CN102912332B - Method for preparing RexCe1-xOy/M2Zr2O7 double-layer buffer layer by chemical solution deposition - Google Patents

Method for preparing RexCe1-xOy/M2Zr2O7 double-layer buffer layer by chemical solution deposition Download PDF

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CN102912332B
CN102912332B CN 201210318962 CN201210318962A CN102912332B CN 102912332 B CN102912332 B CN 102912332B CN 201210318962 CN201210318962 CN 201210318962 CN 201210318962 A CN201210318962 A CN 201210318962A CN 102912332 B CN102912332 B CN 102912332B
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film
buffer layer
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rare earth
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CN102912332A (en
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雷鸣
赵勇
武伟
蒲明华
张勇
张欣
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西南交通大学
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Abstract

本发明公开了一种化学溶液沉积法制备RexCe1-xOy/M2Zr2O7双层缓冲层的方法,其具体作法是:a、M2Zr2O7薄膜的制备:将M(NO3)3.6H2O和ZrO(NO3)3.2H2O按照离子浓度M+3:Zr+4为1:1溶于羟乙基甲基醚,加入氧化聚乙烯20000合成胶体;将胶体涂覆于Ni基合金基带上,干燥后放入H2/Ar还原气氛保护的热处理炉内分解成相;b、RexCe1-xOy薄膜的制备:按稀土离子(Re)与铈离子(Ce)比x:1-x,0≤x≤0.5配制稀土硝酸盐混合物,将混合物溶解于高分子有机溶剂合成胶体,将胶体涂覆于M2Zr2O7基底上,干燥后放入气氛烧结炉中,在H2/Ar还原气氛保护下分解成相。 The present invention discloses a method of chemical solution deposition Preparation RexCe1-xOy / M2Zr2O7 bilayer buffer layer, the specific practice: a, preparing M2Zr2O7 film: the M (NO3) 3.6H2O and ZrO (NO3) 3.2H2O in accordance ion concentration in M ​​+ 3: Zr + 4 1: 1 was dissolved in hydroxyethyl methyl ether, polyethylene oxide added 20,000 synthetic colloids; colloidal applied to Ni-base alloy strip group, after drying into H2 / Ar reducing atmosphere heat treatment furnace is decomposed into phase protection; preparation b, RexCe1-xOy film: by rare earth ions (Re) and cerium ions (Ce) ratio of x: 1-x, 0≤x≤0.5 formulated mixture of rare earth nitrates, and the mixture was polymer is dissolved in an organic solvent synthetic colloids, colloidal M2Zr2O7 coated on a substrate, and dried into a sintering furnace atmosphere, reducing atmosphere protection phase decomposed into H2 / Ar. 本发明采用全硝酸盐体系化学溶液沉积法,来制备RexCe1-xOy/M2Zr2O7双层缓冲层,该制备方法与物理法相比简单易行、成本低、无污染、可大规模工业化生产。 The present invention employs a full system chemical solution deposition nitrate, prepared RexCe1-xOy / M2Zr2O7 bilayer buffer layer, the preparation process is simple compared with physical methods, low cost, pollution, industrial production can.

Description

—种化学溶液沉积法制备RexCei_x0y/M2Zr207双层缓冲层的方法 - Method for preparing chemical solution deposition method RexCei_x0y / M2Zr207 bilayer buffer layer

技术领域 FIELD

[0001] 本发明属于高温超导涂层导体研究领域,具体来讲涉及一种化学溶液沉积法制备RexCe1^xOy/ M2Zr2O7双层缓冲层的方法。 [0001] The present invention belongs to the field of coated conductor HTS research, and specifically relates to a method for preparing a chemical solution deposition method RexCe1 ^ xOy / M2Zr2O7 bilayer buffer layer.

背景技术 Background technique

[0002] 第二代高温超导带材,由于其优良的本征电磁特性,尤其是其在高磁场下优良的载流能力,在电力系统中拥有广阔的应用前景。 [0002] The second-generation high temperature superconducting tapes, because of their excellent intrinsic electromagnetic properties, in particular its has broad application prospects in the power system in an excellent current carrying capacity at high magnetic fields.

[0003] 高温超导涂层导体组成包括三部分,基底、缓冲层、超导层,缓冲层材料在其中既作为生长模板,又充当阻隔层,作用重大。 [0003] HTS coated conductors consists of three parts, a base, a buffer layer, a superconducting layer, a buffer layer material in which growth both as a template, and as a barrier layer, a significant effect. La2Zr2O7由于热稳定性以及与NiW基底和YBCO很好的化学匹配性,已成为涂层导体研究的热点。 La2Zr2O7 thermal stability and a YBCO NiW substrate and good chemical matching, has become a hot research coated conductor. 而CeO2由于其具有与超导层极佳的匹配度和良好的化学稳定性,目前仍然是首选的缓冲层材料。 CeO2 and the superconducting layer due to its excellent matching and good chemical stability, is still the preferred buffer layer material. 但是化学法制备的CeO2单层缓冲层存在临界厚度较小的问题,不足以起到阻隔作用。 There is a small but critical thickness of a single layer problem CeO2 buffer layer chemical method, do not act as a barrier effect. 而在La2Zr2O7上很难获得高性能的YBCO超导层。 In the La2Zr2O7 difficult to obtain a high-performance superconducting YBCO layer. 所以RexCei_x0y/La2Zr207双层缓冲层成为目前较为流行的缓冲层框架形式。 Therefore RexCei_x0y / La2Zr207 bilayer buffer layer it becomes more popular form of a frame buffer layer.

发明内容 SUMMARY

[0004] 本发明的目的在于提供一种价格低廉,有利于大规模工业化生产的制备RexCei_x0y/M2Zr207双层缓冲层的方法,该制备方法与物理法相比简单易行、成本低、无污染、可大规模工业化生产。 [0004] The object of the present invention is to provide a low price, a process for preparing large-scale industrial production RexCei_x0y / M2Zr207 bilayer buffer layer is beneficial, the preparation process is simple compared with physical methods, low cost, non-polluting, can large-scale industrial production.

[0005] 本发明解决其技术问题所采用的技术方案为,一种化学溶液沉积法制备RexCei_x0y/M2Zr207双层缓冲层的方法,其特征在于:依次由以下步骤构成: [0005] aspect of the present invention to solve the technical problem is, prepare a chemical solution deposition method RexCei_x0y M2Zr207 method bilayer buffer layer /, wherein: constituted by sequentially the following steps:

[0006] a、M2Zr2O7 薄膜的制备: [0006] a, M2Zr2O7 Thin Film:

[0007] 将M(NO3)3.6H20和ZrO(NO3)3.2H20按照离子浓度M+3 =Zr+4为1:1溶于羟乙基甲基醚中,加入氧化聚乙烯20000合成胶体,将胶体涂覆于Ni基合金基带上,干燥后放入通有H2/Ar还原气氛的热处理炉内分解成相。 [0007] The M (NO3) 3.6H20 and ZrO (NO3) 3.2H20 in accordance with the ion concentration of M + 3 = Zr + 4 1: 1 was dissolved in hydroxyethyl methyl ether, polyethylene oxide added 20,000 colloid synthesis, the colloidal coated Ni-base alloy base band, after drying has placed on H2 / Ar reducing atmosphere heat treatment furnace is broken down into phases.

[0008] b、稀土RexCei_x0y 薄膜的制备: [0008] b, rare earth RexCei_x0y Thin Film:

[0009] 按稀土(Re)离子与铈(Ce)离子比x:1 — X,O < x < 0.5配制稀土硝酸盐混合物,将混合物溶解在高分子有机溶剂中,将溶液涂覆于M2Zr2O7基底上,干燥后放入H2/Ar还原气氛保护的气氛烧结炉中,分解成相。 [0009] Press rare earth (Re) ions to cerium (Ce) ion ratio x: 1 - X, O <x ​​<0.5 formulated mixture of rare earth nitrates, the polymer mixture is dissolved in an organic solvent, the solution is coated on a substrate M2Zr2O7 the dried into H2 / Ar reducing atmosphere sintering furnace protective atmosphere, broken down into phases.

[0010] 根据本发明所述的一种化学溶液沉积法制备Rexcei_x0y/M2zr207双层缓冲层的方法,其特征在于:所述a步中,稀土(M)为镧(La)或钆(Gd)。 [0010] The method for preparing a chemical solution deposition method Rexcei_x0y the present invention / M2zr207 bilayer buffer layer, wherein: said step a, the rare earth (M) of lanthanum (La) and gadolinium (Gd) .

[0011] 根据本发明所述的一种化学溶液沉积法制备Rexcei_x0y/M2zr207双层缓冲层的方法,其特征在于:所述a步中,硝酸钆、硝酸锆和羟乙基甲基醚的用量比为:1摩尔(硝酸钆+硝酸锆):0.5 — 3升体积羟乙基甲基醚。 [0011] The method for preparing a chemical solution deposition method Rexcei_x0y the present invention / M2zr207 bilayer buffer layer, wherein: said step a, the amount of gadolinium nitrate, zirconium nitrate and hydroxyethyl methyl ether ratio: 1 mole of (+ zirconium nitrate gadolinium nitrate): 0.5 --3 liter volume hydroxyethyl methyl ether.

[0012] 根据本发明所述的一种化学溶液沉积法制备Rexcei_x0y/M2zr207双层缓冲层的方法,其特征在于:所述a步中,氧化聚乙烯20000的加入量为前驱溶液总质量的3wt.% -5wt.% ο [0012] The method for preparing a chemical solution deposition method Rexcei_x0y the present invention / M2zr207 bilayer buffer layer, wherein: said step a, an oxidized polyethylene added in an amount of 20,000 is the total mass of the precursor solution of 3wt .% -5wt.% ο

[0013] 据本发明所述的一种化学溶液沉积法制备RexCei_x0y/M2Zr207双层缓冲层的方法,其特征在于:所述a步中,分解成相过程为先以1°C /min -5°C /min速率升温至350°C —600°C,让有机物和硝酸盐充分分解,后直接升温至110(TC — 120(TC成相温度,保温I 一2 [0013] According to the method of Preparation RexCei_x0y a chemical solution deposition method of the present invention / M2Zr207 bilayer buffer layer, wherein: said step a, the process is decomposed into the first phase at 1 ° C / min -5 ° C / min heating rate to 350 ° C -600 ° C, so that organic matter and nitrates decompose sufficiently, the temperature was raised directly to 110 (TC - 120 (TC to temperature phase, I an insulation 2

小时,获得RexCei_x0y薄膜。 Hours to obtain RexCei_x0y film.

[0014] 据本发明所述的一种化学溶液沉积法制备RexCei_x0y/M2Zr207双层缓冲层的方法,其特征在于:所述b步中,稀土为钇(Y)、镧(La)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钦(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)中的一种。 [0014] According to the method of Preparation RexCei_x0y a chemical solution deposition method of the present invention / M2Zr207 bilayer buffer layer, wherein: said step b, the rare earth is yttrium (Y), lanthanum (La), praseodymium ( Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), Chin (Ho), erbium (Er), thulium (Tm), ytterbium ( yb), one kind of (Lu) in lutetium.

[0015] 据本发明所述的一种化学溶液沉积法制备RexCei_x0y/M2Zr207双层缓冲层的方法,其特征在于:所述b步中,高分子有机溶剂为聚甲基丙烯酸或丙烯酸与NN 二甲基甲酰胺的聚合物。 [0015] According to the method of Preparation RexCei_x0y a chemical solution deposition method of the present invention / M2Zr207 bilayer buffer layer, wherein: said step b, the polymer solvent is an organic acid or polymethacrylic acid with two NN polymer dimethylformamide.

[0016] 据本发明所述的一种化学溶液沉积法制备RexCei_x0y/M2Zr207双层缓冲层的方法,其特征在于:所述b步中,分解成相过程为将炉温以TC /min 一5°C /min速率升至350oC - 550 oC,保证高分子有机物和硝酸盐充分分解,后升温至1000°C - 1200°C成相温度,保温I — 2小时,RexCe1^xOy结晶成相。 [0016] According to the method of Preparation RexCei_x0y a chemical solution deposition method according to the present invention / M2Zr207 bilayer buffer layer, wherein: said step b, the process is decomposed into the furnace with at TC / min a 5 ° C / min rate was raised to 350oC - 550 oC, to ensure full decomposition of nitrates and organic polymer, the temperature was raised to 1000 ° C - 1200 ° C with respect to temperature, heat I - 2 hours, RexCe1 ^ xOy crystal phase.

[0017] 据本发明所述的一种化学溶液沉积法制备RexCei_x0y/M2Zr207双层缓冲层的方法,其特征在于:所述a步和b步中,涂覆方法可为旋涂法、提拉法或狭缝喷涂法。 [0017] According to the method of Preparation RexCei_x0y a chemical solution deposition method of the present invention / M2Zr207 bilayer buffer layer, wherein: said step a and step b, a coating method may be spin coating, dip or slit coating method.

[0018] 本发明的有益效果在于:与现有技术相比,其一,本发明采用全硝酸盐体系化学溶液沉积法,极大地降低了制备成本,并且化学法更易大规模工业化生产;其二,采用高分子有机溶剂来制备的稀土掺杂的CeO2缓冲层,其临界厚度得到大幅度提高;其三,采用RexCei_x0y/M2Zr207双层缓冲层的框架,既有效保证了缓冲层的厚度足以良好地起到阻隔层作用,其上的RexCei_x0y缓冲层又能确保后续制备高性能的YBCO超导层。 [0018] Advantageous effects of the present invention is that: compared with the prior art, First, the present invention employs the whole nitrate solution chemical deposition system, greatly reducing the manufacturing cost, and more chemical industrial production; Second , prepared using the high molecular organic solvent rare-earth doped CeO2 buffer layer, the critical thickness has been greatly improved; Third, using frame RexCei_x0y / M2Zr207 bilayer buffer layer, not only to ensure the effective thickness of the buffer layer is good enough plays the role of a barrier layer, RexCei_x0y buffer layer thereon while ensuring the subsequent preparation of YBCO superconducting layer performance.

附图说明 BRIEF DESCRIPTION

[0019] 图1是本发明实施案例Sma2Cea8O1VLa2Zr2CVNiW缓冲层的XRD图谱; [0019] FIG. 1 is an XRD pattern of Case Sma2Cea8O1VLa2Zr2CVNiW embodiment of the present invention the buffer layer;

[0020] 图2是本发明实施案例Sma2Cea8O1VLa2Zr2CVNiW缓冲层的SEM图谱。 [0020] FIG 2 is a SEM spectrum case Sma2Cea8O1VLa2Zr2CVNiW embodiment of the present invention the buffer layer.

具体实施方式 Detailed ways

[0021] 下面结合附图和具体实施例对本发明作详细说明: Drawings and specific embodiments of the present invention will be described in detail [0021] below with:

[0022] 近年来,有关化学溶液沉积法制备La2Zr2O7 (LZO)的报道很多,但都是采用价格昂贵的金属醇盐为原料,为了进一步降低生产成本,提高薄膜的性能,本发明中采用硝酸盐La (NO3) 3- 6H20和ZrO (NO3) 3.2H20为前驱物来制备高品质的LZO薄膜。 [0022] In recent years, reports on chemical solution deposition method La2Zr2O7 (LZO), many, but they are expensive to use a metal alkoxide as a raw material, in order to further reduce production costs and improve the properties of the film used in the present invention, Nitrate la (NO3) 3- 6H20 and ZrO (NO3) 3.2H20 to prepare high-quality thin film is a precursor LZO. 目前有采用物理真空制备法来制备CeO2Zla2Zr2O7双层缓冲层,并未见采用价格便宜的硝酸盐全化学法。 There CeO2Zla2Zr2O7 double buffer layer prepared by physical vapor preparation method and no use an inexpensive full nitrate chemistry. Gd2Zr2O7和La2Zr2O7 —样是具有烧绿石结构的复合氧化物材料,从与YBCO和NiW晶格匹配角度来讲,Gd2Zr2O7也满足作为缓冲层的条件。 Gd2Zr2O7 and La2Zr2O7 - like material is a composite oxide having a pyrochlore structure, the lattice matching with YBCO NiW and perspective, Gd2Zr2O7 satisfies the conditions as the buffer layer. 在此本发明提供一种有利于大规模工业化发展的制备RexCei_x0y/M2Zr207双层缓冲层高性能方法。 In this preparation RexCei_x0y present invention provides an environment conducive to the development of large scale industrial / M2Zr207 high performance double layer buffer method.

[0023] 按照如下方式实施: [0023] The embodiment as follows:

[0024] 实施例一:一种化学溶液沉积法制备Sma2Cea8Oh9Zla2Zr2O7双层缓冲层的方法,依次由以下步骤构成: A [0024] Example: A chemical solution process Sma2Cea8Oh9Zla2Zr2O7 bilayer deposition method of the buffer layer, in turn consists of the following steps:

[0025] a、La2Zr2O7 (LZO)薄膜的制备: [0025] a, La2Zr2O7 (LZO) Preparation of films:

[0026] 将适量的La(NO3) 3.6Η20和ZrO(NO3) 3.2Η20按照离子浓度La+3 =Zr+4为1:1溶于乙二醇甲醚中,其中按照I摩尔(硝酸钆+硝酸锆):0.5 一3升体积比例加入羟乙基甲基醚,加入5wt.%氧化聚乙烯20000合成胶体。 [0026] An appropriate amount of La (NO3) 3.6Η20 and ZrO (NO3) 3.2Η20 ion concentration according to La + 3 = Zr + 4 1: 1 dissolved in ethylene glycol monomethyl ether, wherein the molar I (gadolinium nitrate + zirconium nitrate): 0.5 ratio of a volume of 3 liters was added hydroxyethyl methyl ether, polyethylene oxide added 20,000 5wt% synthetic colloids. 将胶体均匀旋涂于NiW基带上,获得的湿膜干燥后去除水份,然后放入通有H2/Ar还原气氛的热处理炉内,先以5°C/min速率升温至350°C,让有机物与硝酸盐充分分解,后直接升温至1100°C成相温度,保温2小时,获得La2Zr207/NiW薄膜。 Colloidal uniformly spin-coated NiW baseband, after removal of water to obtain a wet film was dried, and then placed on a heat treatment furnace with a H2 / Ar reducing atmosphere, heated to 350 ° C first at 5 ° C / min rate, so that and organic nitrates decompose sufficiently warmed directly to the C phase to a temperature of 1100 °, holding time 2 hours to obtain La2Zr207 / NiW film.

[0027] b、稀土Smtl 2Cetl 8O19 薄膜的制备: [0027] b, rare earth Smtl 2Cetl 8O19 Thin Film:

[0028] 按稀土Sm离子与铈Ce离子比0.2:0.8配制稀土硝酸盐与硝酸亚铈混合物,将配制的混合物溶解在聚丙烯酸与NN 二甲基甲酰胺的聚合物中获得胶体,将胶体旋涂于La2Zr2O7/ Niff基底上,后在红外干燥设备中去除水分,然后将Sma 2Ce0.80L 9/La2Zr207/ Niff放入气氛烧结炉中,在仏/^!.还原气氛保护下,将炉温以l°C/min速率升至550 °e,保证高分子有机物和硝酸盐充分分解,后升温至1100°C,保温I小时,保证Sma2Cea8O1VLa2Zr2O7/Niff结晶成相。 [0028] Sm rare earth ions by cerium Ce ion ratio 0.2: preparing a mixture of rare earth nitrate, cerium nitrate and 0.8, the obtained formulation was dissolved in a colloidal polyacrylic acid polymer with NN-dimethyl formamide, colloidal spin Apply La2Zr2O7 / Niff on the substrate, after removal of water in an infrared drying device, and then the Sma 2Ce0.80L 9 / La2Zr207 / Niff into the sintering furnace atmosphere at Fo / ^ !. reducing protective atmosphere, the temperature of the furnace l ° C / min rate was raised to 550 ° e, to ensure full decomposition of nitrates and organic polymer, the temperature was raised to 1100 ° C, I hour incubation to ensure Sma2Cea8O1VLa2Zr2O7 / Niff crystal phase.

[0029] 实施例二:一种化学溶液沉积法制备Gda3Cetl.Pu5AM2Zr2O7双层缓冲层的方法,依次由以下步骤构成: Two [0029] Example: A chemical solution process Gda3Cetl.Pu5AM2Zr2O7 bilayer deposition method of the buffer layer, in turn consists of the following steps:

[0030] a、Gd2Zr2O 7 (GZO)薄膜的制备: [0030] a, Gd2Zr2O 7 (GZO) thin films prepared:

[0031] 将适量的Gd(NO3)3.6H20和ZrO(NO3)3.2H20按照离子浓度Gd+3 =Zr+4为1:1溶于乙二醇甲醚中,其中按照I摩尔(硝酸钆+硝酸锆):0.5-3升体积比例加入羟乙基甲基醚,加入3wt.%氧化聚乙烯20000合成胶体。 [0031] An appropriate amount of Gd (NO3) 3.6H20 and ZrO (NO3) 3.2H20 in accordance with the ion concentration of Gd + 3 = Zr + 4 1: 1 dissolved in ethylene glycol monomethyl ether, wherein the molar I (gadolinium nitrate + zirconium nitrate): 0.5 liter volume ratio was added hydroxyethyl methyl ether, polyethylene oxide added 3wt% 20,000 synthetic colloids. 将胶体采用提拉法涂覆在NiW基带上,获得的湿膜干燥后去除水份,然后放入通有仏/^!.还原气氛的热处理炉内,先以TC /min速率升温至600°C,让有机物与硝酸盐充分分解,后直接升温至1200°C成相温度,保温I小时,获得Gd2Zr207/Niff 薄膜。 The colloid coated NiW Czochralski method baseband, after removal of water to obtain a wet film was dried, and then placed on there Fo / ^ !. reducing atmosphere heat treatment furnace, heated to 600 ° prior to TC / min rate C, so that organic substances and nitrate decompose sufficiently warmed directly to the C phase to a temperature of 1200 °, I hour incubation to obtain Gd2Zr207 / Niff film.

[0032] b、稀土Gda3Cea7Ou5 薄膜的制备: [0032] b, rare earth Gda3Cea7Ou5 Thin Film:

[0033] 按稀土Gd离子与铈Ce离子比0.3:0.7配制稀土硝酸盐与硝酸亚铈混合物,将配制的混合物溶解在丙烯酸与NN 二甲基甲酰胺的聚合物中来合成胶体,将胶体采用提拉法涂覆于Gd2Zr2O7/ NiW基底上,后在红外干燥设备中去除水分,然后将Gda 3Ce0.70L JGd2Zr2O7/ Niff放入气氛烧结炉中,在H2/Ar还原气氛保护下,将炉温以5°C /min速率升至350°C,保证高分子有机物和硝酸盐充分分解,后升温至1200°C,保温0.5小时,保证Gd0.3Ce0.70L 85/Gd2Zr207/Niff 结晶成相。 [0033] Press of Gd Ce ions to cerium ion ratio 0.3: 0.7 mixture formulation of rare earth nitrates and cerium nitrate, the mixture was formulated with polymers of acrylic acid was dissolved in NN-dimethylformamide in the synthesized colloids, colloid employed Czochralski coated on Gd2Zr2O7 / NiW substrate, after removal of water in an infrared drying device, and then Gda 3Ce0.70L JGd2Zr2O7 / Niff into the sintering furnace atmosphere, reducing atmosphere protection H2 / Ar, the temperature of the furnace 5 ° C / min rate was raised to 350 ° C, to ensure full decomposition of nitrates and organic polymer, the temperature was raised to 1200 ° C, for 0.5 hour to ensure Gd0.3Ce0.70L 85 / Gd2Zr207 / Niff crystal phase.

[0034] 实施例1和实施例2中,以稀土Sm和稀土Gd进行实施,其中稀土钇(Y)、镧(La)、镨(Pr)、钕(Nd)、铕(Eu)、铽(Tb)、镝(Dy)、钦(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)均可按照以上方式实施。 [0034] Example 1 and in Example 2, rare earth Sm and of Gd carried out, wherein yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), europium (Eu), terbium ( Tb), dysprosium (Dy), Chin (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu) may be embodiments in the above manner.

[0035] 图1为实施案例制得的Sma2Cea8Oh9Zla2Zr2O7/ NiW缓冲层的X射线衍射图谱,由图可见,所有制得的双层缓冲层都具有很好的双轴织构;图2实施案例制得的Sma2Cea8Ou/La2Zr2O7/ NiW双层缓冲层的SEM图片,从图中可见缓冲层表面平整致密、无微裂纹、具有很好的表面性能。 [0035] FIG. 1 is a case of X-ray diffraction pattern obtained embodiment Sma2Cea8Oh9Zla2Zr2O7 / NiW buffer layer, can be seen from the figure, the double buffer layer ownership obtained have good biaxial texture; Embodiment 2 FIG case prepared Sma2Cea8Ou / La2Zr2O7 / SEM image NiW double buffer layer, seen from the drawing surface of the buffer layer is smooth and compact without cracking, having good surface properties.

Claims (2)

1.一种化学溶液沉积法制备Sma2Cea8Oh9ZLa2Zr2O7双层缓冲层的方法,其特征在于:依次由以下步骤构成: a、La2Zr2O7 (LZO)薄膜的制备: 将适量的La(NO3)3.6H20和ZrO(NO3)3.2H20按照离子浓度La+3 =Zr+4为1:1溶于乙二醇甲醚中,其中按照I摩尔(La(NO3)3.6H20 + ZrO(NO3)3- 2H20):0.5 — 3升体积比例加入羟乙基甲基醚,加入5wt.%氧化聚乙烯20000合成胶体; 将胶体均匀旋涂于NiW基带上,获得的湿膜干燥后去除水份,然后放入通有H2/Ar还原气氛的热处理炉内,先以5°C /min速率升温至350°C,让有机物与硝酸盐充分分解,后直接升温至1100°C成相温度,保温2小时,获得La2Zr207/NiW薄膜; b、稀土 Sma2Cea8Oh9薄膜的制备: 按稀土Sm离子与铈Ce离子比0.2:0.8配制稀土硝酸盐与硝酸亚铈混合物,将配制的混合物溶解在聚丙烯酸与NN 二甲基甲酰胺的聚合物中获得胶体,将胶体旋涂于La2Zr2O7/Niff基底上,后在红外干燥设 A method for chemical solution deposition method Sma2Cea8Oh9ZLa2Zr2O7 double buffer layer, wherein: the step of successively consists: a, Preparation of La2Zr2O7 (LZO) Film: An appropriate amount of La (NO3) 3.6H20 and ZrO (NO3 ) 3.2H20 ion concentration according to La + 3 = Zr + 4 1: 1 dissolved in ethylene glycol monomethyl ether, wherein the molar accordance I (La (NO3) 3.6H20 + ZrO (NO3) 3- 2H20): 0.5 - 3 liter volume ratio was added hydroxyethyl methyl ether, polyethylene oxide added 5wt% synthetic colloids 20,000;. colloidal uniformly spin-coated NiW baseband, after removal of water obtained by drying the wet film, there is then placed on H2 / Ar reducing atmosphere heat treatment furnace, heated to the first 5 ° C / min rate to 350 ° C, so that organic substances and nitrate decompose sufficiently, the temperature was raised to 1100 ° C directly into phase temperature, holding time 2 hours to obtain La2Zr207 / NiW film; B, producing a rare earth Sma2Cea8Oh9 film: Sm rare earth ions by cerium Ce ion ratio 0.2: preparing a mixture of rare earth nitrate, cerium nitrate and 0.8, the preparation was dissolved in the polyacrylic acid polymer with NN-dimethyl formamide obtained colloid, colloidal spin-coated on La2Zr2O7 / Niff substrate, after the infrared drying provided 中去除水份,然后将Sma2Cea8O1VLa2Zr2O7/ Niff放入气氛烧结炉中,在H2/Ar还原气氛保护下,将炉温以1°C /min速率升至550°C,保证高分子有机物和硝酸盐充分分解,后升温至1100°C,保温I小时,保证Sma2Cea8O1VLa2Zr2CVNiW结晶成相。 The removal of water, then Sma2Cea8O1VLa2Zr2O7 / Niff sintering furnace into an atmosphere at H2 / Ar protective reducing atmosphere, the furnace temperature at 1 ° C / min rate was raised to 550 ° C, to ensure full nitrates and organic polymer decomposition temperature was raised to 1100 ° C, I hour incubation to ensure Sma2Cea8O1VLa2Zr2CVNiW crystal phase.
2.一种化学溶液沉积法制备Gda3Cea7Ou5AM2Zr2O7双层缓冲层的方法,其特征在于:依次由以下步骤构成: a、Gd2Zr2O7 (GZO)薄膜的制备: 将适量的Gd(NO3)3.6H20和ZrO(NO3)3.2H20按照离子浓度Gd+3 =Zr+4为1:1溶于乙二醇甲醚中,其中按照I摩尔(Gd(NO3)3.6H20 + ZrO(NO3)3- 2H20):0.5 — 3升体积比例加入羟乙基甲基醚,加入3wt.%氧化聚乙烯20000合成胶体; 将胶体采用提拉法涂覆在NiW基带上,获得的湿膜干燥后去除水份,然后放入通有H2/Ar还原气氛的热处理炉内,先以1°C /min速率升温至600°C,让有机物与硝酸盐充分分解,后直接升温至1200°C成相温度,保温I小时,获得Gd2Zr207/NiW薄膜; b、稀土 Gda3Cea7Oh85薄膜的制备: 按稀土Gd离子与铈Ce离子比0.3:0.7配制稀土硝酸盐与硝酸亚铈混合物,将配制的混合物溶解在丙烯酸与NN 二甲基甲酰胺的聚合物中来合成胶体,将胶体采用提拉法涂覆于Gd2Zr2O7/ NiW基底上 2. A method of chemical solution deposition method Gda3Cea7Ou5AM2Zr2O7 double buffer layer, wherein: the step of successively consists: a, Preparation of Gd2Zr2O7 (GZO) film: The appropriate amount of Gd (NO3) 3.6H20 and ZrO (NO3 ) 3.2H20 ion concentration according Gd + 3 = Zr + 4 1: 1 dissolved in ethylene glycol monomethyl ether, wherein the molar accordance I (Gd (NO3) 3.6H20 + ZrO (NO3) 3- 2H20): 0.5 - 3 liter volume ratio was added hydroxyethyl methyl ether, polyethylene oxide added 3wt% synthetic colloids 20,000; the colloidal Czochralski method with tape coated NiW substrate, after removal of water to obtain a wet film was dried, and then placed there through H2 / Ar reducing atmosphere heat treatment furnace, heated in the first 1 ° C / min rate to 600 ° C, so that organic substances and nitrate decompose sufficiently, the temperature was raised to 1200 ° C directly into phase temperature, incubated I hour to obtain Gd2Zr207 / NiW film; preparation B, rare earth Gda3Cea7Oh85 film: according to cerium Ce ions of Gd ion ratio 0.3: preparing a mixture of rare earth nitrate, cerium nitrate and 0.7, the preparation of acrylic acid was dissolved in NN-dimethylformamide with a polymer be synthesized colloids, colloid coated using the Czochralski method Gd2Zr2O7 / NiW substrate ,后在红外干燥设备中去除水份,然后将Gda3Cea7Oh85AM2Zr2O7/Niff放入气氛烧结炉中,在H2/Ar还原气氛保护下,将炉温以5°C /min速率升至350°C,保证高分子有机物和硝酸盐充分分解,后升温至1200°C,保温0.5小时,保证Gda3Cea7Oh85/Gd2Zr207/NiW 结晶成相。 After removal of water in an infrared drying device, and then Gda3Cea7Oh85AM2Zr2O7 / Niff into the sintering furnace atmosphere, reducing atmosphere protection H2 / Ar, the furnace temperature at 5 ° C / min rate was raised to 350 ° C, to ensure high organic molecules and nitrates decompose sufficiently, the temperature was raised to 1200 ° C, for 0.5 hour to ensure Gda3Cea7Oh85 / Gd2Zr207 / NiW crystal phase.
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