CN116197096A - Silicon nitride heating film and preparation method thereof - Google Patents
Silicon nitride heating film and preparation method thereof Download PDFInfo
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- CN116197096A CN116197096A CN202211636755.1A CN202211636755A CN116197096A CN 116197096 A CN116197096 A CN 116197096A CN 202211636755 A CN202211636755 A CN 202211636755A CN 116197096 A CN116197096 A CN 116197096A
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 94
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 78
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 62
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052788 barium Inorganic materials 0.000 claims abstract description 24
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052738 indium Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 13
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical group [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical group Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 11
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005485 electric heating Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
- B05D3/0453—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
本发明属于发热膜技术领域，提供了一种氮化硅发热膜的制备方法。本发明以锡源、铟源、钡源和溶剂为原料制备喷涂液，钡和铟作为掺杂元素，有利于降低发热膜的电阻率；然后向氮化硅基体喷涂喷涂液，采用喷涂的涂覆方式能够很好的控制发热膜的厚度，从而控制发热膜的电阻率，而采用氮化硅基体有利于得到耐高温性能好的氮化硅发热膜，延长发热膜的使用寿命；最后经过焙烧在氮化硅基体表面形成了掺杂钡和铟的氧化锡发热膜。实施例的结果显示，本发明提供的制备方法制备的氮化硅发热膜的电阻率为1.13×10‑4Ω·cm，工作温度为580℃，热导率为82W/m·k。The invention belongs to the technical field of heating films and provides a method for preparing a silicon nitride heating film. The present invention uses tin source, indium source, barium source and solvent as raw materials to prepare spraying liquid, and barium and indium are used as doping elements, which is beneficial to reduce the resistivity of heating film; The coating method can well control the thickness of the heating film, thereby controlling the resistivity of the heating film, and the use of silicon nitride substrate is conducive to obtaining a silicon nitride heating film with good high temperature resistance and prolonging the service life of the heating film; A tin oxide heating film doped with barium and indium is formed on the surface of the silicon nitride substrate. The results of the examples show that the resistivity of the silicon nitride heating film prepared by the preparation method provided by the present invention is 1.13×10 -4 Ω·cm, the working temperature is 580°C, and the thermal conductivity is 82W/m·k.
Description
技术领域technical field
本发明涉及发热膜技术领域，尤其涉及一种氮化硅发热膜及其制备方法。The invention relates to the technical field of heating films, in particular to a silicon nitride heating film and a preparation method thereof.
背景技术Background technique
电发热膜是一种很有发展前途的电热元件，80年代后期，国外电发热膜的应用已相当广泛。电发热膜加热属于电阻加热方式，与电阻丝相同。但电热膜很薄，厚度一般只有0.01～1mm，其材料多由高价氧化物组成，作为暖风机一类电暖器的发热元件，电热膜有以下明显优点：由于是面发热元件，不需要再安装金属散热器；工作时本身温度不高，无明火，安全可靠，不氧化。Electric heating film is a promising electric heating element. In the late 1980s, the application of electric heating film abroad has been quite extensive. Electric heating film heating belongs to the resistance heating method, which is the same as resistance wire. However, the electric heating film is very thin, generally only 0.01-1mm in thickness, and its material is mostly composed of high-valent oxides. As the heating element of electric heaters such as heaters, the electric heating film has the following obvious advantages: because it is a surface heating element, it does not need to be reheated. Install a metal radiator; the temperature itself is not high when working, there is no open flame, it is safe and reliable, and it does not oxidize.
然而，当前发热市场大多采用石英管作为发热膜的基体，但石英玻璃管强度低，其抗弯强度仅为80MPa，且热导率低，其热导率<2W/m·k，用作发热体的基体时，发热体的功耗高，导致发热体的寿命缩短，这大大限制了大功率发热产品的发展。而且，现有电发热膜技术还普遍存在热稳定性低、电阻率高等问题，制约了电发热膜技术的普及和推广。因此，亟需一种耐高温性能好、使用寿命长且电阻率低的电发热膜。However, in the current heating market, most of the quartz tubes are used as the substrate of the heating film, but the strength of the quartz glass tube is low, and its bending strength is only 80MPa, and the thermal conductivity is low, and its thermal conductivity is less than 2W/m·k. When the substrate of the body is used, the power consumption of the heating element is high, resulting in shortened life of the heating element, which greatly limits the development of high-power heating products. Moreover, the existing electric heating film technology generally has problems such as low thermal stability and high resistivity, which restrict the popularization and promotion of the electric heating film technology. Therefore, there is an urgent need for an electric heating film with good high temperature resistance, long service life and low resistivity.
发明内容Contents of the invention
本发明的目的在于提供一种氮化硅发热膜及其制备方法，本发明提供的氮化硅发热膜具有良好的耐高温性能好、使用寿命长且电阻率低。The object of the present invention is to provide a silicon nitride heating film and a preparation method thereof. The silicon nitride heating film provided by the present invention has good high temperature resistance, long service life and low resistivity.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种氮化硅发热膜的制备方法，包括以下步骤：The invention provides a method for preparing a silicon nitride heating film, comprising the following steps:
(1)将锡源、铟源、钡源和溶剂混合，得到喷涂液；(1) Mix tin source, indium source, barium source and solvent to obtain spraying liquid;
(2)向氮化硅基体喷涂所述步骤(1)得到的喷涂液，得到氮化硅发热膜前驱体；(2) spraying the spraying solution obtained in the step (1) to the silicon nitride substrate to obtain a silicon nitride heating film precursor;
(3)将所述步骤(2)得到的氮化硅发热膜前驱体进行焙烧，得到氮化硅发热膜。(3) Calcining the silicon nitride heating film precursor obtained in the step (2) to obtain a silicon nitride heating film.
优选地，所述步骤(1)中的锡源为四氯化锡；所述铟源为三氯化铟；所述钡源为氧化钡。Preferably, the tin source in the step (1) is tin tetrachloride; the indium source is indium trichloride; and the barium source is barium oxide.
优选地，所述步骤(1)中的溶剂为无水乙醇。Preferably, the solvent in the step (1) is absolute ethanol.
优选地，所述步骤(1)中锡源、铟源和钡源的质量比为(50～80)：(3～6)：(0.05～0.2)。Preferably, the mass ratio of tin source, indium source and barium source in the step (1) is (50-80):(3-6):(0.05-0.2).
优选地，所述步骤(2)中喷涂的工艺参数为：喷涂距离30～50cm，喷涂时间10～30min，喷涂速度2～4cm/s，喷涂液流量1.2～1.4mL/s。Preferably, the process parameters of spraying in the step (2) are: spraying distance 30-50cm, spraying time 10-30min, spraying speed 2-4cm/s, spraying liquid flow rate 1.2-1.4mL/s.
优选地，所述步骤(3)中焙烧的温度为500～650℃，焙烧的时间为50～80min。Preferably, the temperature of the calcination in the step (3) is 500-650° C., and the calcination time is 50-80 minutes.
优选地，所述步骤(3)中焙烧的温度为560～620℃，焙烧的时间为55～65min。Preferably, the calcination temperature in the step (3) is 560-620° C., and the calcination time is 55-65 minutes.
优选地，所述步骤(3)中焙烧的气氛为氧气。Preferably, the atmosphere for firing in step (3) is oxygen.
本发明还提供了上述技术方案所述制备方法制备得到的氮化硅发热膜，所述氮化硅发热膜包括氮化硅基体和发热膜。The present invention also provides a silicon nitride heating film prepared by the preparation method described in the above technical solution, and the silicon nitride heating film includes a silicon nitride substrate and a heating film.
优选地，所述发热膜的厚度为800～1200nm。Preferably, the thickness of the heating film is 800-1200 nm.
本发明提供了一种氮化硅发热膜的制备方法，包括以下步骤：(1)将锡源、铟源、钡源和溶剂混合，得到喷涂液；(2)向氮化硅基体喷涂所述步骤(1)得到的喷涂液，得到氮化硅发热膜前驱体；(3)将所述步骤(2)得到的氮化硅发热膜前驱体进行焙烧，得到氮化硅发热膜。本发明以锡源、铟源、钡源和溶剂为原料制备喷涂液，钡和铟作为掺杂元素，有利于降低发热膜的电阻率；然后向氮化硅基体喷涂喷涂液，采用喷涂的涂覆方式能够很好的控制发热膜的厚度，从而控制发热膜的电阻率，而采用氮化硅基体有利于得到耐高温性能好的氮化硅发热膜，延长发热膜的使用寿命；最后经过焙烧在氮化硅基体表面形成了掺杂钡和铟的氧化锡发热膜。实施例的结果显示，本发明提供的制备方法制备的氮化硅发热膜的电阻率为1.13×10-4Ω·cm，工作温度为580℃，热导率为82W/m·k。The invention provides a method for preparing a silicon nitride heating film, comprising the following steps: (1) mixing a tin source, an indium source, a barium source and a solvent to obtain a spraying liquid; (2) spraying the silicon nitride substrate with the The spraying solution obtained in step (1) is used to obtain a silicon nitride heating film precursor; (3) the silicon nitride heating film precursor obtained in the step (2) is fired to obtain a silicon nitride heating film. The present invention uses tin source, indium source, barium source and solvent as raw materials to prepare spraying liquid, and barium and indium are used as doping elements, which is beneficial to reduce the resistivity of heating film; The coating method can well control the thickness of the heating film, thereby controlling the resistivity of the heating film, and the use of silicon nitride substrate is conducive to obtaining a silicon nitride heating film with good high temperature resistance and prolonging the service life of the heating film; A tin oxide heating film doped with barium and indium is formed on the surface of the silicon nitride substrate. The results of the examples show that the resistivity of the silicon nitride heating film prepared by the preparation method provided by the present invention is 1.13×10 -4 Ω·cm, the working temperature is 580°C, and the thermal conductivity is 82 W/m·k.
具体实施方式Detailed ways
本发明提供了一种氮化硅发热膜的制备方法，包括以下步骤：The invention provides a method for preparing a silicon nitride heating film, comprising the following steps:
(1)将锡源、铟源、钡源和溶剂混合，得到喷涂液；(1) Mix tin source, indium source, barium source and solvent to obtain spraying liquid;
(2)向氮化硅基体喷涂所述步骤(1)得到的喷涂液，得到氮化硅发热膜前驱体；(2) spraying the spraying solution obtained in the step (1) to the silicon nitride substrate to obtain a silicon nitride heating film precursor;
(3)将所述步骤(2)得到的氮化硅发热膜前驱体进行焙烧，得到氮化硅发热膜。(3) Calcining the silicon nitride heating film precursor obtained in the step (2) to obtain a silicon nitride heating film.
本发明将锡源、铟源、钡源和溶剂混合，得到喷涂液。The invention mixes the tin source, the indium source, the barium source and the solvent to obtain the spraying liquid.
本发明对所述锡源、铟源、钡源和溶剂混合的操作没有特殊的限定，采用本领域技术人员熟知的混合方式即可。在本发明中，所述混合优选在搅拌的条件下进行；所述搅拌的速率优选为300～500r/min；所述搅拌的时间优选为20～30min。In the present invention, there is no special limitation on the operation of mixing the tin source, indium source, barium source and solvent, and a mixing method well known to those skilled in the art can be used. In the present invention, the mixing is preferably carried out under the condition of stirring; the stirring speed is preferably 300-500 r/min; the stirring time is preferably 20-30 min.
在本发明中，所述锡源优选为四氯化锡。本发明中的锡源用于制备氧化锡膜，作为发热膜的主体，有利于提高氮化硅发热膜的隔热性能，保证氮化硅发热膜的耐高温性能，同时有利于得到低电阻率的氮化硅发热膜。In the present invention, the tin source is preferably tin tetrachloride. The tin source in the present invention is used to prepare the tin oxide film, as the main body of the heating film, it is beneficial to improve the heat insulation performance of the silicon nitride heating film, ensure the high temperature resistance of the silicon nitride heating film, and at the same time help to obtain low resistivity silicon nitride heating film.
在本发明中，所述铟源优选为三氯化铟。本发明中铟源作为掺杂元素，有利于降低发热膜的电阻率。In the present invention, the indium source is preferably indium trichloride. In the present invention, the indium source is used as a doping element, which is beneficial to reduce the resistivity of the heating film.
在本发明中，所述钡源优选为氧化钡。本发明中钡源作为掺杂元素，有利于降低发热膜的电阻率。本发明对所述锡源、铟源和钡源的来源没有特殊的限定，采用本领域技术人员熟知的市售产品即可。In the present invention, the barium source is preferably barium oxide. In the present invention, the barium source is used as a doping element, which is beneficial to reduce the resistivity of the heating film. In the present invention, there is no special limitation on the sources of the tin source, indium source and barium source, and commercially available products well known to those skilled in the art can be used.
在本发明中，所述溶剂优选为无水乙醇。In the present invention, the solvent is preferably absolute ethanol.
在本发明中，所述锡源、铟源和钡源的质量比优选为(50～80)：(3～6)：(0.05～0.2)，更优选为(55～75)：(3～5)：(0.05～0.1)。本发明优选将所述锡源、铟源和钡源的质量比控制在上述范围内，有利于得到电阻率低的氮化硅发热膜。In the present invention, the mass ratio of the tin source, indium source and barium source is preferably (50-80): (3-6): (0.05-0.2), more preferably (55-75): (3- 5): (0.05～0.1). In the present invention, the mass ratio of the tin source, indium source and barium source is preferably controlled within the above range, which is beneficial to obtain a silicon nitride heating film with low resistivity.
在本发明中，以锡源的用量为50～80g计，所述溶剂的用量优选为100～150mL。In the present invention, based on the tin source being used in an amount of 50-80 g, the solvent is preferably used in an amount of 100-150 mL.
得到喷涂液后，本发明向氮化硅基体喷涂所述喷涂液，得到氮化硅发热膜前驱体。本发明采用喷涂的涂覆方式能够很好的控制发热膜的厚度，从而控制发热膜的电阻率，而采用氮化硅基体有利于得到耐高温性能好的氮化硅发热膜，延长发热膜的使用寿命。After the spraying liquid is obtained, the present invention sprays the spraying liquid on the silicon nitride substrate to obtain a silicon nitride heating film precursor. In the present invention, the coating method of spraying can well control the thickness of the heating film, thereby controlling the resistivity of the heating film, and the use of a silicon nitride substrate is beneficial to obtain a silicon nitride heating film with good high temperature resistance, and prolong the life of the heating film. service life.
本发明对所述喷涂的操作没有特殊的限定，采用本领域技术人员熟知的喷涂的技术方案即可。In the present invention, there is no special limitation on the spraying operation, and the technical solutions of spraying well known to those skilled in the art can be adopted.
在本发明中，所述喷涂的工艺参数优选为：喷涂距离30～50cm，喷涂时间10～30min，喷涂速度2～4cm/s，喷涂液流量1.2～1.4mL/s；更优选为：喷涂距离35～45cm，喷涂时间20～30min，喷涂速度2～3cm/s，喷涂液流量1.2～1.3mL/s。本发明将所述喷涂的工艺参数控制在上述范围内，有利于得到表面光滑平整且电阻率低的氮化硅发热膜。In the present invention, the process parameters of the spraying are preferably: spraying distance 30-50cm, spraying time 10-30min, spraying speed 2-4cm/s, spraying liquid flow rate 1.2-1.4mL/s; more preferably: spraying distance 35-45cm, spraying time 20-30min, spraying speed 2-3cm/s, spraying liquid flow rate 1.2-1.3mL/s. In the present invention, the process parameters of the spraying are controlled within the above range, which is beneficial to obtain a silicon nitride heating film with a smooth surface and low resistivity.
本发明对所述氮化硅基体的来源没有特殊的限定，采用本领域技术人员熟知的市售产品即可。In the present invention, there is no special limitation on the source of the silicon nitride substrate, and commercially available products well known to those skilled in the art can be used.
得到氮化硅发热膜前驱体后，本发明将所述氮化硅发热膜前驱体进行焙烧，得到氮化硅发热膜。After the silicon nitride heating film precursor is obtained, the present invention bakes the silicon nitride heating film precursor to obtain a silicon nitride heating film.
在本发明中，所述焙烧的温度优选为500～650℃，更优选为560～620℃；所述焙烧的时间优选为50～80min，更优选为55～65min。本发明优选将所述焙烧的温度和时间控制在上述范围内，有利于得到电阻率低的氮化硅发热膜。In the present invention, the calcination temperature is preferably 500-650°C, more preferably 560-620°C; the calcination time is preferably 50-80min, more preferably 55-65min. In the present invention, the temperature and time of the calcination are preferably controlled within the above range, which is beneficial to obtain a silicon nitride heating film with low resistivity.
在本发明中，所述焙烧的气氛优选为氧气。本发明优选在氧气气氛中进行焙烧，有利于得到氧化锡膜。In the present invention, the calcination atmosphere is preferably oxygen. In the present invention, the firing is preferably carried out in an oxygen atmosphere, which is beneficial to obtain the tin oxide film.
本发明以锡源、铟源、钡源和溶剂为原料制备喷涂液，钡和铟作为掺杂元素，有利于降低发热膜的电阻率；然后向氮化硅基体喷涂喷涂液，采用喷涂的涂覆方式能够很好的控制发热膜的厚度，从而控制发热膜的电阻率，而采用氮化硅基体有利于得到耐高温性能好的氮化硅发热膜，延长发热膜的使用寿命；最后经过焙烧在氮化硅基体表面形成了掺杂钡和铟的氧化锡发热膜。The present invention uses tin source, indium source, barium source and solvent as raw materials to prepare spraying liquid, and barium and indium are used as doping elements, which is beneficial to reduce the resistivity of heating film; The coating method can well control the thickness of the heating film, thereby controlling the resistivity of the heating film, and the use of silicon nitride substrate is conducive to obtaining a silicon nitride heating film with good high temperature resistance and prolonging the service life of the heating film; A tin oxide heating film doped with barium and indium is formed on the surface of the silicon nitride substrate.
本发明还提供了上述技术方案所述制备方法制备得到的氮化硅发热膜，所述氮化硅发热膜包括氮化硅基体和发热膜。本发明提供的氮化硅发热膜具有良好的耐高温性能好、使用寿命长且电阻率低。The present invention also provides a silicon nitride heating film prepared by the preparation method described in the above technical solution, and the silicon nitride heating film includes a silicon nitride substrate and a heating film. The silicon nitride heating film provided by the invention has good high temperature resistance, long service life and low resistivity.
在本发明中，所述发热膜的厚度优选为800～1200nm，更优选为850～1100nm。In the present invention, the thickness of the heat generating film is preferably 800-1200 nm, more preferably 850-1100 nm.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
(1)将80g四氯化锡、5g三氯化铟、0.1g氧化钡和150mL无水乙醇在350r/min的速率下搅拌混合20min，得到喷涂液；其中，四氯化锡、三氯化铟和氧化钡的质量比为80：5：0.1；(1) Stir and mix 80g tin tetrachloride, 5g indium trichloride, 0.1g barium oxide and 150mL absolute ethanol at a rate of 350r/min for 20min to obtain a spray coating; wherein, tin tetrachloride, trichloride The mass ratio of indium and barium oxide is 80:5:0.1;
(2)向氮化硅基体喷涂步骤(1)得到的喷涂液，得到氮化硅发热膜前驱体；其中，喷涂的工艺参数为：喷涂距离35cm，喷涂时间20min，喷涂速度2cm/s，喷涂液流量1.2mL/s；(2) Spray the spraying solution obtained in step (1) to the silicon nitride substrate to obtain the silicon nitride heating film precursor; wherein, the process parameters of spraying are: spraying distance 35cm, spraying time 20min, spraying speed 2cm/s, spraying Liquid flow 1.2mL/s;
(3)在氧气气氛中，将步骤(2)得到的氮化硅发热膜前驱体在620℃下焙烧55min，得到厚度为850nm的氮化硅发热膜。(3) In an oxygen atmosphere, the silicon nitride heating film precursor obtained in step (2) was fired at 620° C. for 55 minutes to obtain a silicon nitride heating film with a thickness of 850 nm.
实施例2Example 2
(1)将75g四氯化锡、4g三氯化铟、0.05g氧化钡和140mL无水乙醇在350r/min的速率下搅拌混合20min，得到喷涂液；其中，四氯化锡、三氯化铟和氧化钡的质量比为75：4：0.05；(1) Stir and mix 75g tin tetrachloride, 4g indium trichloride, 0.05g barium oxide and 140mL absolute ethanol at a rate of 350r/min for 20min to obtain a spray coating; wherein, tin tetrachloride, trichloride The mass ratio of indium and barium oxide is 75:4:0.05;
(2)向氮化硅基体喷涂步骤(1)得到的喷涂液，得到氮化硅发热膜前驱体；其中，喷涂的工艺参数为：喷涂距离35cm，喷涂时间30min，喷涂速度2cm/s，喷涂液流量1.2mL/s；(2) Spray the spraying solution obtained in step (1) to the silicon nitride substrate to obtain the silicon nitride heating film precursor; wherein, the process parameters of spraying are: spraying distance 35cm, spraying time 30min, spraying speed 2cm/s, spraying Liquid flow 1.2mL/s;
(3)在氧气气氛中，将步骤(2)得到的氮化硅发热膜前驱体在620℃下焙烧55min，得到厚度为900nm的氮化硅发热膜。(3) In an oxygen atmosphere, the silicon nitride heating film precursor obtained in step (2) was fired at 620° C. for 55 minutes to obtain a silicon nitride heating film with a thickness of 900 nm.
实施例3Example 3
(1)将68g四氯化锡、3g三氯化铟、0.15g氧化钡和130mL无水乙醇在350r/min的速率下搅拌混合20min，得到喷涂液；其中，四氯化锡、三氯化铟和氧化钡的质量比为68：3：0.15；(1) Stir and mix 68g tin tetrachloride, 3g indium trichloride, 0.15g barium oxide and 130mL absolute ethanol at a speed of 350r/min for 20min to obtain a spray coating; wherein tin tetrachloride, trichloride The mass ratio of indium and barium oxide is 68:3:0.15;
(2)向氮化硅基体喷涂步骤(1)得到的喷涂液，得到氮化硅发热膜前驱体；其中，喷涂的工艺参数为：喷涂距离40cm，喷涂时间25min，喷涂速度2cm/s，喷涂液流量1.2mL/s；(2) Spray the spray liquid obtained in step (1) to the silicon nitride substrate to obtain the silicon nitride heating film precursor; wherein, the process parameters of spraying are: spraying distance 40cm, spraying time 25min, spraying speed 2cm/s, spraying Liquid flow 1.2mL/s;
(3)在氧气气氛中，将步骤(2)得到的氮化硅发热膜前驱体在580℃下焙烧65min，得到厚度为880nm的氮化硅发热膜。(3) In an oxygen atmosphere, the silicon nitride heating film precursor obtained in step (2) was fired at 580° C. for 65 minutes to obtain a silicon nitride heating film with a thickness of 880 nm.
对比例1Comparative example 1
与实施例1的不同之处在于，步骤(1)中省略了三氯化铟，其余步骤同实施例1。The difference from Example 1 is that indium trichloride is omitted in step (1), and the rest of the steps are the same as in Example 1.
对比例2Comparative example 2
与实施例1的不同之处在于，步骤(2)中喷涂时间为10min，其余步骤同实施例1。The difference from Example 1 is that the spraying time in step (2) is 10min, and all the other steps are the same as in Example 1.
对比例3Comparative example 3
与实施例1的不同之处在于，步骤(3)中在450℃下焙烧55min，其余步骤同实施例1。The difference from Example 1 is that in step (3), it is baked at 450° C. for 55 minutes, and the rest of the steps are the same as in Example 1.
采用四探针法测试实施例1～3和对比例1～3制备的氮化硅发热膜的电阻率；按照《GB/T 22588-2008闪光法测量热扩散系数或导热系数》测试实施例1～3和对比例1～3制备的氮化硅发热膜的热导率；正负极接入220V电压，通电30秒，用红外温度测试仪测试实施例1～3和对比例1～3制备的氮化硅发热膜的表面温度，即为工作温度，测试结果见表1。Using the four-probe method to test the resistivity of the silicon nitride heating film prepared in Examples 1-3 and Comparative Examples 1-3; test Example 1 according to "GB/T 22588-2008 Flash Method for Measuring Thermal Diffusivity or Thermal Conductivity" ～3 and the thermal conductivity of the silicon nitride heating film prepared in Comparative Examples 1～3; the positive and negative poles are connected to 220V voltage, energized for 30 seconds, and the infrared temperature tester is used to test the preparation of Examples 1～3 and Comparative Examples 1～3 The surface temperature of the silicon nitride heating film is the working temperature. The test results are shown in Table 1.
表1实施例1～3和对比例1～3制备的氮化硅发热膜的性能Table 1 The properties of the silicon nitride heating film prepared in Examples 1-3 and Comparative Examples 1-3
由以上实施例可以看出，本发明提供的制备方法制备的氮化硅发热膜的耐高温性能好、使用寿命长且电阻率低，其电阻率为1.13×10-4Ω·cm，工作温度为580℃，热导率为82W/m·k。It can be seen from the above examples that the silicon nitride heating film prepared by the preparation method provided by the present invention has good high temperature resistance, long service life and low resistivity. It is 580°C and the thermal conductivity is 82W/m·k.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
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