CN1185086A - A kind of inorganic composite resistive thin film and preparation method thereof - Google Patents

Abstract

An inorganic composite resistance film, coating an inorganic conductive resistance film 1 on the temperature-resistant insulating outer surface of a heating vessel or the temperature-resistant insulating heating surface 5 of an electric heating element, arranging a conductive electrode film 2 on the periphery of the film 1, arranging a conductive welding spot 3 on the conductive electrode film 2, and coating an insulating protective film 4 on the resistance film 1 and the outer surface of the electrode film. The resistance film is widely used for manufacturing electric heating cups, electric cookers, electric heating showers and various electric heating elements, has the advantages of simple structure, low cost, high heat efficiency, long service life, safety and reliability, is particularly convenient for heating surfaces with special shapes, non-uniform heating or local heating, is very convenient to clean due to water resistance and slight acid and alkali resistance, and greatly enlarges the application range.

Description

Translated fromChinese

一种无机复合电阻薄膜及其制备方法A kind of inorganic composite resistive thin film and preparation method thereof

本发明属于电热元件，具体涉及一种无机复合电阻薄膜及其制备方法。The invention belongs to electric heating elements, and in particular relates to an inorganic composite resistance film and a preparation method thereof.

电热器具自问世以来，有一百多年历史了。通常其电热元件采用电阻丝作为发热体，不仅热效率低，使用寿命短，成本也高。因此，早在50年代，就进行无机电阻薄膜作为电发热体的研制工作，我国在88年也已研制出无机电热膜，这种以无机电阻薄膜作为电发热体，热效率高，使用寿命长，成本也低，但这种无机电阻膜结构比较松散，强度低，由于一般都在裸露状态下使用，因而不仅在使用过程中很容易损坏，而且不耐水和轻度酸和碱，极大地限制了其使用范围。Electric heating appliances have a history of more than 100 years since they came out. Usually, the electric heating element adopts resistance wire as a heating element, which not only has low thermal efficiency, but also has a short service life and high cost. Therefore, as early as the 1950s, the development of inorganic resistance films as electric heating elements was carried out. In 1988, my country also developed inorganic electric heating films. This kind of inorganic resistance films as electric heating elements has high thermal efficiency and long service life. The cost is also low, but the structure of this inorganic resistance film is relatively loose and its strength is low. Since it is generally used in the bare state, it is not only easily damaged during use, but also not resistant to water and mild acid and alkali, which greatly limits its scope of use.

本发明针对上述现有无机电阻薄膜的不足，提供一种无机复合电阻薄膜及其制备方法。The present invention aims at the disadvantages of the above-mentioned existing inorganic resistance films, and provides an inorganic composite resistance film and a preparation method thereof.

本发明所述的无机复合电阻薄膜，是专指一种与加热器皿的耐温绝缘外表面或电热元件的耐温绝缘加热面结合成一体的无机导电电阻薄膜，其特征在于在上述加热器皿的耐温绝缘外表面或电热元件的耐温绝缘加热面(以下简称绝缘底材)上涂复一层厚约0.05～1mm的无机导电电阻薄膜，在该无机导电电阻薄膜的周边设厚约0.1～0.3mm导电电极薄膜，在该导电电极薄膜上设厚约0.1～0.6mm的导电焊点3，在无机导电电阻薄膜及电极薄膜的外表面涂复一层厚约0.1～0.6mm的绝缘保护膜。The inorganic composite resistance film of the present invention refers to an inorganic conductive resistance film integrated with the temperature-resistant insulating outer surface of the heating vessel or the temperature-resistant insulating heating surface of the electric heating element, which is characterized in that A layer of inorganic conductive resistance film with a thickness of about 0.05 to 1 mm is coated on the outer surface of the temperature-resistant insulation or the temperature-resistant and insulating heating surface of the electric heating element (hereinafter referred to as the insulating substrate), and a thickness of about 0.1 to 1 mm is arranged around the inorganic conductive resistance film. 0.3mm conductive electrode film, on which aconductive solder joint 3 with a thickness of about 0.1-0.6mm is arranged, and an insulating protective film with a thickness of about 0.1-0.6mm is coated on the outer surface of the inorganic conductive resistance film and the electrode film .

所述的无机导电电阻薄膜1，其组成范围(重量％)为：Described inorganic conductive resistance thin film 1, its composition scope (weight %) is:

石墨(C)20～60，无机导电电阻交联剂40～80；Graphite (C) 20-60, inorganic conductive resistance cross-linking agent 40-80;

所述的导电电极薄膜2的组成范围(重量％)为：The composition scope (weight %) of describedconductive electrode film 2 is:

石墨(C)0.2～1.5，银粉60～80，铜粉18～40，Graphite (C) 0.2-1.5, silver powder 60-80, copper powder 18-40,

无机导电交联剂0.5～5；Inorganic conductive crosslinking agent 0.5~5;

所述的无机导电焊点3的组成范围(重量％)为：The composition range (weight %) of described inorganicconductive solder joint 3 is:

银粉95～98，无机导电交联剂为2％～5％；Silver powder 95-98, inorganicconductive cross-linking agent 2%-5%;

所述的绝缘保护薄膜4包括(重量％)：Described insulating protection film 4 comprises (weight %):

胶粘剂90％～99％，石英砂(钛白粉)1％～10％；Adhesive 90%~99%, quartz sand (titanium dioxide) 1%~10%;

也可以选用环氧型、聚脂型、环氧聚脂型静电粉沫涂料或任何一种耐高温油漆。You can also choose epoxy type, polyester type, epoxy polyester type electrostatic powder coating or any kind of high temperature resistant paint.

所述的无机导电电阻交联剂组成范围(重量％)为：The composition scope (weight %) of described inorganic conductive resistance cross-linking agent is:

氧化硅(sio₂)3～20，氧化铜(CuO)2～15，Silicon oxide (sio₂ ) 3~20, copper oxide (CuO) 2~15,

氧化硼(B₂O₃)10～45，氧化铅(Pb₂O₃)40～70。Boron oxide (B₂ O₃ ) 10-45, lead oxide (Pb₂ O₃ ) 40-70.

为了增加电阻膜的功率稳定性及其黏结强度，在上述配料中另又加入氧化钴和氧化铝，其组成范围为：In order to increase the power stability and bonding strength of the resistance film, cobalt oxide and aluminum oxide are added to the above ingredients, and the composition range is:

氧化硅(sio₂)3～20，氧化铜(CuO)2～15，Silicon oxide (sio₂ ) 3~20, copper oxide (CuO) 2~15,

氧化硼(B₂O₃)10～45，氧化铅(Pb₂O₃)40～70，Boron oxide (B₂ O₃ ) 10-45, lead oxide (Pb₂ O₃ ) 40-70,

氧化钴(CoO)0.2～5，氧化铝(AL₂O₃)0.2～6。Cobalt oxide (CoO) 0.2-5, aluminum oxide (AL₂ O₃ ) 0.2-6.

其中胶粘剂可以选用应变胶J26、C-2无机胶粉剂、南大703硅胶、C-4无机胶粉剂、JX～18胶粘剂或环氧树脂酚醛树脂组合成的耐200℃以上高温的胶粘剂。Among them, the adhesive can be selected from strain glue J26, C-2 inorganic rubber powder, Nanda 703 silica gel, C-4 inorganic rubber powder, JX~18 adhesive or epoxy phenolic resin, which is resistant to high temperatures above 200°C.

上述构成导电交联剂的组份可以直接采用组份中给出的氧化物，也可以采用化学当量的其它化合物作为交联剂中氧化物的原料。如其中氧化铅(PbO)可以用化学当量的PbO₂、PbCO₃或Pb₃O₄为原料；氧化硼(B₂O₃)也可以用化学当量的H₃BCO₃为原料；氧化硅可以用纯度在98.5％以上的石英砂为原料；氧化铜可以用化学当量的Cu₂O或CuCO₃为原料；氧化钴可以用化学当量的Co₂O₃为原料；氧化铝和氧化硅可以用含氧化硅(SiO₂)63％以上，含氧化铝(Al₂O₃)18.3％以上的长石为原料。The above-mentioned components constituting the conductive cross-linking agent may directly use the oxides given in the components, or other chemically equivalent compounds may be used as raw materials for the oxides in the cross-linking agent. For example, lead oxide (PbO) can use chemical equivalents of PbO₂ , PbCO₃ or Pb₃ O₄ as raw materials; boron oxide (B₂ O₃ ) can also use chemical equivalents of H₃ BCO₃ as raw materials; silicon oxide can use Quartz sand with a purity of more than 98.5% is used as the raw material; copper oxide can be made of chemically equivalent Cu₂ O or CuCO₃ ; cobalt oxide can be made of chemically equivalent Co₂ O₃ ; alumina and silicon oxide can be made of Feldspar containing more than 63% of silicon (SiO₂ ) and more than 18.3% of alumina (Al₂ O₃ ) is used as the raw material.

上述的无机导电电阻薄膜、导电电极、导电焊点的组份中，石墨是电阻填料和界面应力缓冲填料；铜和银是导电填料挂锡金属填料。Among the components of the above-mentioned inorganic conductive resistance film, conductive electrodes, and conductive solder joints, graphite is a resistance filler and an interfacial stress buffer filler; copper and silver are conductive fillers with tin-linked metal fillers.

在无机导电电阻薄膜中，相同厚度的膜，随石墨粉量的增加，膜的功率密度增加，当石墨的含量超过60％后，膜的功率密度的变化逐渐减小，直至恒定，但膜的硬度则随石墨含量的增加而减小，因而，本发明的石墨含量控制在20～60为宜。In the inorganic conductive resistance film, with the same thickness of the film, the power density of the film increases with the increase of the amount of graphite powder. When the content of graphite exceeds 60%, the change of the power density of the film gradually decreases until it becomes constant, but the power density of the film increases. The hardness decreases with the increase of the graphite content, therefore, the graphite content of the present invention is preferably controlled at 20-60.

由氧化铅、氧化硼、氧化硅、氧化铜、氧化钴、氧化铝经高温烧结、球磨过筛制作而成的导电交联剂，作为导电材料的骨架在烧结过程中与绝缘底材牢固地结合在一起，从而形成与底材牢固结合的无机导电电阻薄膜和无机导电极薄膜。其中氧化硅是非晶体结构骨架的主要原料，在高温烧成过程中，体积膨涨，可以补偿膜材的收缩。由于氧化硅的熔点高达1750℃，而交联剂的烧成温度在800℃～1200℃之间，在烧成过程中，藉其它氧化物熔剂而得以混熔。因而，过高的氧化硅的含量，导至难于熔化，未熔化的氧化硅会因晶型转化的体积效应，造成电阻薄膜产生相当大的内应力而形成微裂纹，甚至导致龟裂，影响电阻薄膜的抗震性及机械强度。因此氧化硅的含量控制在3％～20％。Conductive crosslinking agent made of lead oxide, boron oxide, silicon oxide, copper oxide, cobalt oxide, and aluminum oxide through high-temperature sintering and ball milling and sieving. As the skeleton of conductive material, it is firmly combined with the insulating substrate during the sintering process Together, thus forming an inorganic conductive resistance film and an inorganic conductive electrode film firmly combined with the substrate. Among them, silicon oxide is the main raw material of the non-crystalline structure skeleton. During the high-temperature firing process, the volume expands, which can compensate the shrinkage of the membrane material. Since the melting point of silicon oxide is as high as 1750°C, and the firing temperature of the crosslinking agent is between 800°C and 1200°C, during the firing process, other oxide fluxes are used to melt. Therefore, an excessively high silicon oxide content makes it difficult to melt, and the unmelted silicon oxide will cause considerable internal stress in the resistance film due to the volume effect of crystal transformation, forming microcracks, and even causing cracks, affecting the resistance. Shock resistance and mechanical strength of the film. Therefore, the content of silicon oxide is controlled at 3% to 20%.

氧化铅既是非晶结构材料，又是熔剂材料，在烧成过程的温度下能与氧化硅反应生成硅酸铅熔体。一般其含量控制在40～70％之间，过少，会造成氧化硅熔融不充分，影响膜的强度；同样，氧化硼既是非晶结构材料，又是熔剂材料，此外，它可减少交联剂的热膨胀，降低交联剂的固化温度。一般控制在10～45％，若含量过高，会影响交联剂结构，凝固后呈硼玻璃状，发脆；在交联剂中一般加入2～15％氧化铜，用于改善交联剂的非晶结构并提高交联剂与石墨和银的相熔性。若氧化铜过多，会降低膜的功率稳定性，在长时间的高温条件下工作，膜的阻值发生很大变化。Lead oxide is both an amorphous structure material and a flux material, which can react with silicon oxide to form lead silicate melt at the temperature of the firing process. Generally, its content is controlled between 40% and 70%. If it is too small, it will cause insufficient melting of silicon oxide and affect the strength of the film; similarly, boron oxide is not only an amorphous structure material, but also a flux material. In addition, it can reduce crosslinking. The thermal expansion of the agent reduces the curing temperature of the crosslinking agent. Generally, it is controlled at 10-45%. If the content is too high, it will affect the structure of the cross-linking agent. The amorphous structure and improve the phase solubility of the crosslinking agent with graphite and silver. If there is too much copper oxide, the power stability of the film will be reduced, and the resistance value of the film will change greatly when working under high temperature conditions for a long time.

为了进一步改善电阻薄膜与其绝缘载体间的黏结强度，在制作交联剂时最好加入适量的熔融温度相对比较低的含氧化铝的长石以及渗透力强的氧化钴。一般加入0.2～6％的氧化铝、0.2～5％的氧化钴。氧化铝过多，在高温下氧化铝很容易与其它氧化物形成吸潮性很强的分子筛结构，过多的氧化钴，使交联剂的温度敏感性强，使制作而成的电阻膜的阻值受随温度的影响大，导致膜功率不稳定。In order to further improve the bonding strength between the resistance film and its insulating carrier, it is best to add an appropriate amount of alumina-containing feldspar with relatively low melting temperature and cobalt oxide with strong penetration when making the crosslinking agent. Generally, 0.2-6% alumina and 0.2-5% cobalt oxide are added. If there is too much alumina, alumina will easily form a molecular sieve structure with strong moisture absorption with other oxides at high temperatures. Too much cobalt oxide will make the crosslinking agent more sensitive to temperature and make the resistive film produced The resistance value is greatly affected by temperature, resulting in unstable membrane power.

本发明通过采用如喷涂、刷涂、刮涂、浸涂、丝网印刷等制膜工艺将上述三种薄膜浆料分别涂复在如玻璃、搪瓷、陶瓷、云母片以及表面经过绝缘处理的金属等耐温绝缘加热器皿的外表面或电热元件的加热面，经烘干和烧结而永久地与被加热器皿或电热元件制成一体，通过调整膜配方、膜厚及膜的几何形状，准确控制膜的功率密度及膜的总功率，在平面、曲面任一凹凸面上可一次制成任意复杂形状的电阻薄膜。对于非均匀加热或局部加热的情况尤为方便。In the present invention, the above-mentioned three kinds of film pastes are respectively coated on glass, enamel, ceramics, mica sheets and metal surfaces with insulation treatment by adopting film-making processes such as spray coating, brush coating, scraping coating, dip coating, and screen printing. The outer surface of the heat-resistant insulated heating vessel or the heating surface of the electric heating element is permanently integrated with the heated vessel or electric heating element after drying and sintering. By adjusting the film formula, film thickness and film geometry, accurate control The power density of the film and the total power of the film can be made into a resistive film of any complex shape at one time on any concave-convex surface of a plane or a curved surface. Especially convenient for non-uniform or localized heating.

上述无机复合电阻薄膜的制作方法，特征在于：The method for making the above-mentioned inorganic composite resistive film is characterized in that:

1).按上述无机导电交联剂的组份范围，分别称取氧化硼、长石、石英砂、氧化铜、氧化钴，混匀后在800℃～1200℃下烧熔15分钟～60分钟，烧熔好的料块经球磨过筛制成颗粒直径小于或等于50微米的粉末状的无机导电交联剂；1). According to the composition range of the above-mentioned inorganic conductive cross-linking agent, respectively weigh boron oxide, feldspar, quartz sand, copper oxide, and cobalt oxide, mix them and melt at 800°C to 1200°C for 15 minutes to 60 minutes , the sintered block is ball milled and sieved to make a powdered inorganic conductive crosslinking agent with a particle diameter less than or equal to 50 microns;

2).分别按上述无机导电电阻薄膜、无机导电电极薄膜和无机导电焊点的组份范围，将无机导电交联剂分别与石墨粉，石墨粉、银粉、铜粉，银粉混匀，然后添加10％～65％松油醇，调制成无机电阻薄膜浆料、无机导电电极薄膜浆料和无机导电焊点浆料；按上述绝缘保护膜的组成范围制作成绝缘保护膜浆料；2). Mix the inorganic conductive cross-linking agent with graphite powder, graphite powder, silver powder, copper powder and silver powder respectively according to the composition range of the above-mentioned inorganic conductive resistance film, inorganic conductive electrode film and inorganic conductive solder joint, and then add 10% to 65% terpineol, modulated into inorganic resistance film slurry, inorganic conductive electrode film slurry and inorganic conductive solder spot slurry; made into insulating protective film slurry according to the composition range of the above-mentioned insulating protective film;

3).采用如喷涂、刷涂、刮涂、浸涂、丝网印刷等任意一种制膜工艺将上述制作好的无机导电电极薄膜浆料涂复在待制作的预定的加热器皿的耐温绝缘外表面或电热元件的耐温绝缘加热面上，膜厚为0.1mm～0.3mm，在150℃～200℃烘干5～20分钟，再在480℃～650℃下烧结5～45分钟；将上述无机导电电阻薄膜浆料，用上述方法涂复在加热器皿的耐温绝缘外表面或电热元件的耐温绝缘加热面的预定部位，膜厚为0.05mm～0.4mm，在150℃～200℃烘干5～20分钟，再在480℃～650℃下烧结5～45分钟；再将上述无机导电焊点浆料涂复在无机导电电极薄膜上，膜厚为0.1～0.6mm，在150℃～200℃烘干5～20分钟，再在480℃～650℃下烧结5～45分钟。3). Use any film-making process such as spraying, brushing, scraping, dipping, screen printing, etc. to coat the prepared inorganic conductive electrode film slurry on the temperature-resistant surface of the predetermined heating vessel to be produced. The outer surface of the insulation or the heat-resistant insulation heating surface of the electric heating element, the film thickness is 0.1mm ~ 0.3mm, dried at 150°C ~ 200°C for 5 ~ 20 minutes, and then sintered at 480°C ~ 650°C for 5 ~ 45 minutes; Apply the above-mentioned inorganic conductive resistance thin film slurry on the predetermined position of the heat-resistant insulating outer surface of the heating vessel or the heat-resistant insulating heating surface of the electric heating element by the above-mentioned method, with a film thickness of 0.05 mm to 0.4 mm. ℃ drying for 5 to 20 minutes, and then sintering at 480 ℃ to 650 ℃ for 5 to 45 minutes; then the above-mentioned inorganic conductive solder joint paste is coated on the inorganic conductive electrode film with a film thickness of 0.1 to 0.6 mm, at 150 Dry at ℃～200℃ for 5～20 minutes, and then sinter at 480℃～650℃ for 5～45 minutes.

4).将上述绝缘保护膜浆料用刮涂或刷涂法涂复在上述无机导电电阻薄膜、无机导电电极薄膜上，膜厚为0.1～0.6mm，自然干固或根据工艺要求，在50～300℃下烘干。4). Apply the above-mentioned insulating protective film slurry on the above-mentioned inorganic conductive resistance film and inorganic conductive electrode film by scraping or brushing. Dry at ~300°C.

松油醇是用作调节浆料粘度的稀释剂，在烘干、烧结过程中稀释剂完全挥发干净，稀释剂的加入量(重量％)为10％～65％以浆料粘度适于制膜为准。可选用的稀释剂还有：甘油、丙二醇、二丁脂松节油、丙酮、食用油等，可以任选其中一种，也可以混合使用。Terpineol is used as a diluent for adjusting the viscosity of the slurry. During the drying and sintering process, the diluent is completely volatilized. The amount of the diluent (% by weight) is 10% to 65% so that the viscosity of the slurry is suitable for film production. prevail. Optional diluents are: glycerin, propylene glycol, butyl turpentine, acetone, edible oil, etc., you can choose one of them, or mix them.

上述无机导电电极与导电焊点中的银可以用平均颗粒直径为4微米至60微米，纯度为98％以上的银粉，也可以采用化学当量的Ag₂O或Ag₂CO₃作为银的原料；无机导电电阻薄膜与导电电极中的石墨粉，其颗粒直径为4微米至60微米，纯度为90％～99％，铜粉的直径最好在4微米～20微米之间。The silver in the above-mentioned inorganic conductive electrodes and conductive solder joints can be 4 microns to 60 microns with an average particle diameter and a silver powder with a purity of more than 98%, or_Ag2O or_Ag2CO3 of chemical equivalent can be used as the raw material of silver_; The graphite powder in the inorganic conductive resistance film and the conductive electrode has a particle diameter of 4 microns to 60 microns and a purity of 90% to 99%. The copper powder preferably has a diameter of 4 microns to 20 microns.

石英砂(或钛白粉)选用颗粒细度为大于或等于200目，纯度为95以上的石英砂矿粉或钛白粉。Quartz sand (or titanium dioxide) chooses quartz sand ore powder or titanium dioxide with a particle size greater than or equal to 200 mesh and a purity of more than 95.

本发明的无机复合电阻薄膜，通过在导电粉末材料中加入多种氧化物所构成的厚膜交联剂，经烧结的导电粉末相互搭接而形成微观网络式导电通道；无机导电电阻薄膜与被加热器皿或电热元件制成一体，构成最大限度的导热面，传热热阻小；无机导电电阻薄膜在作为发热体发出热量时，其热量以热传导方式直接为受热体(即被加热器皿或电热元件)所吸收，与受热体始终处于平衡状态。例如一块面积为150cm²的900w的无机导电电阻薄直接制备在搪瓷锅的外侧底部，当锅的水温处于100度恒沸状态时，膜温最高只有110～130℃左右，纸张、棉花、香烟直接与膜接触均不会将其引燃，安全可靠；而无机电阻薄膜外侧所附的无机保护薄膜的热阻大，传导率低，这样就大大降低了膜的辐射对流热损失，也解决了在通电加热状态膜材料的氧化问题，使膜的工作寿命长达12000小时以上，热效率高达85％～95％，节能显著；原材料价廉，成本低，膜材料成本以10瓦/cm²计仅为0.45元/千瓦膜，制作工艺也简单，适于大批量工业化生产；由于在电极和无机导电电阻薄膜上面自然涂制一层绝缘保护膜，使其免受水和酸碱的浸蚀，完全可以浸泡在水和略带酸、碱性的溶液中，不仅有效保护了导电膜免受外力所损，而且能经受水及各种洗沽溶液的浸泡，因而清洗十方便，可广泛用于制作如电热杯、电热水瓶、电热饮水桶、电火锅、电饭煲等电热器皿，如电热淋浴器、电暖器电暖风机、电热玻璃仪器、电热医疗器具、电热台板等电热器具以及电热板非金属电热管电热条带、特种微小体积电热元件、各种形状的远红外元件等电热元件，特别对于一些特殊形状的加热面、非均匀加热或局部加热的情况尤为方便，大大扩大了使用范围。In the inorganic composite resistance film of the present invention, a thick-film crosslinking agent composed of various oxides is added to the conductive powder material, and the sintered conductive powders overlap each other to form a microscopic network-type conductive channel; the inorganic conductive resistance film and the substrate The heating vessel or electric heating element is made into one body, which constitutes the maximum heat conduction surface, and the heat transfer resistance is small; when the inorganic conductive resistance film emits heat as a heating element, its heat is directly transferred to the heating element (that is, the heated vessel or electric heating element) by heat conduction. Component) absorbed, and the heating body is always in equilibrium. For example, a 900W inorganic conductive resistor film with an area of^150cm2 is directly prepared on the outer bottom of the enamel pot. When the water temperature of the pot is in a constant boiling state of 100 degrees, the highest film temperature is only about 110-130°C. Paper, cotton, and cigarettes are directly Contact with the film will not ignite it, which is safe and reliable; while the inorganic protective film attached to the outside of the inorganic resistance film has large thermal resistance and low conductivity, which greatly reduces the radiation and convection heat loss of the film, and also solves the problem of The oxidation problem of the membrane material in the state of electric heating makes the working life of the membrane more than 12,000 hours, the thermal efficiency is as high as 85% to 95%, and the energy saving is remarkable; the raw materials are cheap and the cost is low, and the cost of the membrane material is only 10 watts/cm² 0.45 yuan/kW film, the production process is also simple, suitable for large-scale industrial production; because a layer of insulating protective film is naturally coated on the electrode and inorganic conductive resistance film to protect it from water and acid and alkali corrosion, it can be Soaking in water and slightly acidic and alkaline solutions not only effectively protects the conductive film from external damage, but also can withstand soaking in water and various washing solutions, so it is very convenient to clean and can be widely used in making such as Electric cups, electric kettles, electric drinking buckets, electric hot pots, rice cookers and other electric heating utensils, such as electric showers, electric heaters, electric heaters, electric glass instruments, electric medical appliances, electric heating plates and other electric heating appliances, and electric heating plates non-metallic electric heaters Tube electric heating strips, special small-volume electric heating elements, far-infrared elements of various shapes and other electric heating elements are especially convenient for some special-shaped heating surfaces, non-uniform heating or local heating, and greatly expand the scope of use.

以下结合附图对本发明的无机复合电阻薄膜及其制备方法作进一步说明：Below in conjunction with accompanying drawing, inorganic composite resistive thin film of the present invention and preparation method thereof are further described:

图1是本发明无机复合电阻薄膜的结构示意图。Fig. 1 is a schematic structural view of the inorganic composite resistive thin film of the present invention.

图2是图1的俯视示意图。FIG. 2 is a schematic top view of FIG. 1 .

图3是本发明无机复合电阻薄膜的实例示意图。Fig. 3 is a schematic diagram of an example of an inorganic composite resistive thin film of the present invention.

图4是本发明无机复合电阻薄膜的制作程序示意图。Fig. 4 is a schematic diagram of the fabrication procedure of the inorganic composite resistive thin film of the present invention.

如图1、图2和图3所示，本发明无机复合电阻薄膜，在加热器皿的耐温绝缘外表面或电热元件的耐温绝缘加热面5上涂复一层厚约0.05～1mm的无机导电电阻薄膜1，在该无机导电电阻薄膜1的周边设厚约0.1～0.3mm导电电极薄膜2，在该导电电极薄膜2上设厚约0.1～0.6mm的导电焊点3，在无机导电电阻薄膜1及电极薄膜的外表面涂复一层厚约0.2～0.6mm的绝缘保护膜4。As shown in Fig. 1, Fig. 2 and Fig. 3, the inorganic composite resistance film of the present invention is coated with a layer of inorganic resistance film with a thickness of about 0.05 to 1 mm on the temperature-resistant insulating outer surface of the heating vessel or the temperature-resistantinsulating heating surface 5 of the electric heating element. Conductive resistance film 1, on the periphery of this inorganic conductive resistance film 1, aconductive electrode film 2 with a thickness of about 0.1 to 0.3 mm is arranged, and aconductive solder spot 3 with a thickness of about 0.1 to 0.6 mm is set on theconductive electrode film 2. The outer surface of the thin film 1 and the electrode thin film is coated with an insulating protective film 4 with a thickness of about 0.2-0.6 mm.

以下通过实例对本发明的制作过程作详细说明：Below by example the production process of the present invention is described in detail:

一.选取六块如图2的相同的烧杯玻璃备用。1. Select six identical beaker glasses as shown in Figure 2 for subsequent use.

二.分别称取固体粉沫状的50克氧化硅，360克氧化硼，48克氧化铜，720克氧化铅，12克氧化钴及40克长石粉(含18.3％三氧化二铝，63％氧化硅)，混合均匀，放入坩锅内，在920℃下熔融45分钟，制成料块，再在球磨机中细磨24小时，过250目标准筛，得到无机电阻交联剂，备用；Two. Take by weighing 50 grams of silicon oxide of solid powder shape respectively, 360 grams of boron oxide, 48 grams of copper oxide, 720 grams of lead oxide, 12 grams of cobalt oxide and 40 grams of feldspar powder (containing 18.3% aluminum oxide, 63% Silicon oxide), mixed evenly, put into a crucible, melted at 920°C for 45 minutes to make a block, then finely ground in a ball mill for 24 hours, and passed through a 250-mesh standard sieve to obtain an inorganic resistance cross-linking agent for subsequent use;

三.称取上述备用的2克交联剂，30克银粉，15克铜粉，1克石墨，混匀，加入1.5克松油醇调制成浆料，选用60目丝网，分别在六块烧杯玻璃上印制如图2电极图形，然后在200℃下烘干15分钟，再在530℃下烧结12分钟，冷却，制成电极薄膜1备用。3. Weigh the spare 2 grams of cross-linking agent, 30 grams of silver powder, 15 grams of copper powder, and 1 gram of graphite, mix well, add 1.5 grams of terpineol to make a slurry, select a 60-mesh screen, and place them in six pieces Print the electrode pattern shown in Figure 2 on the beaker glass, then dry it at 200°C for 15 minutes, then sinter it at 530°C for 12 minutes, and cool it to make an electrode film 1 for use.

四.称取30克银粉，1克交联剂，加入5克松油醇，调制成焊点浆料2备用。4. Weigh 30 grams of silver powder, 1 gram of cross-linking agent, add 5 grams of terpineol, and prepare solderjoint paste 2 for later use.

五.分别称取20克石墨粉和上述备用的40克无机交联剂，再用20克松油醇调制成浆料3备用；分别称取60克石墨粉和上述备用的40克无机交联剂，用35克松油醇调制成浆料4备用；Five. Take by weighing 20 grams of graphite powder and the above-mentioned standby 40 grams of inorganic cross-linking agent respectively, and then use 20 grams of terpineol to makeslurry 3 for subsequent use; respectively weigh 60 grams of graphite powder and the above-mentioned standby 40 grams of inorganic cross-linking agent agent, modulated into slurry 4 with 35 grams of terpineol for subsequent use;

选用60目丝印网板，在其中三块烧杯玻璃上分别印制成如图2形状的膜厚为0.4毫米的无机电阻薄膜；选用上述已调制好的焊点浆料1，在相应的电极薄膜上涂制如图2的焊点，在200℃下烘干15分钟，再在530℃下烧结12分钟，冷至室温；选用60目丝印网板，在另外三块烧杯玻璃上用浆料3分别印制膜厚为0.1mm、0.3mm及0.8mm的无机电阻薄膜；Select a 60-mesh screen printing screen, and print an inorganic resistance film with a film thickness of 0.4 mm in the shape shown in Figure 2 on three of the beaker glasses; select the above-mentioned prepared solder joint paste 1, and print on the corresponding electrode film Paint the solder joints as shown in Figure 2, dry at 200°C for 15 minutes, then sinter at 530°C for 12 minutes, and cool to room temperature; use a 60-mesh screen printing screen, and useslurry 3 on the other three beaker glasses Print inorganic resistive films with film thicknesses of 0.1mm, 0.3mm and 0.8mm respectively;

选用上述已调制好的焊点浆料，在相应的电极上涂制如图2的焊点，在200℃下烘干15分钟，再在530℃下烧结12分钟，冷至室温。Select the prepared solder joint paste mentioned above, paint the solder joints as shown in Figure 2 on the corresponding electrodes, dry at 200°C for 15 minutes, then sinter at 530°C for 12 minutes, and cool to room temperature.

六.称取环氧树脂型静电粉沫涂料30克，采用静电喷涂方法，在上述六块烧杯玻璃的电阻薄膜及电极薄膜上喷涂一层厚度为0.2mm的保护膜，在250℃下烘干一小时，制得六种无机复合电阻薄膜。6. Weigh 30 grams of epoxy resin type electrostatic powder coating, adopt electrostatic spraying method, spray a protective film with a thickness of 0.2mm on the resistance film and electrode film of the above six beaker glasses, and dry at 250°C In one hour, six kinds of inorganic composite resistive films were prepared.

采用划格法，测得前前三种电阻薄膜的每平方厘米电阻分别为25.6Ω、22.3Ω、19Ω；后三种的电阻分别为87.6Ω、35.6Ω、19.8Ω。Using the cross-cut method, the resistance per square centimeter of the first three types of resistance films were measured to be 25.6Ω, 22.3Ω, and 19Ω; the resistances of the latter three types were 87.6Ω, 35.6Ω, and 19.8Ω, respectively.

Claims (4)

Translated fromChinese

1.一种新型无机复合电阻薄膜，其特征在于在加热器皿的耐温绝缘外表面或电热元件的耐温绝缘加热面5上涂复一层厚约0.05～1mm的无机导电电阻薄膜1，在该无机导电电阻薄膜1的周边设厚约0.1～0.3mm导电电极薄膜2，在该导电电极薄膜2上设厚约0.1～0.6mm的导电焊点3，在无机导电电阻薄膜1及电极薄膜的外表面涂复一层厚约0.1～0.6mm的绝缘保护膜4。1. A novel inorganic composite resistance film is characterized in that the inorganic conductive resistance film 1 with a thickness of about 0.05 to 1 mm is coated on the temperature-resistant insulating outer surface of the heating vessel or the temperature-resistant insulating heating surface 5 of the electric heating element. The periphery of the inorganic conductive resistance film 1 is provided with a conductive electrode film 2 with a thickness of about 0.1 to 0.3 mm, and a conductive solder spot 3 with a thickness of about 0.1 to 0.6 mm is set on the conductive electrode film 2. The outer surface is coated with an insulating protective film 4 with a thickness of about 0.1-0.6 mm.2.如权利要求1所述的无机复合电阻薄膜，其特征在于其组成范围(重量％)为：2. inorganic composite resistance thin film as claimed in claim 1 is characterized in that its composition range (weight %) is:石墨(C)20～60，无机导电电阻交联剂40～80；Graphite (C) 20-60, inorganic conductive resistance cross-linking agent 40-80;所述的导电电极薄膜2的组成范围(重量％)为：The composition scope (weight %) of described conductive electrode film 2 is:石墨(C)0.2～1.5，银粉60～80，铜粉18～40，Graphite (C) 0.2-1.5, silver powder 60-80, copper powder 18-40,无机导电交联剂0.5～5；Inorganic conductive crosslinking agent 0.5~5;所述的无机导电焊点3的组成范围(重量％)为：The composition range (weight %) of described inorganic conductive solder joint 3 is:银粉95～98，无机导电交联剂为2％～5％；Silver powder 95-98, inorganic conductive cross-linking agent 2%-5%;所述的绝缘保护薄膜4包括(重量％)：Described insulating protection film 4 comprises (weight %):胶粘剂90％～99％，石英砂(钛白粉)1％～10％；Adhesive 90%~99%, quartz sand (titanium dioxide) 1%~10%;上述无机导电电阻交联剂组成范围(重量％)为：Above-mentioned inorganic conductive resistance cross-linking agent composition scope (weight %) is:氧化硅(sio₂)3～20，氧化铜(CuO)2～15，Silicon oxide (sio₂ ) 3~20, copper oxide (CuO) 2~15,氧化硼(B₂O₃)0～45，氧化铅(Pb₂O₃)40～70。Boron oxide (B₂ O₃ ) 0-45, lead oxide (Pb₂ O₃ ) 40-70.3.如权利要求2所述的无机复合电阻薄膜，其特征在于所述的无机导电电阻交联剂组成范围(重量％)为：3. Inorganic composite resistance film as claimed in claim 2, is characterized in that described inorganic conductive resistance crosslinking agent composition scope (weight %) is:氧化硅(sio₂)3～20，氧化铜(CuO)2～15，Silicon oxide (sio₂ ) 3~20, copper oxide (CuO) 2~15,氧化硼(B₂O₃)10～45，氧化铅(Pb₂O₃)40～70，Boron oxide (B₂ O₃ ) 10-45, lead oxide (Pb₂ O₃ ) 40-70,氧化钴(CoO)0.2～5，氧化铝(AL₂O₃)0.2～6。Cobalt oxide (CoO) 0.2-5, aluminum oxide (AL₂ O₃ ) 0.2-6.4.如权利要求1，2或3所述无机复合电阻薄膜的制备方法，其特征在于：4. as claimed in claim 1, the preparation method of inorganic composite resistive thin film described in 2 or 3 is characterized in that:1).按上述无机导电交联剂的组份范围，分别称取氧化硼、长石、石英砂、氧化铜、氧化钴，混匀后在800℃～1200℃下烧熔15分钟～60分钟，烧熔好的料块经球磨过筛制成颗粒直径小于或等于50微米的粉末状的无机导电交联剂；1). According to the composition range of the above-mentioned inorganic conductive cross-linking agent, respectively weigh boron oxide, feldspar, quartz sand, copper oxide, and cobalt oxide, mix them and melt at 800°C to 1200°C for 15 minutes to 60 minutes , the sintered block is ball milled and sieved to make a powdered inorganic conductive crosslinking agent with a particle diameter less than or equal to 50 microns;2).分别按上述无机导电电阻薄膜、无机导电电极薄膜和无机导电焊点的组份范围，将无机导电交联剂分别与石墨粉，石墨粉、银粉、铜粉，银粉混匀，然后添加10％～65％松油醇，调制成无机电阻薄膜浆料、无机导电电极薄膜浆料和无机导电焊点浆料；按上述绝缘保护膜的组成范围制作成绝缘保护膜浆料；2). Mix the inorganic conductive cross-linking agent with graphite powder, graphite powder, silver powder, copper powder and silver powder respectively according to the composition range of the above-mentioned inorganic conductive resistance film, inorganic conductive electrode film and inorganic conductive solder joint, and then add 10% to 65% terpineol, modulated into inorganic resistance film slurry, inorganic conductive electrode film slurry and inorganic conductive solder spot slurry; made into insulating protective film slurry according to the composition range of the above-mentioned insulating protective film;3).采用如喷涂、刷涂、刮涂、浸涂、丝网印刷等任意一种制膜工艺将上述制作好的无机导电电极薄膜浆料涂复在待制作的预定的加热器皿的耐温绝缘外表面或电热元件的耐温绝缘加热面上，膜厚为0.1mm～0.3mm，在150℃～200℃烘干5～20分钟，再在480℃～650℃下烧结5～45分钟；将上述无机导电电阻薄膜浆料，用上述方法涂复在加热器皿的耐温绝缘外表面或电热元件的耐温绝缘加热面的预定部位，膜厚为0.05mm～0.4mm，在150℃～200℃烘干5～20分钟，再在480℃～650℃下烧结5～45分钟；再将上述无机导电焊点浆料涂复在无机导电电极薄膜上，膜厚为0.1～0.6mm，在150℃～200℃烘干5～20分钟，再在480℃～650℃下烧结5～45分钟。3). Use any film-making process such as spraying, brushing, scraping, dipping, screen printing, etc. to coat the prepared inorganic conductive electrode film slurry on the temperature-resistant surface of the predetermined heating vessel to be produced. The outer surface of the insulation or the heat-resistant insulation heating surface of the electric heating element, the film thickness is 0.1mm ~ 0.3mm, dried at 150°C ~ 200°C for 5 ~ 20 minutes, and then sintered at 480°C ~ 650°C for 5 ~ 45 minutes; Apply the above-mentioned inorganic conductive resistance thin film slurry on the predetermined position of the heat-resistant insulating outer surface of the heating vessel or the heat-resistant insulating heating surface of the electric heating element by the above-mentioned method, with a film thickness of 0.05 mm to 0.4 mm. ℃ drying for 5 to 20 minutes, and then sintering at 480 ℃ to 650 ℃ for 5 to 45 minutes; then the above-mentioned inorganic conductive solder joint paste is coated on the inorganic conductive electrode film with a film thickness of 0.1 to 0.6 mm, at 150 Dry at ℃～200℃ for 5～20 minutes, and then sinter at 480℃～650℃ for 5～45 minutes.4).将上述绝缘保护膜浆料用刮涂或刷涂法涂复在上述无机导电电阻薄膜、无机导电电极薄膜上，膜厚为0.1～0.6mm，在50～300℃下烘干或自然干固。4). Apply the above-mentioned insulating protective film slurry on the above-mentioned inorganic conductive resistance film and inorganic conductive electrode film by scraping or brushing, with a film thickness of 0.1-0.6mm, and dry at 50-300°C or naturally dry.

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