CN105177712B - A kind of method of growth REBCO high-temperature superconducting blocks - Google Patents
A kind of method of growth REBCO high-temperature superconducting blocks Download PDFInfo
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Abstract
本发明提供一种生长REBCO高温超导块材的方法，包括如下工序：a)按照摩尔比Ba：Cu＝2：3制备Ba2Cu3O5粉末；b)按(0.55～0.8)RE2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的配比制备前驱体；c)将所述前驱体置于生长炉中以籽晶诱导熔融织构法生长REBCO高温超导块材；其中，工序b)中的前驱体为工序a)获得的Ba2Cu3O5粉末按(0.55～0.8)RE2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的比例混合均匀，压制而成的圆柱形前驱体。本发明在前驱体中直接使用摩尔比Ba：Cu＝2：3制备的Ba2Cu3O5粉末，而避免制备RE123、RE211粉末，节约了时间和工艺成本，又能够保证在整个生长过程中的各元素配比保持RE123和RE211的摩尔比约等于1：(0.1～0.4)，从而获得REBCO高温超导块材。
The invention provides a method for growing REBCO high-temperature superconducting bulk material, which includes the following steps: a) preparing Ba2Cu3O5 powder according to the molar ratio Ba:Cu= 2 : 3 ; b) according to ( 0.55-0.8 ) RE2 O 3 +Ba 2 Cu 3 O 5 +(0.3～1.5) wt% CeO 2 to prepare the precursor; c) Place the precursor in the growth furnace to grow REBCO high temperature super Guide block material; wherein, the precursor in step b) is the Ba 2 Cu 3 O 5 powder obtained in step a) according to (0.55~0.8) RE 2 O 3 +Ba 2 Cu 3 O 5 +(0.3~1.5)wt The proportion of %CeO2 is mixed evenly, and the cylindrical precursor is formed by pressing. The present invention directly uses the Ba 2 Cu 3 O 5 powder prepared with a molar ratio of Ba:Cu=2:3 in the precursor, avoids the preparation of RE123 and RE211 powders, saves time and process costs, and can ensure that during the entire growth process The proportion of each element keeps the molar ratio of RE123 and RE211 approximately equal to 1: (0.1-0.4), so as to obtain REBCO high-temperature superconducting bulk material.
Description
技术领域technical field
本发明涉及高温超导材料领域，更具体地，涉及一种生长REBCO高温超导块材的方法。The invention relates to the field of high-temperature superconducting materials, and more specifically, relates to a method for growing REBCO high-temperature superconducting bulk materials.
背景技术Background technique
自REBa2Cu3Ox(简称REBCO、RE123、稀土钡铜氧，RE＝Y、Gd、Sm、Nd等)超导体被发现以来，就引起了人们的广泛关注。由于其具有完全抗磁性、高临界电流密度和高冻结磁场等特性，REBCO超导体在诸如磁悬浮力、磁性轴承、飞轮储能和永磁体等方面有许多潜在的应用。Since the discovery of REBa 2 Cu 3 O x (referred to as REBCO, RE123, rare earth barium copper oxide, RE=Y, Gd, Sm, Nd, etc.) superconductor has attracted widespread attention. Due to its properties such as complete diamagnetism, high critical current density, and high freezing magnetic field, REBCO superconductors have many potential applications in areas such as magnetic levitation forces, magnetic bearings, flywheel energy storage, and permanent magnets.
顶部籽晶熔渗生长法(TSIG)和顶部籽晶熔融生长法(TSMG)都是制备超导单晶块材的常用方法。然而在传统的生长方法中，我们需要制备Y2BaCuO5(Y211),YBa2Cu3Oy(Y123)等多种粉体，过程复杂且费时费力，样品中的Y211粒子含量也不尽如意。Top-seed infiltration growth (TSIG) and top-seed melt growth (TSMG) are common methods for preparing superconducting single crystal bulk. However, in the traditional growth method, we need to prepare Y 2 BaCuO 5 (Y211), YBa 2 Cu 3 O y (Y123) and other powders, the process is complicated and time-consuming, and the content of Y211 particles in the sample is not satisfactory .
目前，顶部籽晶熔融织构法(MT)可有效制备大尺寸的REBCO超导块材以其容易制备、可实现高掺杂并且生长可靠等特点，成为一种极具潜力的REBCO高温超导材料制备方法，但通常要通过掺杂一定量的RE211相，这使样品中RE211颗粒大、含量高。At present, the top-seed melt texture method (MT) can effectively prepare large-sized REBCO superconducting bulk materials, and has become a kind of REBCO high-temperature superconducting material with great potential because of its easy preparation, high doping and reliable growth. Material preparation methods, but usually by doping a certain amount of RE211 phase, which makes the RE211 particles in the sample large and high in content.
因此，本领域的技术人员致力于开发一种利用熔融织构法生长REBCO高温超导块材的方法，相较于现有技术，能够显著优化超导块材内的RE211的尺寸和分布，从而提高REBCO块材的超导性能。Therefore, those skilled in the art are committed to developing a method for growing REBCO high-temperature superconducting bulk materials by using the melt texture method. Compared with the prior art, the size and distribution of RE211 in the superconducting bulk materials can be significantly optimized, thereby Improving the superconducting properties of REBCO bulk materials.
发明内容Contents of the invention
本发明的目的在于针对现有技术的不足，提供一种REBCO高温超导块材的方法，在空气中熔融织构法制备生长REBCO高温超导块材，实现REBCO单畴内RE211的均匀分布和尺寸的细化，满足科研和实际工业化生产的需求。The purpose of the present invention is to address the deficiencies of the prior art, to provide a method for REBCO high-temperature superconducting bulk materials, to prepare and grow REBCO high-temperature superconducting bulk materials by melting texture in air, and to realize the uniform distribution and The refinement of size meets the needs of scientific research and actual industrial production.
本发明解决上述技术问题所采用的技术方案是：The technical solution adopted by the present invention to solve the problems of the technologies described above is:
一种生长REBCO高温超导块材的方法，包括如下工序：A method for growing REBCO high-temperature superconducting bulk material, comprising the following steps:
a)按照摩尔比Ba：Cu＝2：3制备Ba2Cu3O5粉末；a) Prepare Ba 2 Cu 3 O 5 powder according to the molar ratio Ba:Cu=2:3;
b)按(0.55～0.8)RE2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的配比制备前驱体；b) Prepare the precursor according to the ratio of (0.55-0.8) RE 2 O 3 +Ba 2 Cu 3 O 5 +(0.3-1.5) wt% CeO 2 ;
c)将所述前驱体置于生长炉中以籽晶诱导熔融织构法生长REBCO高温超导块材；c) placing the precursor in a growth furnace to grow a REBCO high temperature superconducting bulk material by a seed crystal induced melt texture method;
其中，工序b)中的前驱体为工序a)获得的Ba2Cu3O5粉末按(0.55～0.8)RE2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的比例混合均匀，压制而成的圆柱形前驱体。具体地，前驱体中RE2O3和Ba2Cu3O5的摩尔比为(0.55～0.8):1，CeO2为RE2O3和Ba2Cu3O5粉末的总质量的0.3～1.5％；Wherein, the precursor in step b) is the Ba 2 Cu 3 O 5 powder obtained in step a) according to (0.55-0.8) RE 2 O 3 + Ba 2 Cu 3 O 5 + (0.3-1.5) wt% CeO 2 The proportion is mixed evenly, and the cylindrical precursor is formed by pressing. Specifically, the molar ratio of RE 2 O 3 and Ba 2 Cu 3 O 5 in the precursor is (0.55-0.8):1, and CeO 2 is 0.3-0.3 to the total mass of RE 2 O 3 and Ba 2 Cu 3 O 5 powders 1.5%;
进一步地，工序c)中，所述籽晶置于前驱体的上表面中心处，以顶部籽晶熔融织构生长REBCO高温超导块材。Further, in step c), the seed crystal is placed at the center of the upper surface of the precursor, and the REBCO high-temperature superconducting bulk material is grown with the melt texture of the top seed crystal.
优选地，所述籽晶采用嵌入式籽晶法压制成圆柱形前驱体，并且工序c)中，所述籽晶以嵌入式籽晶法熔融织构生长REBCO高温超导块材。Preferably, the seed crystal is pressed into a cylindrical precursor by an embedded seed crystal method, and in step c), the REBCO high-temperature superconducting bulk material is grown by melt-texturing the seed crystal by an embedded seed crystal method.
其中，嵌入式籽晶法压制成圆柱形前驱体是指：将Ba2Cu3O5粉末按(0.55～0.8)RE2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的配比混合均匀，再压制形成圆柱形的前驱体，并在压制过程中，将籽晶水平固定地嵌入所述前驱体上表面中央区域的内部，所述籽晶的诱导生长面位于所述前驱体的内部，且所述诱导生长面的背面与所述前驱体的上表面共面，形成所述嵌入式籽晶前驱体。Among them, pressing the embedded seed crystal method into a cylindrical precursor refers to: making Ba 2 Cu 3 O 5 powder by (0.55-0.8) RE 2 O 3 + Ba 2 Cu 3 O 5 + (0.3-1.5) wt% CeO 2 , mixed evenly, and then pressed to form a cylindrical precursor, and during the pressing process, the seed crystal was horizontally and fixedly embedded in the central area of the upper surface of the precursor, and the induced growth surface of the seed crystal was located at the The inside of the precursor, and the back surface of the induced growth surface is coplanar with the upper surface of the precursor to form the embedded seed crystal precursor.
进一步地，工序a)包括：第一步骤，按照Ba：Cu＝2：3的摩尔比例将BaCO3和CuO粉末混合，获得BaCO3+CuO粉料；第二步骤，对所述BaCO3+CuO粉料加入无水乙醇混合均匀后进行湿磨，以获得BaCO3+CuO浆料，湿磨时间为2-4小时；第三步骤，烘干上一步骤所得的BaCO3+CuO浆料制备Ba2Cu3O5粉末；第四步骤，将上述步骤Ba2Cu3O5粉末在空气中900℃烧结48小时并重复两次研磨、烧结过程，最终获得Ba2Cu3O5粉末。Further, step a) includes: the first step, mixing BaCO 3 and CuO powder according to the molar ratio of Ba:Cu=2:3 to obtain BaCO 3 +CuO powder; the second step, mixing the BaCO 3 +CuO powder The powder is mixed with absolute ethanol and then wet-milled to obtain BaCO 3 +CuO slurry. The wet-milling time is 2-4 hours; the third step is to dry the BaCO 3 +CuO slurry obtained in the previous step to prepare BaCO 3 +CuO slurry. 2 Cu 3 O 5 powder; the fourth step is to sinter the above-mentioned Ba 2 Cu 3 O 5 powder in air at 900°C for 48 hours and repeat the grinding and sintering process twice to finally obtain Ba 2 Cu 3 O 5 powder.
进一步地，工序c)的熔融织构生长包括以下步骤：使生长炉内的温度在第一时间内升至第一温度；保温2～5小时；使生长炉内的温度在第二时间内降至第二温度；使生长炉内的温度在第三时间内降至第三温度；最后淬火，获得REBCO高温超导块材。Further, the melt texture growth in step c) includes the following steps: raising the temperature in the growth furnace to the first temperature within the first time; keeping the temperature for 2 to 5 hours; lowering the temperature in the growth furnace within the second time. to the second temperature; reducing the temperature in the growth furnace to the third temperature within a third time; and finally quenching to obtain REBCO high-temperature superconducting bulk material.
进一步地，第一时间为3～10小时，第一温度高于REBCO高温超导块材的包晶反应温度30～80℃；第二时间为15～30分钟，第二温度为包晶反应温度；第三时间为10～50小时，第三温度为低于包晶反应温度5～20℃。Further, the first time is 3-10 hours, and the first temperature is 30-80°C higher than the peritectic reaction temperature of REBCO high-temperature superconducting bulk material; the second time is 15-30 minutes, and the second temperature is the peritectic reaction temperature ; The third time is 10-50 hours, and the third temperature is 5-20° C. lower than the peritectic reaction temperature.
进一步地，淬火为：将REBCO高温超导块材随炉冷却。Further, the quenching is: cooling the REBCO high-temperature superconducting block with the furnace.
进一步地，工序c)的籽晶是NdBCO/YBCO/MgO薄膜籽晶。Further, the seed crystals in step c) are NdBCO/YBCO/MgO thin film seed crystals.
进一步地，NdBCO/YBCO/MgO薄膜籽晶为c轴取向，NdBCO/YBCO/MgO薄膜籽晶的尺寸为2mm×2mm。Further, the NdBCO/YBCO/MgO thin film seed crystal is c-axis oriented, and the size of the NdBCO/YBCO/MgO thin film seed crystal is 2mm×2mm.
进一步地，前驱体的直径为15～30mm。Further, the diameter of the precursor is 15-30mm.
进一步地，REBCO为YBCO、NdBCO、SmBCO或GdBCO。Further, REBCO is YBCO, NdBCO, SmBCO or GdBCO.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
1、本发明引入c轴取向的NdBCO/YBCO/MgO薄膜作为籽晶，嵌入式籽晶熔融织构法诱导生长REBCO高温超导块材，该薄膜籽晶具有很高的热稳定性，其熔点高达1120℃，有利于在高温度的生长炉内保证薄膜结构和组分的完整性，用于成功诱导REBCO材料的外延生长。1. The present invention introduces the c-axis oriented NdBCO/YBCO/MgO film as the seed crystal, and the embedded seed crystal melt texture method induces the growth of REBCO high-temperature superconducting bulk material. The film seed crystal has high thermal stability, and its melting point Up to 1120°C, which is beneficial to ensure the integrity of the film structure and components in the high-temperature growth furnace, and is used to successfully induce the epitaxial growth of REBCO materials.
2、本发明在前驱体中直接使用摩尔比Ba：Cu＝2：3制备的Ba2Cu3O5粉末，而避免制备RE123、RE211粉末，节约了时间和工艺成本，又能够保证在整个生长过程中的各元素配比保持RE123和RE211的摩尔比约等于1：(0.1～0.4)，从而获得REBCO高温超导块材。2. The present invention directly uses Ba 2 Cu 3 O 5 powder prepared with a molar ratio of Ba:Cu=2:3 in the precursor, avoids the preparation of RE123 and RE211 powders, saves time and process costs, and can ensure that the entire growth The ratio of each element in the process keeps the molar ratio of RE123 and RE211 approximately equal to 1: (0.1-0.4), so as to obtain REBCO high-temperature superconducting bulk material.
3、本发明采用嵌入式籽晶法，提高高温熔融状态下的前驱体内的稀土元素的浓度，从而有效抑制薄膜籽晶中的稀土元素的溶解和扩散，进而保证薄膜在高温状态的结构完整，提高薄膜的热稳定性。另外，通过实验表明，发明人发现当采用嵌入式籽晶法制备本发明的REBCO高温超导块材时产品的良率更高。3. The present invention adopts the embedded seed crystal method to increase the concentration of rare earth elements in the precursor body in the high-temperature molten state, thereby effectively inhibiting the dissolution and diffusion of rare earth elements in the film seed crystal, thereby ensuring the structural integrity of the film at high temperature. Improve the thermal stability of the film. In addition, experiments show that the inventors found that when the embedded seed crystal method is used to prepare the REBCO high temperature superconducting bulk material of the present invention, the product yield is higher.
以下将结合附图对本发明的构思、具体结构及产生的技术效果作进一步说明，以充分地了解本发明的目的、特征和效果。The idea, specific structure and technical effects of the present invention will be further described below in conjunction with the accompanying drawings, so as to fully understand the purpose, features and effects of the present invention.
附图说明Description of drawings
图1显示为本发明提供的REBCO高温超导块材的方法的流程图。Fig. 1 shows a flow chart of the method for the REBCO high temperature superconducting bulk material provided by the present invention.
图2显示为本发明的实施例一的熔融织构生长工艺的温度程序的示意图。FIG. 2 is a schematic diagram showing the temperature program of the melt texture growth process according to Embodiment 1 of the present invention.
图3显示为本发明的实施例一中获得的YBCO高温超导块材的光学照片。Fig. 3 is an optical photograph of the YBCO high temperature superconducting bulk material obtained in Example 1 of the present invention.
元件标号说明Component designation description
S10～S30 步骤S10～S30 steps
具体实施方式detailed description
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。Embodiments of the present invention are described below through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various modifications or changes can be made to the details in this specification based on different viewpoints and applications without departing from the spirit of the present invention.
本发明提供一种生长REBCO高温超导块材的方法，如图1所示，包括如下工序：The present invention provides a method for growing REBCO high-temperature superconducting bulk material, as shown in Figure 1, comprising the following steps:
S10：按照摩尔比Ba：Cu＝2：3制备Ba2Cu3O5粉末。S10: Prepare Ba 2 Cu 3 O 5 powder according to the molar ratio Ba:Cu=2:3.
S20：按(0.55～0.8)RE2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的配比制备前驱体；其中，RE2O3和CeO2为商业购买，纯度为99.99％。S20: Prepare the precursor according to the ratio of (0.55～0.8) RE 2 O 3 +Ba 2 Cu 3 O 5 +(0.3～1.5)wt% CeO 2 ; among them, RE 2 O 3 and CeO 2 are purchased commercially, the purity is 99.99%.
S30：将所述前驱体置于生长炉中以籽晶诱导熔融织构法生长REBCO高温超导块材。S30: The precursor is placed in a growth furnace to grow a REBCO high temperature superconducting bulk material by a seed crystal induced melt texture method.
其中，前驱体为获得的Ba2Cu3O5粉末按(0.55～0.8)RE2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的比例混合均匀，压制而成的圆柱形前驱体。具体地，前驱体中RE2O3和Ba2Cu3O5的摩尔比大致为(0.55～0.8):1，CeO2为RE2O3和Ba2Cu3O5粉末的总质量的0.3～1.5％。Wherein, the precursor is obtained by mixing the obtained Ba2Cu3O5 powder according to the ratio of ( 0.55-0.8 ) RE2O3 + Ba2Cu3O5 + ( 0.3-1.5 ) wt%CeO2, and pressing it Cylindrical precursors. Specifically, the molar ratio of RE 2 O 3 and Ba 2 Cu 3 O 5 in the precursor is approximately (0.55-0.8):1, and CeO 2 is 0.3 of the total mass of RE 2 O 3 and Ba 2 Cu 3 O 5 powders ~1.5%.
另外，Ba2Cu3O5粉末通过反复研磨、烧结制得，可选地，包括如下工序：第一步骤，按照Ba：Cu＝2：3的摩尔比例将BaCO3和CuO粉末混合，获得BaCO3+CuO粉料；第二步骤，对所述BaCO3+CuO粉料加入无水乙醇混合均匀后进行湿磨，以获得BaCO3+CuO浆料，湿磨时间为2-4小时；第三步骤，烘干上一步骤所得的BaCO3+CuO浆料制备Ba2Cu3O5粉末；第四步骤，将上述步骤Ba2Cu3O5粉末在空气中900℃烧结48小时并重复两次研磨、烧结过程，最终获得Ba2Cu3O5粉末。In addition, the Ba 2 Cu 3 O 5 powder is obtained by repeated grinding and sintering. Optionally, the following steps are included: the first step is to mix BaCO 3 and CuO powder according to the molar ratio of Ba:Cu=2:3 to obtain BaCO 3 +CuO powder; the second step is to add absolute ethanol to the BaCO 3 +CuO powder and mix it evenly, and then perform wet grinding to obtain BaCO 3 +CuO slurry, and the wet grinding time is 2-4 hours; the third The first step is to dry the BaCO 3 +CuO slurry obtained in the previous step to prepare Ba 2 Cu 3 O 5 powder; the fourth step is to sinter the above-mentioned Ba 2 Cu 3 O 5 powder in air at 900°C for 48 hours and repeat twice Through grinding and sintering, Ba 2 Cu 3 O 5 powder is finally obtained.
由此，通过在前驱体中直接使用摩尔比Ba：Cu＝2：3制备的Ba2Cu3O5粉末，而避免制备RE123、RE211粉末，节约了时间和工艺成本，又能够保证在整个生长过程中的各元素配比保持RE123和RE211的摩尔比约等于1：(0.1～0.4)，从而获得REBCO高温超导块材。Therefore, by directly using the Ba 2 Cu 3 O 5 powder prepared with a molar ratio of Ba:Cu=2:3 in the precursor, the preparation of RE123 and RE211 powders is avoided, which saves time and process costs, and ensures that the entire growth The ratio of each element in the process keeps the molar ratio of RE123 and RE211 approximately equal to 1: (0.1-0.4), so as to obtain REBCO high-temperature superconducting bulk material.
进一步地，S30中籽晶置于前驱体的上表面中心处，以顶部籽晶或嵌入式籽晶熔融织构生长REBCO高温超导块材。其中，嵌入式籽晶法压制成圆柱形前驱体是指：将Ba2Cu3O5粉末按(0.55～0.8)RE2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的配比混合均匀，再压制形成圆柱形的前驱体，并在压制过程中，将籽晶水平固定地嵌入所述前驱体上表面中央区域的内部，所述籽晶的诱导生长面位于所述前驱体的内部，且所述诱导生长面的背面与所述前驱体的上表面共面，形成所述嵌入式籽晶前驱体。Further, in S30, the seed crystal is placed at the center of the upper surface of the precursor, and the REBCO high-temperature superconducting bulk material is grown with the top seed crystal or embedded seed crystal melt texture. Among them, pressing the embedded seed crystal method into a cylindrical precursor refers to: making Ba 2 Cu 3 O 5 powder by (0.55-0.8) RE 2 O 3 + Ba 2 Cu 3 O 5 + (0.3-1.5) wt% CeO 2 , mixed evenly, and then pressed to form a cylindrical precursor, and during the pressing process, the seed crystal was horizontally and fixedly embedded in the central area of the upper surface of the precursor, and the induced growth surface of the seed crystal was located at the The inside of the precursor, and the back surface of the induced growth surface is coplanar with the upper surface of the precursor to form the embedded seed crystal precursor.
需要强调的是，本发明采用嵌入式籽晶法，能够提高高温熔融状态下的前驱体内的稀土元素的浓度，从而有效抑制薄膜籽晶中的稀土元素的溶解和扩散，进而保证薄膜在高温状态的结构完整，提高薄膜的热稳定性。另外，通过实验表明，相较于顶部籽晶熔融织构生长法，发明人发现当采用嵌入式籽晶法制备本发明的REBCO高温超导块材时产品的良率更高。这可能也是因为嵌入式籽晶法，能够提高高温熔融状态下的前驱体内的稀土元素的浓度，从而有效抑制薄膜籽晶中的稀土元素的溶解和扩散，有利于前驱体在熔融织构生长过程避免组分的偏离。It should be emphasized that the present invention adopts the embedded seed crystal method, which can increase the concentration of rare earth elements in the precursor body in the high-temperature molten state, thereby effectively inhibiting the dissolution and diffusion of rare earth elements in the film seed crystal, thereby ensuring that the film is in a high-temperature state. The structural integrity of the film improves the thermal stability of the film. In addition, experiments have shown that, compared with the top-seed melting texture growth method, the inventors have found that when the embedded seed method is used to prepare the REBCO high-temperature superconducting bulk material of the present invention, the yield of the product is higher. This may also be because the embedded seed crystal method can increase the concentration of rare earth elements in the precursor in the high-temperature molten state, thereby effectively inhibiting the dissolution and diffusion of rare earth elements in the thin film seed crystal, which is beneficial to the growth process of the precursor in the melt texture. Avoid component deviations.
进一步地，S30的熔融织构生长包括以下步骤：使生长炉内的温度在第一时间内升至第一温度；保温2～5小时；使生长炉内的温度在第二时间内降至第二温度；使生长炉内的温度在第三时间内降至第三温度；最后淬火，获得REBCO高温超导块材。可选地，第一时间为3～10小时，第一温度高于REBCO高温超导块材的包晶反应温度30～80℃；第二时间为15～30分钟，第二温度为包晶反应温度；第三时间为10～50小时，第三温度为低于包晶反应温度5～20℃。Further, the melt texture growth of S30 includes the following steps: raising the temperature in the growth furnace to the first temperature within the first time; keeping the temperature for 2 to 5 hours; reducing the temperature in the growth furnace to the first temperature within the second time. the second temperature; reducing the temperature in the growth furnace to the third temperature within a third time; and finally quenching to obtain REBCO high-temperature superconducting bulk material. Optionally, the first time is 3-10 hours, and the first temperature is 30-80°C higher than the peritectic reaction temperature of REBCO high-temperature superconducting bulk material; the second time is 15-30 minutes, and the second temperature is peritectic reaction Temperature: the third time is 10-50 hours, and the third temperature is 5-20° C. lower than the peritectic reaction temperature.
进一步地，S30的籽晶是NdBCO/YBCO/MgO薄膜籽晶。其中，NdBCO/YBCO/MgO薄膜籽晶为c轴取向，NdBCO/YBCO/MgO薄膜籽晶的尺寸优选剪切为2mm×2mm。Further, the seed crystal of S30 is NdBCO/YBCO/MgO thin film seed crystal. Wherein, the NdBCO/YBCO/MgO film seed crystal is c-axis oriented, and the size of the NdBCO/YBCO/MgO film seed crystal is preferably cut to 2mm×2mm.
本发明引入c轴取向的NdBCO/YBCO/MgO薄膜作为籽晶，嵌入式籽晶熔融织构法诱导生长REBCO高温超导块材，该薄膜籽晶具有很高的热稳定性，其熔点高达1120℃，有利于在高温度的生长炉内保证薄膜结构和组分的完整性，用于成功诱导REBCO材料的外延生长。The present invention introduces the c-axis oriented NdBCO/YBCO/MgO film as the seed crystal, and the embedded seed crystal melt texture method induces the growth of REBCO high-temperature superconducting bulk material. The film seed crystal has high thermal stability, and its melting point is as high as 1120 ℃, which is beneficial to ensure the integrity of the film structure and components in a high-temperature growth furnace, and is used to successfully induce the epitaxial growth of REBCO materials.
实施例1Example 1
一种生长YBCO高温超导块材的方法，包括如下工序：A method for growing YBCO high-temperature superconducting bulk material, comprising the following steps:
1、按照Ba：Cu＝2：3的摩尔比例将BaCO3和CuO粉末混合，获得BaCO3+CuO粉料；1. Mix BaCO 3 and CuO powder according to the molar ratio of Ba:Cu=2:3 to obtain BaCO 3 +CuO powder;
2、对步骤1所述BaCO3+CuO粉料加入无水乙醇混合均匀后进行湿磨，以获得BaCO3+CuO浆料，湿磨时间为2-4小时；2. Add absolute ethanol to the BaCO 3 +CuO powder described in step 1, mix it evenly, and perform wet grinding to obtain BaCO 3 +CuO slurry. The wet grinding time is 2-4 hours;
3、烘干步骤2中所得的BaCO3+CuO浆料制备Ba2Cu3O5粉末；3. Dry the BaCO 3 +CuO slurry obtained in step 2 to prepare Ba 2 Cu 3 O 5 powder;
4、将步骤3中的Ba2Cu3O5粉末在空气中900℃烧结48小时并重复2次此研磨、烧结过程，最终获得Ba2Cu3O5粉末。4. Sinter the Ba 2 Cu 3 O 5 powder in step 3 at 900° C. in air for 48 hours and repeat the grinding and sintering process twice to finally obtain Ba 2 Cu 3 O 5 powder.
5、将步骤4所得Ba2Cu3O5粉末按0.75Y2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的配比配料，充分碾磨混合均匀后，取10g混粉放入模具。5. Mix the Ba 2 Cu 3 O 5 powder obtained in step 4 according to the ratio of 0.75Y 2 O 3 +Ba 2 Cu 3 O 5 +(0.3～1.5)wt% CeO 2 , grind and mix well, then take 10g Mix the powder into the mould.
6、将步骤5所述粉末采用嵌入式籽晶法，将尺寸为2mm×2mm的c轴取向的NdBCO/YBCO/MgO薄膜的籽晶材料压制成直径为20mm的圆柱形的前驱体，其中，2mm×2mm表示薄膜籽晶的长和宽均为2mm。6. Use the embedded seed crystal method to press the powder described in step 5, and press the c-axis-oriented NdBCO/YBCO/MgO film seed crystal material with a size of 2mm×2mm into a cylindrical precursor with a diameter of 20mm, wherein, 2mm×2mm means that the length and width of the film seed are both 2mm.
7、将步骤6中的籽晶材料、前驱体放置于生长炉中进行熔融结构生长，如图2所示，生长炉的具体温度程序为：7. Place the seed crystal material and precursor in step 6 in the growth furnace for molten structure growth, as shown in Figure 2, the specific temperature program of the growth furnace is:
a、从室温开始经过4h升温至900℃，保温2h。a. After 4 hours from room temperature, the temperature is raised to 900°C, and the temperature is kept for 2 hours.
b、继续加热2h，升温至1080℃，保温1.5h。b. Continue heating for 2 hours, raise the temperature to 1080°C, and keep the temperature for 1.5 hours.
c、在35min内，快速降温至1005℃。c. Rapidly cool down to 1005°C within 35 minutes.
d、0.5℃/h生长50h。d. Grow at 0.5°C/h for 50h.
e、淬火制得YBCO高温超导块体材料。e. The YBCO high temperature superconducting bulk material is obtained by quenching.
图3是生长得到的YBCO高温超导块材的照片，生长时间50h，生长最高温度为1080℃。由该图可知，使用嵌入式籽晶法，把Y2O3粉末和Ba2Cu3O5粉末按一定比例混合直接作为前驱体组份，应用熔融织构法可以生长出YBCO高温超导块材。可以看出，该嵌入式籽晶诱导的YBCO高温超导块材由籽晶诱导向外规则生长，形成完整的单畴结构。此外，发明人对制得的YBCO高温超导块材沿籽晶诱导方向的剖面观察，发现Y211的分布均匀，在远离籽晶部位Y211聚集不明显，且Y211的尺寸较小。Fig. 3 is a photo of the grown YBCO high temperature superconducting bulk material, the growth time is 50h, and the highest growth temperature is 1080°C. It can be seen from the figure that YBCO high-temperature superconducting block can be grown by using the embedded seed crystal method, mixing Y 2 O 3 powder and Ba 2 Cu 3 O 5 powder in a certain proportion directly as the precursor component, and applying the melt texture method material. It can be seen that the YBCO high-temperature superconducting bulk material induced by the embedded seed crystal grows outward regularly from the seed crystal to form a complete single-domain structure. In addition, the inventor observed the cross-section of the prepared YBCO high-temperature superconducting bulk material along the direction of seed crystal induction, and found that the distribution of Y211 was uniform, and the accumulation of Y211 was not obvious at the position away from the seed crystal, and the size of Y211 was small.
实施例2Example 2
一种生长NdBCO高温超导块材的方法，包括如下工序：A method for growing NdBCO high-temperature superconducting bulk material, comprising the following steps:
1、按照Ba：Cu＝2：3的比例将BaCO3和CuO粉末混合，获得BaCO3+CuO粉料；1. Mix BaCO 3 and CuO powder according to the ratio of Ba:Cu=2:3 to obtain BaCO 3 +CuO powder;
2、对步骤1所述BaCO3+CuO粉料加入无水乙醇混合均匀后进行湿磨，以获得BaCO3+CuO浆料，湿磨时间为2-4小时；2. Add absolute ethanol to the BaCO 3 +CuO powder described in step 1, mix it evenly, and perform wet grinding to obtain BaCO 3 +CuO slurry. The wet grinding time is 2-4 hours;
3、烘干步骤2中所得的BaCO3+CuO浆料制备Ba2Cu3O5粉末；3. Dry the BaCO 3 +CuO slurry obtained in step 2 to prepare Ba 2 Cu 3 O 5 powder;
4、将步骤3中的Ba2Cu3O5粉末在空气中900℃烧结48小时并重复2次此研磨、烧结过程，最终获得Ba2Cu3O5粉末。4. Sinter the Ba 2 Cu 3 O 5 powder in step 3 at 900° C. in air for 48 hours and repeat the grinding and sintering process twice to finally obtain Ba 2 Cu 3 O 5 powder.
5、将步骤4所得Ba2Cu3O5粉末按0.75Nd2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的配比配料，充分碾磨混合均匀后，取10g混粉放入模具。5. Mix the Ba 2 Cu 3 O 5 powder obtained in step 4 according to the ratio of 0.75Nd 2 O 3 +Ba 2 Cu 3 O 5 +(0.3～1.5)wt% CeO 2 , grind and mix well, then take 10g Mix the powder into the mould.
6、将步骤5所述粉末采用嵌入式籽晶法，将尺寸为2mm×2mm的c轴取向的NdBCO/YBCO/MgO薄膜的籽晶材料压制成直径为20mm的圆柱形的前驱体，其中，2mm×2mm表示薄膜籽晶的长和宽均为2mm。6. Use the embedded seed crystal method to press the powder described in step 5, and press the c-axis-oriented NdBCO/YBCO/MgO film seed crystal material with a size of 2mm×2mm into a cylindrical precursor with a diameter of 20mm, wherein, 2mm×2mm means that the length and width of the film seed are both 2mm.
7、将步骤6中的籽晶材料、前驱体放置于生长炉中进行熔融结构生长，生长炉的具体温度程序为：7. Place the seed crystal material and precursor in step 6 in the growth furnace to grow the molten structure. The specific temperature program of the growth furnace is:
a、从室温开始经过4h升温至900℃，保温2h。a. After 4 hours from room temperature, the temperature is raised to 900°C, and the temperature is kept for 2 hours.
b、继续加热2h，升温至1120℃，保温1.5h。b. Continue heating for 2 hours, raise the temperature to 1120°C, and keep the temperature for 1.5 hours.
c、在35min内，快速降温至1090℃。c. Rapidly cool down to 1090°C within 35 minutes.
d、0.2℃/h缓慢降温生长20h，0.3℃/h缓慢降温生长20h，0.4℃/h缓慢降温生长20h，总共60h。d. Slowly cool down at 0.2°C/h for 20h, grow at 0.3°C/h for 20h, and grow at 0.4°C/h for 20h, a total of 60h.
e、淬火制得NdBCO高温超导块体材料。e. NdBCO high temperature superconducting bulk material is obtained by quenching.
实施例3Example 3
一种生长SmBCO高温超导块材的方法，包括如下工序：A method for growing SmBCO high-temperature superconducting bulk material, comprising the following steps:
1、按照Ba：Cu＝2：3的比例将BaCO3和CuO粉末混合，获得BaCO3+CuO粉料；1. Mix BaCO 3 and CuO powder according to the ratio of Ba:Cu=2:3 to obtain BaCO 3 +CuO powder;
2、对步骤1所述BaCO3+CuO粉料加入无水乙醇混合均匀后进行湿磨，以获得BaCO3+CuO浆料，湿磨时间为2-4小时；2. Add absolute ethanol to the BaCO 3 +CuO powder described in step 1, mix it evenly, and perform wet grinding to obtain BaCO 3 +CuO slurry. The wet grinding time is 2-4 hours;
3、烘干步骤2中所得的BaCO3+CuO浆料制备Ba2Cu3O5粉末；3. Dry the BaCO 3 +CuO slurry obtained in step 2 to prepare Ba 2 Cu 3 O 5 powder;
4、将步骤3中的Ba2Cu3O5粉末在空气中900℃烧结48小时并重复2次此研磨、烧结过程，最终获得Ba2Cu3O5粉末。4. Sinter the Ba 2 Cu 3 O 5 powder in step 3 at 900° C. in air for 48 hours and repeat the grinding and sintering process twice to finally obtain Ba 2 Cu 3 O 5 powder.
5、将步骤4所得Ba2Cu3O5粉末按0.75Sm2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的配比配料，充分碾磨混合均匀后，取10g混粉放入模具。5. Mix the Ba 2 Cu 3 O 5 powder obtained in step 4 according to the ratio of 0.75Sm 2 O 3 +Ba 2 Cu 3 O 5 +(0.3～1.5)wt%CeO 2 , grind and mix well, then take 10g Mix the powder into the mould.
6、将步骤5所述粉末采用嵌入式籽晶法，将尺寸为2mm×2mm的c轴取向的NdBCO/YBCO/MgO薄膜的籽晶材料压制成直径为20mm的圆柱形的前驱体，其中，2mm×2mm表示薄膜籽晶的长和宽均为2mm。6. Use the embedded seed crystal method to press the powder described in step 5, and press the c-axis-oriented NdBCO/YBCO/MgO film seed crystal material with a size of 2mm×2mm into a cylindrical precursor with a diameter of 20mm, wherein, 2mm×2mm means that the length and width of the film seed are both 2mm.
7、将步骤6中的籽晶材料、前驱体放置于生长炉中进行熔融结构生长，生长炉的具体温度程序为：7. Place the seed crystal material and precursor in step 6 in the growth furnace to grow the molten structure. The specific temperature program of the growth furnace is:
a、从室温开始经过4h升温至900℃，保温2h。a. After 4 hours from room temperature, the temperature is raised to 900°C, and the temperature is kept for 2 hours.
b、继续加热2h，升温至1110℃，保温1.5h。b. Continue heating for 2 hours, raise the temperature to 1110°C, and keep the temperature for 1.5 hours.
c、在35min内，快速降温至1060℃。c. Rapidly cool down to 1060°C within 35 minutes.
d、0.2℃/h缓慢降温生长20h，0.3℃/h缓慢降温生长20h，0.4℃/h缓慢降温生长20h，总共60h。d. Slowly cool down at 0.2°C/h for 20h, grow at 0.3°C/h for 20h, and grow at 0.4°C/h for 20h, a total of 60h.
e、淬火制得SmBCO高温超导块体材料。e. Quenching to obtain a SmBCO high-temperature superconducting bulk material.
实施例4Example 4
一种生长GdBCO高温超导块材的方法，包括如下工序：A method for growing a GdBCO high-temperature superconducting bulk material, comprising the following steps:
1、按照Ba：Cu＝2：3的比例将BaCO3和CuO粉末混合，获得BaCO3+CuO粉料；1. Mix BaCO 3 and CuO powder according to the ratio of Ba:Cu=2:3 to obtain BaCO 3 +CuO powder;
2、对步骤1所述BaCO3+CuO粉料加入无水乙醇混合均匀后进行湿磨，以获得BaCO3+CuO浆料，湿磨时间为2-4小时；2. Add absolute ethanol to the BaCO 3 +CuO powder described in step 1, mix it evenly, and perform wet grinding to obtain BaCO 3 +CuO slurry. The wet grinding time is 2-4 hours;
3、烘干步骤2中所得的BaCO3+CuO浆料制备Ba2Cu3O5粉末；3. Dry the BaCO 3 +CuO slurry obtained in step 2 to prepare Ba 2 Cu 3 O 5 powder;
4、将步骤3中的Ba2Cu3O5粉末在空气中900℃烧结48小时并重复2次此研磨、烧结过程，最终获得Ba2Cu3O5粉末。4. Sinter the Ba 2 Cu 3 O 5 powder in step 3 at 900° C. in air for 48 hours and repeat the grinding and sintering process twice to finally obtain Ba 2 Cu 3 O 5 powder.
5、将步骤4所得Ba2Cu3O5粉末按0.75Gd2O3+Ba2Cu3O5+(0.3～1.5)wt％CeO2的配比配料，充分碾磨混合均匀后，取10g混粉放入模具。5. Mix the Ba 2 Cu 3 O 5 powder obtained in step 4 according to the ratio of 0.75Gd 2 O 3 +Ba 2 Cu 3 O 5 +(0.3～1.5)wt% CeO 2 , grind and mix well, then take 10g Mix the powder into the mould.
6、将步骤5所述粉末采用嵌入式籽晶法，将尺寸为2mm×2mm的c轴取向的NdBCO/YBCO/MgO薄膜的籽晶材料压制成直径为20mm的圆柱形的前驱体，其中，2mm×2mm表示薄膜籽晶的长和宽均为2mm。6. Use the embedded seed crystal method to press the powder described in step 5, and press the c-axis-oriented NdBCO/YBCO/MgO film seed crystal material with a size of 2mm×2mm into a cylindrical precursor with a diameter of 20mm, wherein, 2mm×2mm means that the length and width of the film seed are both 2mm.
7、将步骤6中的籽晶材料、前驱体放置于生长炉中进行熔融结构生长，生长炉的具体温度程序为：7. Place the seed crystal material and precursor in step 6 in the growth furnace to grow the molten structure. The specific temperature program of the growth furnace is:
a、从室温开始经过4h升温至900℃，保温2h。a. After 4 hours from room temperature, the temperature is raised to 900°C, and the temperature is kept for 2 hours.
b、继续加热2h，升温至1110℃，保温1.5h。b. Continue heating for 2 hours, raise the temperature to 1110°C, and keep the temperature for 1.5 hours.
c、在35min内，快速降温至1040℃。c. Rapidly cool down to 1040°C within 35 minutes.
d、0.3℃/h缓慢降温生长10h，0.4℃/h缓慢降温生长15h，0.5℃/h缓慢降温生长20h，总共45h。d. Slowly cool down at 0.3°C/h for 10h, grow at 0.4°C/h for 15h, and grow at 0.5°C/h for 20h, totaling 45h.
e、淬火制得GdBCO高温超导块体材料。e. GdBCO high temperature superconducting bulk material obtained by quenching.
以上详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术人员无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。The preferred specific embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make many modifications and changes according to the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning or limited experiments on the basis of the prior art shall be within the scope of protection defined by the claims.
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