WO2017185675A1 - 一种掺杂铬酸镧薄膜型热电偶及其制备方法 - Google Patents

一种掺杂铬酸镧薄膜型热电偶及其制备方法 Download PDF

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WO2017185675A1
WO2017185675A1 PCT/CN2016/102463 CN2016102463W WO2017185675A1 WO 2017185675 A1 WO2017185675 A1 WO 2017185675A1 CN 2016102463 W CN2016102463 W CN 2016102463W WO 2017185675 A1 WO2017185675 A1 WO 2017185675A1
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doped
film type
type thermocouple
hot
strontium chromate
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French (fr)
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史鹏
任巍
刘丹
刘明
田边
蒋庄德
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Xian Jiaotong University
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Definitions

  • the invention relates to the field of sensor preparation technology and high temperature temperature measurement technology, in particular to a doped strontium chromate film type thermocouple and a preparation method thereof.
  • thermocouples In the aeroengine design and verification experiments, in order to verify the combustion efficiency of the engine and the design of the cooling system, it is necessary to accurately test the temperature of the engine turbine blade surface, the inner wall of the combustion chamber, and the like.
  • high-temperature ceramic film thermocouples have the characteristics of small heat capacity, small volume, fast response, etc., which can capture instantaneous temperature changes, and film thermocouples can be directly deposited on the surface of the object to be measured. Does not damage the structure of the tested component, and has little impact on the working environment of the component under test. It is therefore more suitable for surface transient temperature measurement.
  • the surface temperature distribution of the hot end parts can be accurately understood, and the heat transfer and cooling scheme design can be optimized to ensure the optimal working condition of the engine and improve the engine efficiency, and provide a reliable basis for the design of the new generation fighter aircraft and civil aviation aircraft. .
  • NiCr/NiSi thin film thermocouples At present, the research on NiCr/NiSi thin film thermocouples has been relatively mature, but its test temperature range is low, and it is only suitable for low and medium temperature test occasions.
  • precious metals such as platinum and rhodium are usually used as thin film materials, but they are expensive due to their high cost, large error, and susceptibility to oxidation in harsh environments.
  • thin film ITO and In 2 O 3 materials are expected to be the core materials of choice for high temperature measurement.
  • ITO series thin film thermocouples have very high thermal volatilization due to high temperature in the high temperature region of more than 1000 °C, which causes instability of the high temperature measurement and maximum temperature limitation. This seriously restricts the application of ITO film in high temperature measurement fields such as high temperature hot runners.
  • LaCrO 3 As a typical p-type oxide conductive material, LaCrO 3 has a high melting point (2400 ° C) and good electrical conductivity, and is characterized by stable physical and chemical properties in an oxidizing and reducing atmosphere. LaCrO 3 conductivity and high temperature stability can be improved by doping elements of different valence states, and are now widely used in anode and connector materials for solid oxide fuel cells (SOFC). If two kinds of doped strontium chromite materials with different conductivity characteristics are properly combined, it is possible to become a new high temperature type film thermocouple.
  • SOFC solid oxide fuel cells
  • the present invention proposes a doped strontium chromate film type thermocouple which can be used for high temperature measurement requirements in an extreme environment and a preparation method thereof.
  • the technical solution adopted by the present invention is: a doped strontium chromate film type thermocouple comprising two hot electrodes disposed on a ceramic substrate, two hot electrodes overlapping each other, and two hot electrodes
  • the material is a strontium chromate film doped with one or more doping elements of Mg, Ca, Sr, Ba, Co, Cu, Sm, Fe, Ni and V, the two The strontium chromate film used in one of the hot electrodes is doped with different kinds of doping elements or doped with different doping elements of different contents.
  • the content of the doping element in the strontium chromate film is 0-40%.
  • the two hot electrodes are arranged in mirror symmetry along the center line of the ceramic substrate, and the two hot electrodes are overlapped to form a U-shaped structure or a V-shaped structure.
  • Each of the hot electrodes has a length of 8-30 cm, a width of 0.2-1.55 cm, a thickness of 0.3-20 ⁇ m, and a length of the two hot-electrode overlapping regions of 0.5-3 cm.
  • the ceramic substrate is a high temperature resistant structural ceramic of alumina, mullite or SiC.
  • a method for preparing a doped strontium chromate film type thermocouple comprises the steps of: selecting two kinds of hot electrode materials doped with different kinds of doping elements or doped with different doping elements of the same type, using magnetic Controlled sputtering, screen printing, pulsed laser deposition or chemical solution method, a thin film type hot electrode is deposited on a ceramic substrate, and then subjected to high temperature heat treatment to obtain a doped strontium chromate film type thermocouple.
  • the high temperature heat treatment temperature is 600 to 1200 °C.
  • thermocouple of the present invention utilizes the excellent high Seebeck coefficient characteristic exhibited by the doping of the strontium chromate film material, and the film thermocouple is formed by using two films with different conductive properties.
  • the temperature measurement in a high temperature oxidizing atmosphere can stably work for a long period of time at a high temperature of 1200 ° C - 1600 ° C.
  • the thermocouple of the present invention has a high output voltage, so that the sensitivity is high when used for calibration.
  • the invention adopts a novel ceramic thermocouple material, has wider temperature measurement range than ordinary K-type thermocouple, and can adapt to the advantages of oxidation and acid-base environment; compared with other types of high temperature resistant thermocouple materials such as platinum rhodium, etc.
  • the thermocouple cost is low in the same temperature test range; it has higher operating temperature and longer high temperature service time than ceramic film thermocouples such as ITO, and is suitable for extreme ambient temperature testing in aerospace and other fields. .
  • the method of the invention selects two kinds of hot electrode materials doped with different kinds of doping elements or doped with different doping elements, through magnetron sputtering, screen printing, Pulsed laser deposition or chemical solution method, deposited on a high temperature ceramic substrate to prepare a doped strontium chromate oxide film, and then subjected to high temperature heat treatment to finally obtain a film type thermocouple capable of stable output signal at high temperature, used in extreme environments.
  • the preparation method is simple and reliable, and the prepared thermocouple can work stably for a long time at a high temperature of 1200 ° C - 1600 ° C.
  • thermocouple cost is low in the same temperature test range; compared with the traditional ITO ceramic film thermocouple has higher use temperature and more Long high temperature service time and suitable for extreme ambient temperature testing in aerospace and other fields.
  • 1 is a schematic view showing the structure of a La 0.8 Sr 0.2 CrO 3 -LaCrO 3 thick film thermocouple of a U-shaped structure of Example 1, wherein 1-La 0.8 Sr 0.2 CrO 3 thermocouple material, 2-LaCrO 3 thermocouple material, 3 - alumina ceramic substrate, 4-electrode;
  • Example 2 is a view showing XRD results of La 0.8 Sr 0.2 CrO 3 and LaCrO 3 powders for screen printing of Example 1;
  • FIG. 3a is a SEM image of a powder of La 0.8 Sr 0.2 CrO 3 for screen printing of Example 1
  • FIG. 3b is a SEM image of a powder of LaCrO 3 ;
  • Example 4 is a time-temperature-voltage curve of a La 0.8 Sr 0.2 CrO 3 —LaCrO 3 thick film thermocouple prepared by the screen printing process of Example 1.
  • thermocouple of the present invention selects two different doped strontium chromate films as two sets of thermal electrode materials for the film thermocouple, which may be doped with the same element, but with different contents; or may be a single doping of different component elements.
  • Co-doping, doping elements are mainly Mg, Ca, Sr, Ba, Co, Cu, Sm, Fe, Ni, V, etc.; then according to the designed doping components, using magnetron sputtering, screen printing or Chemical spin coating process, depositing oxide film thermocouples for high temperature measurement on high temperature ceramic substrates, and using a pattern technology to form a device structure with thermocouple structure characteristics.
  • the thermocouple can be patterned as V or U.
  • the hot junction coincident region of the thin film thermocouple is formed by the partial overlap region between the two hot electrodes, the length of the coincidence region is between 0.5-3 cm, and the thickness of the hot electrode in the thin film thermocouple is in the range of 0.3-20 micrometers, heat The length of the electrode is between 8-30 cm, and the width of each hot electrode is 0.2-1.55 cm.
  • the prepared thin film thermocouple is heat-treated at 600-1200 ° C for 1-3 hours to increase the density of the film; Gain ability An oxide film type thermocouple that operates stably under a high temperature oxidizing atmosphere.
  • the Seebeck effect also known as the first thermoelectric effect, refers to a thermoelectric phenomenon that causes a voltage difference between two substances due to temperature differences between two different electrical conductors or semiconductors.
  • the Seebeck coefficient S is a material property based on temperature. Knowing the Seebeck coefficient S(T) of a material, the voltage difference between the two hot electrodes can be known from the formula conversion, so that the temperature difference between the hot and cold sections can be indirectly obtained. .
  • LaCrO 3 As a typical p-type oxide conductive material, LaCrO 3 has a high melting point (2400 ° C), good electrical conductivity, and stable physical and chemical properties in an oxidizing and reducing atmosphere. The conductivity and high temperature stability of LaCrO 3 can be improved by different doping. The electrical properties change due to the change of carrier scattering mechanism after doping, and the Fermi level and the intrinsic Seebeck coefficient of the material change. Therefore, we use two different doped strontium chromate films as the two sets of thermal electrode materials for the film thermocouple, which can form a film type thermocouple that can work stably at high temperatures.
  • the La 0.8 Sr 0.2 CrO 3 and LaCrO 3 powders were selected as the thermocouple electrode materials, and a thick film electrode was deposited on the alumina ceramic substrate 3 having a thickness of 1 mm by a screen printing process, and the ceramic paste for screen printing was respectively used.
  • the powders of La 0.8 Sr 0.2 CrO 3 and LaCrO 3 have a particle size of about 200 nm, and a mixed solution of ethyl cellulose and terpineol 1:2 is used as an organic solvent, and the ceramic powder is added in a ratio of 1:1.
  • the organic matter was vigorously stirred and mixed as a ceramic slurry for screen printing.
  • a U-shaped structural mask having a length of 12 cm and a width of 0.8 cm was used for screen printing of a thick film electrode, and the screen used was 200 mesh.
  • the ITO thick film is printed on the substrate, and then the indium oxide thick film is printed.
  • the thick film sample is heat treated at 700 ° C for 1 hour in a muffle furnace, and the temperature increase rate is maintained at 5 ° C / min.
  • a La 0.8 Sr 0.2 CrO 3 -LaCrO 3 thick film type thermocouple with a U-shaped structure with a thick film thickness of 50 ⁇ m was prepared.
  • Figure 1 is a schematic diagram of a U-shaped structure of a La 0.8 Sr 0.2 CrO 3 -LaCrO 3 thin film thermocouple.
  • the La 0.8 Sr 0.2 CrO 3 thermal couple electrode material 1 and the LaCrO 3 thermal couple electrode material 2 are joined to form a U-shaped thermocouple, and the thermoelectricity The two ends are connected to the electrode 4,
  • Fig. 2 is the results of La 0.8 Sr 0.2 CrO 3 and LaCrO 3 powder XRD for screen printing, and the SEM image of La 0.8 Sr 0.2 CrO 3 and LaCrO 3 for screen printing in Fig. 3
  • the time-temperature-voltage curve of the thick film thermocouple of the structure prepared by the printing process indicates that the oxide thick film thermocouple can work stably at 1270 °C.
  • the La 0.9 Sr 0.1 CrO 3 and LaCrO 3 powders were selected as the thermocouple electrode materials, and thick film electrodes were deposited on the alumina ceramic substrate with a thickness of 3 mm by screen printing.
  • the ceramic paste used for screen printing was respectively The powders of La 0.9 Sr 0.1 CrO 3 and LaCrO 3 have a particle size of about 100 nm.
  • a mixed solution of ethyl cellulose and terpineol 1:2 is used as an organic solvent, and the ceramic powder is added in a ratio of 2:3. The organic matter was vigorously stirred and mixed as a ceramic slurry for screen printing.
  • a U-shaped structural mask with a length of 25 cm and a width of 1.5 cm was selected for screen printing of thick film electrodes.
  • a LaCrO 3 thick film is printed on the substrate, and then a La 0.9 Sr 0.1 CrO 3 thick film is printed.
  • the thick film sample is heat treated at 1200 ° C for 5 hours in a muffle furnace, and the temperature rise rate is maintained.
  • a La 0.9 Sr 0.1 CrO 3 -LaCrO 3 thick film type thermocouple with a U-shaped structure with a thick film thickness of 40 ⁇ m was finally prepared.
  • the La 0.8 Sr 0.2 CrO 3 and La 0.9 Sr 0.1 CrO 3 powders were selected as thermocouple electrode materials, and thick film electrodes were deposited on a 10 mm thick alumina ceramic substrate by screen printing process for screen printing ceramics.
  • the powders of La 0.8 Sr 0.2 CrO 3 and La 0.9 Sr 0.1 CrO 3 each have a particle size of about 200 nm, and a mixed solution of ethyl cellulose and terpineol 1:2 is used as an organic solvent, and the ceramic powder is used. It was added to the organic matter in a ratio of 1:1 and vigorously stirred and mixed as a ceramic slurry for screen printing.
  • a U-shaped structural mask having a length of 20 cm and a width of 1.0 cm was used for screen printing of a thick film electrode, and the screen used was 200 mesh.
  • the ITO thick film is printed on the substrate, and then the indium oxide thick film is printed.
  • the thick film sample is heat treated at 700 ° C for 3 hours in a muffle furnace, and the temperature increase rate is maintained at 5 ° C / min.
  • a La 0.8 Sr 0.2 CrO 3 -La 0.9 Sr 0.1 CrO 3 thick film type thermocouple having a U-shaped structure with a thick film thickness of 50 ⁇ m was prepared.
  • the strontium chromate film with different doping amount of Ca was selected as the two sets of hot electrode materials for the film thermocouple.
  • the doping concentrations were 10% and 30%, respectively, which were recorded as LCC1 and LCC3, respectively.
  • the deposition and preparation of the film was carried out on a 2 mm 99 alumina substrate. First, an oxide ceramic target identical to the design component was synthesized for sputtering of the film.
  • sputtering was performed for 8 hours to obtain a thickness of 5 ⁇ m, the length of the hot electrode was 20 cm, and the hot electrode was A LCC1-LCC3 thin film type thermocouple having a width of 0.6 cm and a U-shaped structure, the length of the hot end overlap region between the two hot electrodes is 1.5 cm.
  • the prepared thin film thermocouple was heat-treated at 800 ° C for 3 hours to finally obtain an oxide thin film type thermocouple capable of stably operating under a high temperature oxidizing atmosphere.
  • thermode materials Two different elements of Sr and Ca doped strontium chromate films were selected as the two sets of thermode materials for the film thermocouples.
  • the doping concentrations were 40% and 10%, respectively, which were recorded as LSC4 and LCC1, respectively, using chemical solution deposition techniques.
  • Film deposition and preparation Firstly, a stoichiometric ratio of Sr-doped and Ca-doped barium titanate sol precursor solution (solution concentration) For 0.4 mol/L), the film was prepared by a spin coating process.
  • the LSC4 film was prepared by spin coating first, and then the LCC1 film was prepared.
  • the spin coating speed of the film was set to 2500 rpm, and the wet film obtained by spin coating was dried at 400 ° C for 5 minutes, heat treated at 650 ° C for 10 minutes, and then spin-coated again, and each hot electrode was repeated 15 times to obtain a thickness.
  • the length of the hot electrode is 20 cm
  • the width of the hot electrode is 0.3 cm
  • the LSC4-LCC1 thin film type thermocouple having a U-shaped structure, and the length of the hot end overlap region between the two hot electrodes is 1.2 cm.
  • the prepared thin film thermocouple was heat-treated at 900 ° C for 4 hours to finally obtain an oxide thin film type thermocouple capable of stably operating under a high temperature oxidizing atmosphere.
  • the strontium chromate films with different co-doping contents of Sr and Ni were selected as the two sets of thermode materials for the film thermocouples, and the doping concentrations were 10%, 20%, 10%, and 40%, respectively, which were recorded as LSCN2 and LSCN4, respectively.
  • the deposition and preparation of the film was carried out on a 99 mm thick substrate having a thickness of 2 mm by magnetron sputtering. First, an oxide ceramic target identical to the design component was synthesized for sputtering of the film.
  • sputtering was performed for 8 hours to obtain a thickness of 5 ⁇ m, the length of the hot electrode was 20 cm, and the hot electrode was A LSCN2-LSCN4 thin film type thermocouple having a width of 0.6 cm and a U-shaped structure, the length of the hot end overlap region between the two hot electrodes is 1.5 cm.
  • the prepared thin film thermocouple was heat-treated at 800 ° C for 3 hours to finally obtain an oxide thin film type thermocouple capable of stably operating under a high temperature oxidizing atmosphere.

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Abstract

一种掺杂铬酸镧薄膜型热电偶，包括设置在陶瓷基片（3）上的两个热电极（1，2），两个热电极（1，2）相互搭接，两个热电极（1，2）的材料均采用铬酸镧薄膜，铬酸镧薄膜中掺杂有Mg、Ca、Sr、Ba、Co、Cu、Sm、Fe、Ni和V中的一种或几种掺杂元素，,两个热电极（1，2）采用的铬酸镧薄膜中掺杂有不同种掺杂元素，或者掺杂有含量不同的同种掺杂元素。还公开了一种掺杂铬酸镧薄膜型热电偶的制备方法。

Description

一种掺杂铬酸镧薄膜型热电偶及其制备方法 技术领域
本发明涉及传感器制备技术及高温温度测量技术领域，具体涉及一种掺杂铬酸镧薄膜型热电偶及其制备方法。
背景技术
在航空发动机设计及验证实验中，为了验证发动机的燃烧效率以及冷却系统的设计，需要准确测试发动机涡轮叶片表面、燃烧室内壁等部位的温度。与传统的线形和块形热电偶相比，高温陶瓷型薄膜热电偶具有热容量小、体积小、响应速度快等特点，能够捕捉瞬时温度变化，同时薄膜热电偶可直接沉积在被测对象的表面，不破坏被测部件结构，而且对被测部件工作环境影响小。因此更适合用于表面瞬态温度测量。通过薄膜热电偶可准确了解热端部件表面温度分布状况，可以优化传热、冷却方案设计，进而保证发动机工作在最优工作状态、提高发动机效率，为新一代战斗机和民航客机的设计提供可靠依据。
目前对NiCr/NiSi薄膜热电偶的研究，已经相对成熟，但是其测试温度范围低，只适应与中低温度测试场合。在高温测试领域，通常采用铂、铑等贵金属为薄膜材料，但是由于其存在成本高、误差大、恶劣环境易氧化等问题。迫切需要研制一种耐高温、性能稳定的新型陶瓷薄膜热电偶。现有的研究中，薄膜型的ITO和In2O3材料有望成为高温测量的核心首选材料。但是进一步的研究发现，ITO系列薄膜热电偶由于在大于1000℃的高温区域会出现非常剧烈的热挥发，从而造成其高温测量的不稳定以及最高温度的限制。这一点严重制约着ITO薄膜在高温热流道等高温测量领域的应用。
LaCrO3作为一种典型的p型氧化物导电材料，具有熔点高(2400℃)和较好的导电能力，且在氧化和还原气氛中物理化学性质稳定等特点。通过掺杂不同价态的元素能够提高 LaCrO3导电能力和高温稳定性，现在已被广泛应用于固体氧化物燃料电池(SOFC)的阳极和连接体材料。如果将两种不同导电特性的掺杂铬酸镧材料通过合理的组合，就有可能成为一种新的高温型薄膜热电偶。
发明内容
为了解决现有技术中的问题，本发明提出一种能够用于极端环境下的高温测量需求的掺杂铬酸镧薄膜型热电偶及其制备方法。
为了实现以上目的，本发明所采用的技术方案为：一种掺杂铬酸镧薄膜型热电偶，包括设置在陶瓷基片上的两个热电极，两个热电极相互搭接，两个热电极的材料均采用铬酸镧薄膜，铬酸镧薄膜中掺杂有Mg、Ca、Sr、Ba、Co、Cu、Sm、Fe、Ni和V中的一种或几种掺杂元素，所述两个热电极采用的铬酸镧薄膜中掺杂有不同种掺杂元素，或者掺杂有含量不同的同种掺杂元素。
所述铬酸镧薄膜中掺杂元素的含量为0-40％。
所述两个热电极沿陶瓷基片中心线呈镜像对称设置，两个热电极搭接形成U型结构或V型结构。
所述每个热电极的长度在8-30cm，宽度为0.2-1.55cm，厚度为0.3-20μm，两个热电极搭接重合区的长度为0.5-3cm。
所述陶瓷基片为氧化铝、莫来石或SiC的耐高温结构陶瓷。
一种掺杂铬酸镧薄膜型热电偶的制备方法，包括以下步骤：选择掺杂有不同种掺杂元素，或者掺杂有含量不同的同种掺杂元素的两个热电极材料，采用磁控溅射、丝网印刷、脉冲激光沉积或者化学溶液法，在陶瓷基片上沉积成薄膜型热电极，再经过高温热处理，即得到掺杂铬酸镧薄膜型热电偶。
所述高温热处理温度为600-1200℃。
与现有技术相比，本发明的热电偶利用铬酸镧薄膜材料掺杂改性后所表现出来的优异的高塞贝克系数特性，采用两种不同导电特性的薄膜构成薄膜型热电偶，用于高温氧化气氛中的温度测量，能够在1200℃-1600℃高温下长期稳定工作，本发明的热电偶具有输出电压较高，从而在校准使用时灵敏度较高。本发明采用新型陶瓷热电偶材料，相比普通K型热电偶，具有测温范围更广，而且能够适应氧化和酸碱环境的优点；相比其他类型耐高温热电偶材料如铂铑等，在相同的温度测试范围内，其热电偶成本低；相比于传统ITO等陶瓷薄膜热电偶具有更高的使用温度和更长的高温服役时间，且适用于在航天航空等领域的极端环境温度测试。
与现有技术相比，本发明的方法选择掺杂有不同种掺杂元素，或者掺杂有含量不同的同种掺杂元素的两个热电极材料，通过磁控溅射、丝网印刷、脉冲激光沉积或者化学溶液法，在高温陶瓷基片上沉积制备出掺杂铬酸镧氧化物薄膜，再经过高温热处理最终获得能在高温下稳定输出信号的薄膜型热电偶，用于极端环境下的高温测量需求，制备方法过程简单可靠，制得的热电偶能够在1200℃-1600℃高温下长期稳定工作，相比普通K型热电偶，具有测温范围更广，而且能够适应氧化和酸碱环境的优点；相比其他类型耐高温热电偶材料如铂铑等，在相同的温度测试范围内，其热电偶成本低；相比于传统ITO等陶瓷薄膜热电偶具有更高的使用温度和更长的高温服役时间，且适用于在航天航空等领域的极端环境温度测试。
附图说明
图1为实施例1的U型结构La0.8Sr0.2CrO3-LaCrO3厚膜热电偶结构示意图，其中1-La0.8Sr0.2CrO3热偶电极材料，2-LaCrO3热偶电极材料，3-氧化铝陶瓷基板、4-电极；
图2为实施例1丝网印刷用La0.8Sr0.2CrO3和LaCrO3粉体的XRD结果图；
图3a为实施例1丝网印刷用La0.8Sr0.2CrO3的粉体SEM图，图3b为LaCrO3的粉体SEM图；
图4为实施例1丝网印刷工艺制备得到的La0.8Sr0.2CrO3-LaCrO3厚膜热电偶的时间-温度- 电压曲线。
具体实施方式
下面结合具体实施例对本发明作进一步的解释说明。
本发明的热电偶选取两种不同掺杂的铬酸镧薄膜作为薄膜热电偶的两组热电极材料，可以是同一元素掺杂，但是含量不同；也可以是不同组份元素的单一掺杂和共掺杂，掺杂元素主要为Mg、Ca、Sr、Ba、Co、Cu、Sm、Fe、Ni、V等；然后按照设计好的掺杂组份，采用磁控溅射、丝网印刷或者化学旋涂工艺，在高温陶瓷基片上沉积制备可用于高温温度测量的氧化物薄膜热电偶，并采用图形化技术组成具有热电偶结构特征的器件结构，热电偶的图形化可以为V型或者U型，两个热电极之间通过部分重叠区域构成薄膜热电偶的热端重合区，重合区的长度为0.5-3cm之间，薄膜热电偶中热电极的厚度在0.3-20微米范围内，热电极的长度在8-30cm之间，每个热电极的宽度为0.2-1.55cm；最后，将制备得到的薄膜热电偶在600-1200℃高温热处理1-3小时，提高薄膜的致密度；最终获得能够在高温氧化气氛下稳定工作的氧化物薄膜型热电偶。
按照化学计量法，各种元素掺杂后形成的化学式为：
Mg部分取代Cr：LaCr1-xMgxO3；
Ca部分取代La：La1-xCaxCrO3；
Sr部分取代La：La1-xSrxCrO3；
Ba部分取代La：La1-xBaxCrO3；
Fe部分取代Cr：LaCr1-xFexO3；
Sm部分取代La：La1-xSmxCrO3；
Cu部分取代Cr：LaCr1-xCuxO3；
Co部分取代Cr：LaCr1-xCoxO3；
Ni部分取代Cr：LaCr1-xNixO3；
本发明的原理：塞贝克(Seebeck)效应，又称作第一热电效应，它是指由于两种不同电导体或半导体的温度差异而引起两种物质间的电压差的热电现象。而塞贝克系数S是基于温度的材质特性，知道一个材质的塞贝克系数S(T)，从公式转化即可得知两个热电极间的电压差，从而可以间接得到冷热段的温度差。
Figure PCTCN2016102463-appb-000001
从上面公式可以看出，随着温度的上升，费米分布函数中的能量也快速攀升，所以受热端的每电子平均能量较高，相应的，受热端的电子不断向冷段发散，直到形成一个电压差阻止其进一步发散。进一步通过数理推导可以得出赛贝克系数的表达式为：
Figure PCTCN2016102463-appb-000002
其中，EFO为0K时的费米能。从公式可以看出，塞贝克系数与材料本身的费米能有关，也和实际绝对温度值有关。那么，对于两组热电极材料，如果冷热端温度确定，它们之间的温差和电压差就是固定的。这正是作为高温型热电偶所必须的基本要求。同样，当两个热电极材料的赛贝克系数不一致时就会在两个热电极的冷锻形成可以感知的热电势差值。
LaCrO3作为一种典型的p型氧化物导电材料，具有熔点高(2400℃)、导电能力好，且在氧化和还原气氛中物理化学性质稳定等特点。通过不同的掺杂能够提高LaCrO3导电能力和高温稳定性,由于掺杂后载流子散射机制变化而导致电学性能改变，材料的费米能级和本征赛贝克系数均发生改变。因此，我们选用两种不同掺杂的铬酸镧薄膜作为薄膜热电偶的两组热电极材料，就能够构成能够在高温下稳定工作的薄膜型热电偶。
实施例1
选用的La0.8Sr0.2CrO3和LaCrO3粉体作为热电偶电极材料，采用丝网印刷工艺在厚度为1mm的氧化铝陶瓷基板3上沉积厚膜电极，用于丝网印刷的陶瓷浆料分别由La0.8Sr0.2CrO3和 LaCrO3的粉体其粒度均为200nm左右，采用乙基纤维素和松油醇1：2的混合溶液作为有机溶剂，将陶瓷粉体按照1：1的比例加入到有机物中并进行强力搅拌混合，作为用于丝网印刷的陶瓷浆料。为了获得良好的图形化，选取热电极长度为12cm，宽度为0.8cm的U型结构掩模板进行厚膜电极的丝网印刷制备，所用网版为200目。先在基板上印刷ITO厚膜，然后再印刷氧化铟厚膜，两种厚膜材料都沉积结束以后，将厚膜样品在马弗炉中700℃热处理1小时，升温速度保持在5℃/min，最终制备出厚膜厚度为50微米的具有U型结构的La0.8Sr0.2CrO3-LaCrO3厚膜型热电偶。图1为U型结构La0.8Sr0.2CrO3-LaCrO3薄膜热电偶结构示意图，La0.8Sr0.2CrO3热偶电极材料1和LaCrO3热偶电极材料2搭接形成U型结构热电偶，热电偶两端连接电极4，图2丝网印刷用La0.8Sr0.2CrO3和LaCrO3粉体XRD结果，图3丝网印刷用La0.8Sr0.2CrO3和LaCrO3的SEM图，图4丝网印刷工艺制备得到的该结构的厚膜热电偶的时间-温度-电压曲线，表明该氧化物厚膜热电偶能够在1270℃下稳定工作。
实施例2
选用的La0.9Sr0.1CrO3和LaCrO3粉体作为热电偶电极材料，采用丝网印刷工艺在厚度为3mm的氧化铝陶瓷基板上沉积厚膜电极，用于丝网印刷的陶瓷浆料分别由La0.9Sr0.1CrO3和LaCrO3的粉体其粒度均为100nm左右，采用乙基纤维素和松油醇1：2的混合溶液作为有机溶剂，将陶瓷粉体按照2：3的比例加入到有机物中并进行强力搅拌混合，作为用于丝网印刷的陶瓷浆料。为了获得良好的图形化，选取热电极长度为25cm，宽度为1.5cm的U型结构掩模板进行厚膜电极的丝网印刷制备。先在基板上印刷LaCrO3厚膜，然后再印刷La0.9Sr0.1CrO3厚膜，两种厚膜材料都沉积结束以后，将厚膜样品在马弗炉中1200℃热处理5小时，升温速度保持在3℃/min，最终制备出厚膜厚度为40微米的具有U型结构的La0.9Sr0.1CrO3-LaCrO3厚膜型热电偶。
实施例3
选用的La0.8Sr0.2CrO3和La0.9Sr0.1CrO3粉体作为热电偶电极材料，采用丝网印刷工艺在厚度为10mm的氧化铝陶瓷基板上沉积厚膜电极，用于丝网印刷的陶瓷浆料分别由La0.8Sr0.2CrO3和La0.9Sr0.1CrO3的粉体其粒度均为200nm左右，采用乙基纤维素和松油醇1：2的混合溶液作为有机溶剂，将陶瓷粉体按照1：1的比例加入到有机物中并进行强力搅拌混合，作为用于丝网印刷的陶瓷浆料。为了获得良好的图形化，选取热电极长度为20cm，宽度为1.0cm的U型结构掩模板进行厚膜电极的丝网印刷制备，所用网版为200目。先在基板上印刷ITO厚膜，然后再印刷氧化铟厚膜，两种厚膜材料都沉积结束以后，将厚膜样品在马弗炉中700℃热处理3小时，升温速度保持在5℃/min，最终制备出厚膜厚度为50微米的具有U型结构的La0.8Sr0.2CrO3-La0.9Sr0.1CrO3厚膜型热电偶。
实施实例4
选取Ca元素不同掺杂量的铬酸镧薄膜作为薄膜热电偶的两组热电极材料，掺杂浓度分别为10％、30％，分别记作LCC1和LCC3，采用磁控溅射技术在厚度为2mm的99氧化铝基片上进行薄膜的沉积和制备。首先，合成出与设计组份完全相同的氧化物陶瓷靶材用于薄膜的溅射。通过调整溅射工艺中的溅射气压(5Pa)、氧氩比(1:6)和溅射功率(120w)，溅射8小时获得厚度为5微米、热电极的长度为20cm，热电极的宽度为0.6cm，具有U型结构的LCC1-LCC3薄膜型热电偶，两个热电极之间热端重合区长度为1.5cm。最后，将制备得到的薄膜热电偶在800℃热处理3小时，最终获得能够在高温氧化气氛下稳定工作的氧化物薄膜型热电偶。
实施实例5
选取Sr、Ca两种不同元素掺杂的铬酸镧薄膜作为薄膜热电偶的两组热电极材料，掺杂浓度分别为40％和10％，分别记作LSC4和LCC1，采用化学溶液沉积技术进行薄膜的沉积和制备。首先，分别合成出符合化学计量比的掺Sr和掺Ca的钛酸锶溶胶前驱体溶液(溶液浓度 为0.4mol/L)，采用旋涂工艺进行薄膜的制备。先旋涂制备LSC4薄膜，然后再制备LCC1薄膜。设定薄膜的旋涂转速为2500rpm，每次旋涂得到的湿膜先后在400℃干燥5分钟、650℃热处理10分钟后再重复进行旋涂沉积，每个热电极均重复15次，获得厚度为1微米、热电极的长度为20cm，热电极的宽度为0.3cm，具有U型结构的LSC4-LCC1薄膜型热电偶，两个热电极之间热端重合区长度为1.2cm。最后，将制备得到的薄膜热电偶在900℃热处理4小时，最终获得能够在高温氧化气氛下稳定工作的氧化物薄膜型热电偶。
实施实例6
选取Sr、Ni元素不同共掺杂量的铬酸镧薄膜作为薄膜热电偶的两组热电极材料，掺杂浓度分别为10％、20％和10％、40％，分别记作LSCN2和LSCN4，采用磁控溅射技术在厚度为2mm的99氧化铝基片上进行薄膜的沉积和制备。首先，合成出与设计组份完全相同的氧化物陶瓷靶材用于薄膜的溅射。通过调整溅射工艺中的溅射气压(5Pa)、氧氩比(1:6)和溅射功率(120w)，溅射8小时获得厚度为5微米、热电极的长度为20cm，热电极的宽度为0.6cm，具有U型结构的LSCN2-LSCN4薄膜型热电偶，两个热电极之间热端重合区长度为1.5cm。最后，将制备得到的薄膜热电偶在800℃热处理3小时，最终获得能够在高温氧化气氛下稳定工作的氧化物薄膜型热电偶。

Claims (7)

  1. 一种掺杂铬酸镧薄膜型热电偶，其特征在于，包括设置在陶瓷基片上的两个热电极，两个热电极相互搭接，两个热电极的材料均采用铬酸镧薄膜，铬酸镧薄膜中掺杂有Mg、Ca、Sr、Ba、Co、Cu、Sm、Fe、Ni和V中的一种或几种掺杂元素，所述两个热电极采用的铬酸镧薄膜中掺杂有不同种掺杂元素，或者掺杂有含量不同的同种掺杂元素。
  2. 根据权利要求1所述的一种掺杂铬酸镧薄膜型热电偶，其特征在于，所述铬酸镧薄膜中掺杂元素的含量为0-40％。
  3. 根据权利要求1所述的一种掺杂铬酸镧薄膜型热电偶，其特征在于，所述两个热电极沿陶瓷基片中心线呈镜像对称设置，两个热电极搭接形成U型结构或V型结构。
  4. 根据权利要求3所述的一种掺杂铬酸镧薄膜型热电偶，其特征在于，所述每个热电极的长度在8-30cm，宽度为0.2-1.55cm，厚度为0.3-20μm，两个热电极搭接重合区的长度为0.5-3cm。
  5. 根据权利要求1所述的一种掺杂铬酸镧薄膜型热电偶，其特征在于，所述陶瓷基片为氧化铝、莫来石或SiC的耐高温结构陶瓷。
  6. 如权利要求1-5任一项所述的一种掺杂铬酸镧薄膜型热电偶的制备方法，其特征在于，包括以下步骤：选择掺杂有不同种掺杂元素，或者掺杂有含量不同的同种掺杂元素的两个热电极材料，采用磁控溅射、丝网印刷、脉冲激光沉积或者化学溶液法，在陶瓷基片上沉积成薄膜型热电极，再经过高温热处理，即得到掺杂铬酸镧薄膜型热电偶。
  7. 根据权利要求6所述的一种掺杂铬酸镧薄膜型热电偶的制备方法，其特征在于，所述高温热处理温度为600-1200℃。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116295896A (zh) * 2023-04-07 2023-06-23 昆明理工大学 一种超级热电偶及其制备方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105823569B (zh) * 2016-04-27 2018-10-30 西安交通大学 一种掺杂铬酸镧薄膜型热电偶及其制备方法
CN106679838B (zh) * 2016-12-27 2020-04-28 西安交通大学 一种具有超大输出电压的薄膜型热电偶及其制备方法
CN109378381A (zh) * 2018-10-19 2019-02-22 包头稀土研究院 高温热电单元及其制造方法
CN110319945B (zh) * 2019-06-20 2021-09-24 西安交通大学 一种耐高温高灵敏柔性碳化硅基温度传感器及制作方法
WO2021237602A1 (zh) * 2020-05-28 2021-12-02 南昌欧菲显示科技有限公司 薄膜式热电偶、温度传感器及智能穿戴设备
CN112194507B (zh) * 2020-09-21 2022-02-15 江苏大学 一种抗高温热震、宽光谱高吸收的光热涂层及其制备方法
CN112729580B (zh) * 2020-12-23 2023-04-28 西安交通大学 一种柔性温度传感器及其制备方法
CN113174568B (zh) * 2021-04-20 2022-11-22 中国航发北京航空材料研究院 制备晶面择优取向氧化铟锡-氧化铟薄膜热电偶的方法
CN115855292A (zh) * 2022-11-25 2023-03-28 西安交通大学 一种高熵氧化物作为热电极制备高温温度传感器的方法
CN119437457B (zh) * 2023-08-04 2026-03-13 中国科学院物理研究所 高熵二维材料在温度计中的用途和温度计

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1323074A (zh) * 2001-07-06 2001-11-21 清华大学 高温热源－氧浓差电池堆联合发电装置
US20020108856A1 (en) * 2000-11-27 2002-08-15 Akira Kunimoto Gas sensing and oxygen pumping device, and apparatus using the same
CN101281065A (zh) * 2007-04-06 2008-10-08 洛阳市西格马仪器制造有限公司 氧化锆温度传感器
CN103017922A (zh) * 2011-09-26 2013-04-03 中国电子科技集团公司第四十八研究所 一种快速响应薄膜热电偶温度传感器及其制造方法
CN103900728A (zh) * 2014-04-23 2014-07-02 大连交通大学 一种陶瓷薄膜热电偶及其制备方法
CN105300544A (zh) * 2015-11-12 2016-02-03 西安交通大学 一种氧化物薄膜型热电偶及其制备方法
CN105823569A (zh) * 2016-04-27 2016-08-03 西安交通大学 一种掺杂铬酸镧薄膜型热电偶及其制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001326392A (ja) * 2000-05-17 2001-11-22 Unitika Ltd 高温用ｐ型熱電素子材料
JP4257419B2 (ja) * 2003-11-07 2009-04-22 独立行政法人産業技術総合研究所 ｎ型熱電変換特性を有する複合酸化物
JP4670017B2 (ja) * 2004-03-25 2011-04-13 独立行政法人産業技術総合研究所 熱電変換素子及び熱電変換モジュール
US20100252086A1 (en) * 2007-07-25 2010-10-07 Kyocera Corporation Thermoelectric Element, Thermoelectric Module, and Method for Manufacturing Thermoelectric Element
CN101452762B (zh) * 2008-09-18 2010-12-15 天津市天发重型水电设备制造有限公司 一种磁极线圈编绕成型方法
DE102012110845A1 (de) * 2012-11-12 2014-05-15 Epcos Ag Temperaturfühler und Verfahren zur Herstellung eines Temperaturfühlers
DE102014110065A1 (de) * 2014-07-17 2016-01-21 Epcos Ag Material für ein thermoelektrisches Element und Verfahren zur Herstellung eines Materials für ein thermoelektrisches Element
CN105444911A (zh) * 2015-11-12 2016-03-30 西安交通大学 一种掺杂钛酸锶薄膜型热电偶

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020108856A1 (en) * 2000-11-27 2002-08-15 Akira Kunimoto Gas sensing and oxygen pumping device, and apparatus using the same
CN1323074A (zh) * 2001-07-06 2001-11-21 清华大学 高温热源－氧浓差电池堆联合发电装置
CN101281065A (zh) * 2007-04-06 2008-10-08 洛阳市西格马仪器制造有限公司 氧化锆温度传感器
CN103017922A (zh) * 2011-09-26 2013-04-03 中国电子科技集团公司第四十八研究所 一种快速响应薄膜热电偶温度传感器及其制造方法
CN103900728A (zh) * 2014-04-23 2014-07-02 大连交通大学 一种陶瓷薄膜热电偶及其制备方法
CN105300544A (zh) * 2015-11-12 2016-02-03 西安交通大学 一种氧化物薄膜型热电偶及其制备方法
CN105823569A (zh) * 2016-04-27 2016-08-03 西安交通大学 一种掺杂铬酸镧薄膜型热电偶及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116295896A (zh) * 2023-04-07 2023-06-23 昆明理工大学 一种超级热电偶及其制备方法

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