTC properties and enhanced far-infrared properties is obtained.
比较例1Comparative example 1
采用CN101407628A专利中实施例1的方法制备出的水溶性PTC功能导电碳浆。A water-soluble PTC functional conductive carbon paste prepared by the method of Example 1 of the CN101407628A patent.
实验例1Experimental example 1
将实施例3与比较例1制备出的碳浆做温度随时间的变化曲线图，具体结果可见说明书附图1，从图1中可以看出比较例1添加了有机物PTC材料的碳浆电阻对于温度的响应具有一定延迟，在高温阶段停留时间比较长后电阻才逐渐增大从而降低温度。而本发明实施例3的无机PTC材料达到温度警戒点后立刻电阻增大并迅速把温度将下来，后续过程整体平稳，正是因为本发明这种 材料在温度上具有足够的平稳性，使得后续使用时大大延长了材料本身的寿命。The carbon paste prepared in Example 3 and Comparative Example 1 was subjected to temperature change with time. The specific results can be seen in the accompanying drawings of FIG. 1. It can be seen from FIG. 1 that the carbon paste resistance of the organic material PTC material added in Comparative Example 1 is The response of the temperature has a certain delay, and the resistance is gradually increased to lower the temperature after the residence time is longer in the high temperature phase. When the inorganic PTC material of Embodiment 3 of the present invention reaches the temperature warning point, the resistance increases immediately and the temperature is quickly lowered, and the subsequent process is stable overall, precisely because of the present invention. The material has sufficient smoothness in temperature, which greatly extends the life of the material itself in subsequent use.
另外，将其他实施例与比较例1通过作图对比后，也会呈现相同的实验结果。In addition, after comparing other examples with Comparative Example 1, the same experimental results were also exhibited.
尽管已用具体实施例来说明和描述了本发明，然而应意识到，在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。 While the invention has been illustrated and described with reference to the embodiments of the present invention, it will be understood that many modifications and changes can be made without departing from the spirit and scope of the invention. Accordingly, it is intended to embrace in the appended claims

Claims (10)

  1. 一种PTC无机复合材料，其特征在于，主要由以下原料制得：以质量百分比计，纳米陶瓷材料75-95％，石墨类碳材料包覆剂1-20％，分散剂0.5-5％。A PTC inorganic composite material, which is mainly prepared from the following raw materials: 75-95% of nano ceramic materials, 1-20% of graphite-based carbon material coating agent, and 0.5-5% of dispersing agent.
  2. 根据权利要求1所述的一种PTC无机复合材料，其特征在于，以质量百分比计，纳米陶瓷材料80-91％，石墨类碳材料包覆剂5-16％，分散剂1-4％。A PTC inorganic composite material according to claim 1, wherein the nano ceramic material is 80-91% by mass, the graphite-based carbon material coating agent is 5-16%, and the dispersing agent is 1-4%.
  3. 根据权利要求1或2所述的一种PTC无机复合材料，其特征在于，以质量百分比计，纳米陶瓷材料85％，石墨类碳材料包覆剂13％，分散剂2％。A PTC inorganic composite material according to claim 1 or 2, wherein the nano ceramic material is 85% by mass, the graphite-based carbon material coating agent is 13%, and the dispersing agent is 2%.
  4. 根据权利要求1或2所述的一种PTC无机复合材料，其特征在于，所述纳米陶瓷材料主要由金属氧化物、非金属氧化物、金属硼化物中的一种或几种组成；The PTC inorganic composite material according to claim 1 or 2, wherein the nano ceramic material is mainly composed of one or more of a metal oxide, a non-metal oxide, and a metal boride;
    优选地，所述纳米陶瓷材料的粒径控制在0.1-10μm。Preferably, the nano ceramic material has a particle size controlled between 0.1 and 10 μm.
  5. 根据权利要求4所述的一种PTC无机复合材料，其特征在于，所述纳米陶瓷材料中所含的元素包括Ti、Si、Ba、Sn、Cu、Fe、Ag、B、O、C元素中的一种或几种；The PTC inorganic composite material according to claim 4, wherein the elements contained in the nano ceramic material comprise Ti, Si, Ba, Sn, Cu, Fe, Ag, B, O, and C elements. One or several
    优选地，所述分散剂包括聚乙烯醇、聚乙二醇、聚丙二醇中的一种或几种。Preferably, the dispersing agent comprises one or more of polyvinyl alcohol, polyethylene glycol, and polypropylene glycol.
    所述石墨类碳材料包覆剂为纳米片层碳材料，所述纳米片层碳材料的厚度在100nm以下，优选在50nm以下，更优选30nm以下，包括纳米级石墨，氧化石墨烯，石墨烯中的一种或几种的混合。The graphite-based carbon material coating agent is a nano-sheet carbon material, and the nano-sheet carbon material has a thickness of 100 nm or less, preferably 50 nm or less, more preferably 30 nm or less, including nano-scale graphite, graphene oxide, graphene. a mixture of one or several of them.
  6. 权利要求1-5任一项所述的PTC无机复合材料的制备方法，其特征在于，包括如下步骤：The method for preparing a PTC inorganic composite material according to any one of claims 1 to 5, comprising the steps of:
    将纳米陶瓷材料与石墨类碳材料包覆剂混合后，加入分散剂及适量乙醇 混合均匀得到均一溶液，惰性气体保护条件下不高于200℃进行热处理，即可。After mixing the nano ceramic material with the graphite-based carbon material coating agent, adding a dispersing agent and an appropriate amount of ethanol The mixture is uniformly mixed to obtain a uniform solution, and the heat treatment is carried out under an inert gas protection condition of not higher than 200 ° C.
  7. 根据权利要求6所述的PTC无机复合材料的制备方法，其特征在于，加入分散剂及适量乙醇后混合均匀的方式包括超声、球磨以及搅拌中的其中一种。The method for preparing a PTC inorganic composite according to claim 6, wherein one of ultrasonication, ball milling, and agitation is performed by adding a dispersant and an appropriate amount of ethanol.
  8. 根据权利要求7所述的PTC无机复合材料的制备方法，其特征在于，球磨的时间控制在2-3h，转速控制在400-500rpm；The method for preparing a PTC inorganic composite material according to claim 7, wherein the ball milling time is controlled at 2-3 hours, and the rotation speed is controlled at 400-500 rpm;
    优选地，搅拌的时间控制在30-40min，转速控制在700-800rpm；Preferably, the stirring time is controlled at 30-40 min, and the rotation speed is controlled at 700-800 rpm;
    优选地，超声的功率控制在700-900W，超声的时间控制在60-70min。Preferably, the power of the ultrasound is controlled at 700-900 W and the time of ultrasound is controlled at 60-70 min.
  9. 根据权利要求7所述的PTC无机复合材料的制备方法，其特征在于，热处理的温度控制在80-150℃，时间为40-80min。The method of preparing a PTC inorganic composite according to claim 7, wherein the temperature of the heat treatment is controlled at 80 to 150 ° C for 40 to 80 minutes.
  10. 权利要求1-5任一项所述的PTC无机复合材料在碳晶发热板方面的应用，其特征在于，将PTC无机复合材料与碳浆均匀混合，即可；优选地，所述PTC无机复合材料的添加量为所述碳浆质量的2-5wt％。 The use of the PTC inorganic composite material according to any one of claims 1 to 5 in a carbon crystal heating plate, characterized in that the PTC inorganic composite material and the carbon slurry are uniformly mixed; preferably, the PTC inorganic composite The material is added in an amount of 2 to 5% by weight based on the mass of the carbon paste.
PCT/CN2017/085396 2016-05-20 2017-05-22 Ptc inorganic composite material, and manufacturing method and application thereof WO2017198233A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106467412B (en) * 2016-05-20 2020-02-04 济南圣泉集团股份有限公司 PTC inorganic composite material and preparation method and application thereof
CN107374941A (en) * 2017-05-23 2017-11-24 于长江 Quantum, moxibustion material and its application for moxibustion
CN108383521A (en) * 2018-05-16 2018-08-10 奥普家居股份有限公司 A kind of BaTiO3The preparation method of potsherd
CN110611964B (en) * 2018-06-14 2022-05-24 浙江汉纳新材料科技有限公司 Heating film material with PTC effect and preparation method thereof
CN111099917B (en) * 2018-10-29 2022-01-04 中国石油化工股份有限公司 Porous composite material for generating electric arc in microwave and preparation method thereof
CN115475743B (en) * 2022-10-28 2023-05-23 江苏萃隆精密铜管股份有限公司 Condenser tube manufacturing process of condenser

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1632886A (en) * 2004-12-27 2005-06-29 天津大学 Ni/graphite (Ba-[1-x-y],Sr-[x],Pb-[y])TiO-[3] base composite PTC thermistor and preparing method
CN101407415A (en) * 2008-11-24 2009-04-15 天津大学 Ni/graphite/BaTiO3-based composite positive temperature coefficient thermistor and preparation thereof
CN102532669A (en) * 2012-01-12 2012-07-04 上海交通大学 High polymer-based graphene composite material with positive resistance temperature coefficient and preparation method
CN106467412A (en) * 2016-05-20 2017-03-01 济南圣泉集团股份有限公司 A kind of PTC inorganic composite materials and preparation method thereof, application

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008239747A (en) * 2007-03-27 2008-10-09 Tokai Rubber Ind Ltd Elastomer composite material
CN101407628B (en) * 2008-11-21 2011-05-04 天津市华林伟业科技发展有限公司 Method for producing water-soluble PTC functional conductive carbon paste
CN101550330A (en) * 2009-05-18 2009-10-07 浙江大学 Lightweight high heat conductive composite material and preparation method thereof
CN205069250U (en) * 2015-02-04 2016-03-02 上海长园维安电子线路保护有限公司 Novel PTC temperature sensitive element

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1632886A (en) * 2004-12-27 2005-06-29 天津大学 Ni/graphite (Ba-[1-x-y],Sr-[x],Pb-[y])TiO-[3] base composite PTC thermistor and preparing method
CN101407415A (en) * 2008-11-24 2009-04-15 天津大学 Ni/graphite/BaTiO3-based composite positive temperature coefficient thermistor and preparation thereof
CN102532669A (en) * 2012-01-12 2012-07-04 上海交通大学 High polymer-based graphene composite material with positive resistance temperature coefficient and preparation method
CN106467412A (en) * 2016-05-20 2017-03-01 济南圣泉集团股份有限公司 A kind of PTC inorganic composite materials and preparation method thereof, application

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