CN104953023A - Preparation method of high-density Fe(Se,Te) superconducting material - Google Patents
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- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 127
- 239000000463 material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 187
- 239000011669 selenium Substances 0.000 claims abstract description 125
- 239000011812 mixed powder Substances 0.000 claims abstract description 92
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 92
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000005245 sintering Methods 0.000 claims abstract description 52
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 32
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract description 19
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
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- 229910018110 Se—Te Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种高密度Fe(Se,Te)超导材料的制备方法，该方法为：一、将由铁粉、硒粉和碲粉混合而成的混合粉体置于真空球磨罐中；二、对混合粉体进行高能球磨处理；三、对混合粉体进行压制处理，得到Fe(Se,Te)坯体；四、对Fe(Se,Te)坯体进行烧结处理得到Fe(Se,Te)超导材料。本发明通过调控混合粉体中铁粉、硒粉和碲粉的摩尔比，优化生成的四方相Fe(Se,Te)中的铁含量，然后利用高能球磨机将混合粉体在较短的时间内进行高能球磨处理，消除了烧结处理时扩散过程对反应速率的限制，避免了硒粉熔化后导致的孔洞，得到具有高超导相含量和高密度的Fe(Se,Te)超导材料。
The invention discloses a method for preparing a high-density Fe(Se,Te) superconducting material. The method comprises the following steps: 1. Put a mixed powder formed by mixing iron powder, selenium powder and tellurium powder in a vacuum ball mill tank; 2. Perform high-energy ball milling on the mixed powder; 3. Press the mixed powder to obtain the Fe(Se,Te) body; 4. Sinter the Fe(Se,Te) body to obtain Fe(Se,Te) Te) superconducting material. The present invention optimizes the iron content in the generated tetragonal phase Fe(Se, Te) by adjusting and controlling the molar ratio of iron powder, selenium powder and tellurium powder in the mixed powder, and then uses a high-energy ball mill to grind the mixed powder in a short period of time. The high-energy ball milling treatment eliminates the limitation of the reaction rate by the diffusion process during the sintering treatment, avoids the holes caused by the melting of the selenium powder, and obtains Fe(Se,Te) superconducting materials with high superconducting phase content and high density.
Description
技术领域technical field
本发明属于超导材料制备技术领域，具体涉及一种高密度Fe(Se,Te)超导材料的制备方法。The invention belongs to the technical field of superconducting material preparation, and in particular relates to a method for preparing a high-density Fe (Se, Te) superconducting material.
背景技术Background technique
2008年，日本Hosono课题组发现了具有26K临界温度的LaO1-xFxFeAs铁基高温超导材料，随后Fe基高温超导材料(FHTS)发展迅速。目前，按阻隔层不同可分为四个主要体系，分别是“1111”体系(如LaFeAsOF)，“122”体系(如BaFe2As2)，“111”体系(如LiFeAs)和“11”体系(如FeSe)。与高温铜氧化物超导体(CHTS)类似，FHTS的晶体结构都为层状结构，由-FeAs-层(或-FeSe-层)作为超导层。In 2008, the Japanese Hosono research group discovered the LaO 1-x F x FeAs iron-based high-temperature superconducting material with a critical temperature of 26K, and then Fe-based high-temperature superconducting materials (FHTS) developed rapidly. At present, it can be divided into four main systems according to different barrier layers, namely "1111" system (such as LaFeAsOF), "122" system (such as BaFe 2 As 2 ), "111" system (such as LiFeAs) and "11" system (such as FeSe). Similar to high-temperature copper oxide superconductors (CHTS), the crystal structure of FHTS is a layered structure, with -FeAs-layer (or -FeSe-layer) as the superconducting layer.
FHTS迅速发展的主要原因有，首先，一般认为Fe的磁性对常规超导体中的电子配对有破坏作用，故在FHTS中，磁性和超导性的共存为探索高温超导机制提供了新途径；其次，FHTS具有较高的超导性能，并且各向异性弱，适合实际应用的需要，而且FHTS的上临界磁场(Hc2)远高于金属基低温超导材料，如Nb3Sn、NbTi和MgB2等，一般FHTS在4.2K左右时Hc2可达到50T以上，是Nb3Sn(Hc2为30T)的两倍左右，而Sr0.6K0.4Fe2As2的Hc2更是达到了140T左右，同时FHTS的载流性能在磁场下的衰减较慢，即使是在20T的磁场条件下，许多FHTS的临界电流密度(Jc)也能达到105A/cm-2以上；此外，FHTS的Jc较高，如SmFeAsOF单晶在5K的Jc为2×106A/cm-2，Ba0.6K0.4Fe2A2单晶在4.2K时Jc为4×105A/cm-2，FeTe0.61Se0.39的Jc在低于其临界温度14K时即可达到1×105A/cm-2，这些性能保证了FHTS实际应用的可能性。在众多FHTS中，尽管FeSe基超导材料的临界转变温度较低，但是在液氦温度下，其临界电流密度可以达到应用的要求，并且，其原料无贵金属，无毒性，储备丰富，使其在工业化生产过程中具有更大的优势。因此，制备出具有实际应用潜力的FeSe基带材是目前该体系铁基超导材料的研究重点。在FeSe基超导材料中性能更好的Fe(Se,Te)超导材料是我们关注的重点，相对于FeSe超导材料来说，Fe(Se,Te)超导材料的临界温度更高(15K)，临界电流密度更大，因此制备出性能良好的Fe(Se,Te)超导材料带材对铁基超导的实用化至关重要。The main reasons for the rapid development of FHTS are as follows. First, it is generally believed that the magnetism of Fe has a destructive effect on the electron pairing in conventional superconductors. Therefore, in FHTS, the coexistence of magnetism and superconductivity provides a new way to explore the mechanism of high-temperature superconductivity; secondly. , FHTS has high superconducting properties and weak anisotropy, which is suitable for practical applications, and the upper critical magnetic field (Hc 2 ) of FHTS is much higher than that of metal-based low-temperature superconducting materials, such as Nb 3 Sn, NbTi and MgB 2 , etc. Generally, when FHTS is around 4.2K, Hc 2 can reach more than 50T, which is about twice that of Nb 3 Sn (Hc 2 is 30T), and the Hc 2 of Sr 0.6 K 0.4 Fe 2 As 2 even reaches about 140T , at the same time, the current-carrying performance of FHTS decays slowly under the magnetic field. Even under the condition of 20T magnetic field, the critical current density (Jc) of many FHTS can reach more than 10 5 A/cm -2 ; in addition, the Jc of FHTS Higher, such as the Jc of SmFeAsOF single crystal at 5K is 2×10 6 A/cm -2 , the Jc of Ba 0.6 K 0.4 Fe 2 A 2 single crystal at 4.2K is 4×10 5 A/cm -2 , FeTe 0.61 The Jc of Se 0.39 can reach 1×10 5 A/cm -2 when it is lower than its critical temperature of 14K. These properties guarantee the possibility of practical application of FHTS. In many FHTS, although the critical transition temperature of FeSe-based superconducting materials is low, its critical current density can meet the application requirements at the temperature of liquid helium, and its raw materials are free of precious metals, non-toxic, and abundant in reserves, making it It has greater advantages in the process of industrial production. Therefore, the preparation of FeSe-based tapes with practical application potential is the current research focus of this system of iron-based superconducting materials. Among FeSe-based superconducting materials, Fe(Se,Te) superconducting materials with better performance are the focus of our attention. Compared with FeSe superconducting materials, the critical temperature of Fe(Se,Te) superconducting materials is higher ( 15K), the critical current density is higher, so the preparation of Fe(Se,Te) superconducting material strips with good performance is very important for the practical application of iron-based superconductors.
而现有技术在Fe(Se,Te)超导材料制备过程中存在的最主要问题是：由于Fe(Se,Te)具有两种晶体结构，一种是六方相，其中，Fe:(Se,Te)比例略低于1:1，由于结构的限制六方相Fe(Se,Te)不具备超导性能；另一种是四方相，这种结构中-Fe(Se,Te)-呈片层状分布，即成为了与-FeAs-和-CuO-相似的超导层结构，因此，在14K左右发生超导转变。在材料的烧结过程中，这两种结构之间具有相互转化的关系。目前，采用传统烧结方法，或通过对前驱体粉末进行普通球磨后再烧结的方法仅能通过提高烧结温度和延长烧结时间的手段获得超导相含量的提高，烧结效率差，这一方法不仅消耗大量的能源，而且最佳四方相含量也仅能达到80％以下，并且所获得样品的密度极低，低的芯丝密度对超导线材的制备带来很大负面影响，这种情况下，超导相很难达到联通，材料的载流性能较低，因此现有技术中亟需开发新型的Fe(Se,Te)超导材料制备方法，对后续高性能Fe(Se,Te)超导线材以及Fe基超导材料超导机理的探索都具有重要的意义。And the most important problem that existing technology exists in Fe(Se, Te) superconducting material preparation process is: because Fe(Se, Te) has two kinds of crystal structures, one is hexagonal phase, wherein, Fe:(Se, Te) ratio is slightly lower than 1:1, due to the limitation of the structure, the hexagonal phase Fe(Se,Te) does not have superconducting properties; the other is the tetragonal phase, in which -Fe(Se,Te)-is a sheet shape distribution, that is, it becomes a superconducting layer structure similar to -FeAs- and -CuO-, so the superconducting transition occurs around 14K. During the sintering process of the material, there is a mutual transformation relationship between the two structures. At present, the traditional sintering method or the method of sintering the precursor powder after ordinary ball milling can only increase the superconducting phase content by increasing the sintering temperature and prolonging the sintering time, and the sintering efficiency is poor. This method not only consumes A large amount of energy, and the best tetragonal phase content can only reach below 80%, and the density of the obtained sample is extremely low, and the low core filament density has a great negative impact on the preparation of the superconducting wire. In this case, The superconducting phase is difficult to achieve Unicom, and the current-carrying performance of the material is low. Therefore, it is urgent to develop a new method for preparing Fe(Se,Te) superconducting materials in the prior art, and it is necessary for the follow-up high-performance Fe(Se,Te) superconducting The exploration of the superconducting mechanism of wires and Fe-based superconducting materials is of great significance.
发明内容Contents of the invention
本发明所要解决的技术问题在于针对上述现有技术中的不足，提供一种高密度Fe(Se,Te)超导材料的制备方法，该方法消除了烧结处理时扩散过程对反应速率的限制，避免了硒粉熔化后导致的孔洞，得到具有高超导相含量和高密度的Fe(Se,Te)超导材料，具有能耗小，工艺流程短，可重复性强等优点。The technical problem to be solved by the present invention is to provide a method for preparing a high-density Fe(Se,Te) superconducting material for the deficiencies in the above-mentioned prior art, which eliminates the limitation of the reaction rate by the diffusion process during the sintering process, The hole caused by the melting of selenium powder is avoided, and the Fe(Se,Te) superconducting material with high superconducting phase content and high density is obtained, which has the advantages of low energy consumption, short process flow and strong repeatability.
为解决上述技术问题，本发明采用的技术方案是：一种高密度Fe(Se,Te)超导材料的制备方法，其特征在于，包括以下步骤：In order to solve the above-mentioned technical problems, the technical solution adopted in the present invention is: a kind of preparation method of high-density Fe (Se, Te) superconducting material, it is characterized in that, comprises the following steps:
步骤一、在充满惰性气体的手套箱中，将混合粉体置于真空球磨罐中，然后将真空球磨罐密封后取出；所述混合粉体由摩尔比为(0.9～1.4):x：(1-x)的铁粉、硒粉和碲粉混合而成，所述x＝0.2～0.8；Step 1. In a glove box filled with inert gas, place the mixed powder in a vacuum ball mill jar, then seal the vacuum ball mill jar and take it out; the molar ratio of the mixed powder is (0.9～1.4):x:( 1-x) is formed by mixing iron powder, selenium powder and tellurium powder, said x=0.2～0.8;
步骤二、将步骤一中装有混合粉体的真空球磨罐置于高能球磨机中进行高能球磨处理，具体过程为：Step 2. Place the vacuum ball milling tank containing the mixed powder in step 1 in a high-energy ball mill for high-energy ball milling. The specific process is:
步骤201、在高能球磨机的转速不低于1500r/min的条件下将混合粉体高能球磨处理5min～30min，然后将真空球磨罐取出后浸泡于液氮中冷却；所述高能球磨处理的过程中混合粉体的温度不高于60℃，所述高能球磨处理的球料比为1:(1～20)；Step 201: Under the condition that the rotational speed of the high-energy ball mill is not lower than 1500r/min, the mixed powder is high-energy ball milled for 5 minutes to 30 minutes, and then the vacuum ball mill tank is taken out and soaked in liquid nitrogen to cool; during the process of the high-energy ball mill The temperature of the mixed powder is not higher than 60°C, and the ball-to-material ratio of the high-energy ball milling treatment is 1:(1～20);
步骤202、重复步骤201,直至将混合粉体累计高能球磨处理0.5h～12h；Step 202, repeating step 201 until the mixed powder is accumulatively processed by high-energy ball milling for 0.5h to 12h;
步骤三、在充满惰性气体的手套箱中，将步骤二中经高能球磨处理后的混合粉体从真空球磨罐中取出放入不锈钢模具中，将不锈钢模具密封后从手套箱中取出，然后将不锈钢模具置于压片机上，在压片机的压力为5MPa～10MPa的条件下将经高能球磨处理后的混合粉体压制处理2min～30min，得到Fe(Se,Te)坯体；Step 3. In a glove box filled with inert gas, take the mixed powder processed by high-energy ball milling in step 2 out of the vacuum ball mill tank and put it into a stainless steel mold. After sealing the stainless steel mold, take it out of the glove box, and then put The stainless steel mold is placed on the tablet press, and under the condition of the pressure of the tablet press at 5MPa-10MPa, the mixed powder after high-energy ball milling is pressed for 2min-30min to obtain the Fe(Se,Te) green body;
步骤四、在充满惰性气体的手套箱中，将步骤三中所述Fe(Se,Te)坯体从不锈钢模具中取出置于石英管中，将石英管密封后从手套箱中取出，然后将石英管置于烧结炉中，在烧结炉的温度为500℃～700℃条件下对Fe(Se,Te)坯体烧结处理8h～25h，再以不高于30℃/h的降温速率降至室温，得到Fe(Se,Te)超导材料；所述Fe(Se,Te)超导材料的密度不低于5.02g/cm3，所述烧结处理在真空或氩气气氛中进行。Step 4. In a glove box full of inert gas, the Fe(Se, Te) body described in step 3 is taken out from the stainless steel mold and placed in a quartz tube, and the quartz tube is sealed and taken out of the glove box, and then The quartz tube is placed in a sintering furnace, and the Fe(Se, Te) green body is sintered for 8h to 25h at a temperature of 500°C to 700°C in the sintering furnace, and then dropped to At room temperature, Fe(Se,Te) superconducting material is obtained; the density of the Fe(Se,Te) superconducting material is not lower than 5.02g/cm 3 , and the sintering treatment is carried out in vacuum or argon atmosphere.
上述的一种高密度Fe(Se,Te)超导材料的制备方法，其特征在于，步骤一中所述铁粉为还原铁粉，所述铁粉的质量纯度不低于99％，所述硒粉的质量纯度不低于99％，所述碲粉的质量纯度不低于99％。The above-mentioned method for preparing a high-density Fe(Se, Te) superconducting material is characterized in that the iron powder described in step 1 is reduced iron powder, and the mass purity of the iron powder is not less than 99%. The mass purity of the selenium powder is not lower than 99%, and the mass purity of the tellurium powder is not lower than 99%.
上述的一种高密度Fe(Se,Te)超导材料的制备方法，其特征在于，步骤一中所述铁粉、硒粉和碲粉的摩尔比为(1.0～1.2):x：(1-x)，所述x＝0.4～0.6。A kind of preparation method of above-mentioned high-density Fe (Se, Te) superconducting material is characterized in that, the molar ratio of iron powder, selenium powder and tellurium powder described in step 1 is (1.0～1.2): x: (1 -x), said x=0.4～0.6.
上述的一种高密度Fe(Se,Te)超导材料的制备方法，其特征在于，所述铁粉、硒粉和碲粉的摩尔比为1.1:0.5:0.5。The above-mentioned method for preparing a high-density Fe(Se, Te) superconducting material is characterized in that the molar ratio of the iron powder, selenium powder and tellurium powder is 1.1:0.5:0.5.
上述的一种高密度Fe(Se,Te)超导材料的制备方法，其特征在于，步骤201中所述高能球磨处理的球料比为1:(3～6)，步骤202中累计高能球磨处理的时间为2h～6h。The above-mentioned method for preparing a high-density Fe(Se, Te) superconducting material is characterized in that the ball-to-material ratio of the high-energy ball milling process described in step 201 is 1:(3～6), and the cumulative high-energy ball milling process in step 202 The processing time is 2h～6h.
上述的一种高密度Fe(Se,Te)超导材料的制备方法，其特征在于，所述高能球磨处理的球料比为1:6，累计高能球磨处理的时间为4h。The above-mentioned method for preparing a high-density Fe(Se, Te) superconducting material is characterized in that the ball-to-material ratio of the high-energy ball milling treatment is 1:6, and the cumulative high-energy ball milling treatment time is 4 hours.
上述的一种高密度Fe(Se,Te)超导材料的制备方法，其特征在于，步骤三中所述压制处理的压力为8MPa～10MPa，压制处理的时间为5min～20min。The above-mentioned method for preparing a high-density Fe(Se, Te) superconducting material is characterized in that the pressure of the pressing treatment in step 3 is 8MPa-10MPa, and the time of the pressing treatment is 5min-20min.
上述的一种高密度Fe(Se,Te)超导材料的制备方法，其特征在于，所述压制处理的压力为10MPa，压制处理的时间为10min。The above-mentioned method for preparing a high-density Fe(Se, Te) superconducting material is characterized in that the pressure of the pressing treatment is 10 MPa, and the time of the pressing treatment is 10 minutes.
上述的一种高密度Fe(Se,Te)超导材料的制备方法，其特征在于，步骤四中所述烧结处理的温度为600℃～700℃，烧结处理的时间为10h～24h。The above-mentioned method for preparing a high-density Fe(Se, Te) superconducting material is characterized in that the temperature of the sintering treatment in step 4 is 600°C-700°C, and the time of the sintering treatment is 10h-24h.
上述的一种高密度Fe(Se,Te)超导材料的制备方法，其特征在于，所述烧结处理的温度为650℃，烧结处理的时间为15h。The above-mentioned method for preparing a high-density Fe(Se, Te) superconducting material is characterized in that the temperature of the sintering treatment is 650° C., and the time of the sintering treatment is 15 hours.
本发明与现有技术相比具有以下优点：Compared with the prior art, the present invention has the following advantages:
1、本发明采用高能球磨辅助烧结的工艺过程制备得到高密度的Fe(Se,Te)超导材料，其中，通过调控混合粉体中铁粉、硒粉和碲粉的摩尔比，优化生成的四方相Fe(Se,Te)中的铁含量，然后利用高能球磨机将混合粉体在较短的时间内进行高能球磨处理，在缩小混合粉体原始颗粒尺寸的同时，获得了Fe-Se-Te三元固溶体，使混合粉体中的Fe、Se和Te达到原子级的混合，消除了烧结处理时扩散过程对反应速率的限制，并且避免了由于铁粉分布不均匀而生成六方相Fe(Se,Te)的缺陷以及硒粉熔化后导致的孔洞，再将混合粉体压片后经过烧结处理，得到具有高超导相含量和高密度的超导材料，具有能耗小，工艺流程短，可重复性强等优点。1. The present invention adopts high-energy ball milling-assisted sintering process to prepare high-density Fe(Se, Te) superconducting materials, wherein, by adjusting and controlling the molar ratio of iron powder, selenium powder and tellurium powder in the mixed powder, the generated tetragonal Fe(Se,Te) in the phase Fe(Se,Te), and then use the high-energy ball mill to perform high-energy ball milling on the mixed powder in a short period of time. While reducing the original particle size of the mixed powder, the Fe-Se-Te three Elemental solid solution, so that Fe, Se and Te in the mixed powder can be mixed at the atomic level, eliminating the limitation of the reaction rate by the diffusion process during sintering, and avoiding the formation of hexagonal phase Fe(Se, Te) defects and holes caused by the melting of selenium powder, and then the mixed powder is pressed into tablets and then sintered to obtain a superconducting material with high superconducting phase content and high density, which has low energy consumption, short process flow, and can be used Strong repeatability and other advantages.
2、本发明中通过高能球磨产生的机械能使混合粉体合金化，这种机械合金化进程可以使铁粉、硒粉和碲粉之间的结合更加紧密，并且可以避免硒粉的熔化，在烧结过程中使气孔率降低，得到高密度的Fe(Se,Te)超导材料，而采用传统工艺制备无Te掺杂的FeSe超导材料时高能球磨并不会对材料密度有所影响。2. In the present invention, the mixed powder is alloyed by the mechanical energy produced by high-energy ball milling. This mechanical alloying process can make the combination between iron powder, selenium powder and tellurium powder tighter, and can avoid the melting of selenium powder. During the sintering process, the porosity is reduced to obtain a high-density Fe(Se,Te) superconducting material, while the high-energy ball milling does not affect the material density when the traditional process is used to prepare the Te-free FeSe superconducting material.
3、与传统的行星球磨辅助烧结工艺制备超导材料的方法相比，本发明采用高能球磨机进行高能球磨处理的工艺不仅极大的缩短了球磨所需时间(行星球磨需20h以上)，避免了长时间球磨可能引起混合粉体被氧化的缺陷，而且减小了能耗，此外，经高能球磨处理后混合粉体中的Fe、Se和Te分布更均匀，经烧结处理后获得四方相Fe(Se,Te)的含量更高，相对于未球磨样品的密度更大，本发明制备的Fe(Se,Te)超导材料能够满足后续实验及工业应用对铁基超导材料纯度和性能的要求，适于工业化大规模生产。3. Compared with the traditional planetary ball mill-assisted sintering process for preparing superconducting materials, the present invention uses a high-energy ball mill for high-energy ball milling, which not only greatly shortens the time required for ball milling (more than 20 hours for planetary ball milling), but also avoids Long-time ball milling may cause the defect that the mixed powder is oxidized, and reduces energy consumption. In addition, the distribution of Fe, Se and Te in the mixed powder is more uniform after high-energy ball milling, and the tetragonal phase Fe ( The content of Se, Te) is higher, and the density is higher than that of the sample without ball milling. The Fe(Se, Te) superconducting material prepared by the present invention can meet the requirements of subsequent experiments and industrial applications on the purity and performance of iron-based superconducting materials. , suitable for large-scale industrial production.
下面通过附图和实施例，对本发明的技术方案做进一步的详细描述。The technical solutions of the present invention will be described in further detail below with reference to the accompanying drawings and embodiments.
附图说明Description of drawings
图1为本发明实施例1中混合粉体经高能球磨处理前的SEM照片。Fig. 1 is a SEM photo of the mixed powder in Example 1 of the present invention before being processed by high-energy ball milling.
图2为本发明实施例1中混合粉体经高能球磨处理后的SEM照片。Fig. 2 is a SEM photo of the mixed powder in Example 1 of the present invention after high-energy ball milling.
图3为本发明实施例1制备的Fe(Se,Te)超导材料的XRD谱图。Fig. 3 is the XRD spectrum of the Fe(Se, Te) superconducting material prepared in Example 1 of the present invention.
图4为本发明实施例1制备的Fe(Se,Te)超导材料的超导转变温度曲线。Fig. 4 is the superconducting transition temperature curve of the Fe(Se, Te) superconducting material prepared in Example 1 of the present invention.
图5为本发明实施例2制备的Fe(Se,Te)超导材料的XRD谱图。Fig. 5 is the XRD spectrum of the Fe(Se, Te) superconducting material prepared in Example 2 of the present invention.
具体实施方式Detailed ways
实施例1Example 1
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、在充满惰性气体的手套箱中，将混合粉体置于真空球磨罐中，然后将真空球磨罐密封后取出；所述混合粉体由摩尔比为1.1:0.5:0.5的铁粉、硒粉和碲粉混合而成；所述铁粉为还原铁粉，所述铁粉的质量纯度不低于99％，所述硒粉的质量纯度不低于99％，所述碲粉的质量纯度不低于99％；Step 1. In a glove box filled with an inert gas, place the mixed powder in a vacuum ball mill jar, then seal the vacuum ball mill jar and take it out; the mixed powder is composed of iron powder with a molar ratio of 1.1:0.5:0.5, Selenium powder and tellurium powder are mixed; the iron powder is reduced iron powder, the mass purity of the iron powder is not less than 99%, the mass purity of the selenium powder is not less than 99%, and the mass purity of the tellurium powder is Purity not less than 99%;
步骤二、将步骤一中装有混合粉体的真空球磨罐置于高能球磨机中进行高能球磨处理，具体过程为：Step 2. Place the vacuum ball milling tank containing the mixed powder in step 1 in a high-energy ball mill for high-energy ball milling. The specific process is:
步骤201、在高能球磨机的转速为1740r/min的条件下将混合粉体高能球磨处理10min，然后将真空球磨罐取出后浸泡于液氮中冷却；所述高能球磨处理的过程中混合粉体的温度不高于60℃，所述高能球磨处理的球料比为1:6；Step 201: Under the condition that the rotating speed of the high-energy ball mill is 1740r/min, the mixed powder is subjected to high-energy ball milling treatment for 10 minutes, and then the vacuum ball milling tank is taken out and soaked in liquid nitrogen to cool; during the high-energy ball milling process, the mixed powder The temperature is not higher than 60°C, and the ball-to-material ratio of the high-energy ball milling treatment is 1:6;
步骤202、重复步骤201,直至将混合粉体累计高能球磨处理4h；Step 202, repeating step 201 until the mixed powder is accumulatively treated by high-energy ball milling for 4 hours;
步骤三、在充满惰性气体的手套箱中，将步骤二中经高能球磨处理后的混合粉体从真空球磨罐中取出放入不锈钢模具中，将不锈钢模具密封后从手套箱中取出，然后将不锈钢模具置于压片机上，在压片机的压力为10MPa的条件下将经高能球磨处理后的混合粉体压制处理10min，得到Fe(Se,Te)坯体；Step 3. In a glove box filled with inert gas, take the mixed powder processed by high-energy ball milling in step 2 out of the vacuum ball mill tank and put it into a stainless steel mold. After sealing the stainless steel mold, take it out of the glove box, and then put The stainless steel mold is placed on the tablet press, and under the condition that the pressure of the tablet press is 10MPa, the mixed powder processed by high-energy ball milling is pressed for 10 minutes to obtain a Fe(Se,Te) green body;
步骤四、在充满惰性气体的手套箱中，将步骤三中所述Fe(Se,Te)坯体从不锈钢模具中取出置于石英管中，将石英管密封后从手套箱中取出，然后将石英管置于烧结炉中，在烧结炉的温度为650℃条件下对Fe(Se,Te)坯体烧结处理15h，再以25℃/h的降温速率降至室温，得到Fe(Se,Te)超导材料；所述烧结处理在氩气气氛中进行。Step 4. In a glove box full of inert gas, the Fe(Se, Te) body described in step 3 is taken out from the stainless steel mold and placed in a quartz tube, and the quartz tube is sealed and taken out of the glove box, and then The quartz tube was placed in a sintering furnace, and the Fe(Se, Te) green body was sintered for 15 hours at a temperature of 650 °C in the sintering furnace, and then cooled to room temperature at a rate of 25 °C/h to obtain Fe(Se, Te ) superconducting material; the sintering treatment is carried out in an argon atmosphere.
结合图1和图2可对比看出，经高能球磨处理后，混合粉末的微观颗粒尺寸发生了较大的变化，平均颗粒尺寸由50μm以上，减小到了10μm以下，由图3可看出，本实施例制备的Fe(Se,Te)为四方相Fe(Se,Te)结构，无杂相，由图4可看出，本实施例制备的Fe(Se,Te)超导材料的超导转变温度(Tc)为11.1K，表现出了良好的超导性能，测试本实施例制备的Fe(Se,Te)超导材料的密度为5.61g/cm3，而未采用高能球磨，仅经相同压制和烧结工艺得到Fe(Se,Te)超导材料的密度为2.29g/cm3，由此可知，高能球磨辅助烧结的工艺可大大提高制备的Fe(Se,Te)超导材料的密度，为今后制备高密度超导带材芯丝打下基础。Combining Figure 1 and Figure 2, it can be seen that after the high-energy ball milling treatment, the microscopic particle size of the mixed powder has changed greatly, and the average particle size has been reduced from more than 50 μm to less than 10 μm. It can be seen from Figure 3 that, The Fe(Se, Te) prepared in this example has a tetragonal phase Fe(Se, Te) structure without impurity phases. As can be seen from Figure 4, the superconductivity of the Fe(Se, Te) superconducting material prepared in this example is The transition temperature (Tc) is 11.1K, showing good superconducting properties. The density of the Fe(Se,Te) superconducting material prepared in this example is 5.61g/cm 3 . The density of the Fe(Se,Te) superconducting material obtained by the same pressing and sintering process is 2.29g/cm 3 . It can be seen that the high-energy ball milling-assisted sintering process can greatly increase the density of the prepared Fe(Se,Te) superconducting material , laying the foundation for the preparation of high-density superconducting tape core wire in the future.
实施例2Example 2
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、在充满惰性气体的手套箱中，将混合粉体置于真空球磨罐中，然后将真空球磨罐密封后取出；所述混合粉体由摩尔比为1.2:0.5:0.5的铁粉、硒粉和碲粉混合而成；所述铁粉为还原铁粉，所述铁粉的质量纯度不低于99％，所述硒粉的质量纯度不低于99％，所述碲粉的质量纯度不低于99％；Step 1. In a glove box filled with an inert gas, place the mixed powder in a vacuum ball mill jar, then seal the vacuum ball mill jar and take it out; the mixed powder is composed of iron powder with a molar ratio of 1.2:0.5:0.5, Selenium powder and tellurium powder are mixed; the iron powder is reduced iron powder, the mass purity of the iron powder is not less than 99%, the mass purity of the selenium powder is not less than 99%, and the mass purity of the tellurium powder is Purity not less than 99%;
步骤二、将步骤一中装有混合粉体的真空球磨罐置于高能球磨机中进行高能球磨处理，具体过程为：Step 2. Place the vacuum ball milling tank containing the mixed powder in step 1 in a high-energy ball mill for high-energy ball milling. The specific process is:
步骤201、在高能球磨机的转速为1800r/min的条件下将混合粉体高能球磨处理20min，然后将真空球磨罐取出后浸泡于液氮中冷却；所述高能球磨处理的过程中混合粉体的温度不高于60℃，所述高能球磨处理的球料比为1:6；Step 201: Under the condition that the speed of the high-energy ball mill is 1800r/min, the mixed powder is high-energy ball milled for 20 minutes, and then the vacuum ball mill tank is taken out and soaked in liquid nitrogen to cool; The temperature is not higher than 60°C, and the ball-to-material ratio of the high-energy ball milling treatment is 1:6;
步骤202、重复步骤201,直至将混合粉体累计高能球磨处理2h；Step 202, repeating step 201 until the mixed powder is accumulatively treated by high-energy ball milling for 2 hours;
步骤三、在充满惰性气体的手套箱中，将步骤二中经高能球磨处理后的混合粉体从真空球磨罐中取出放入不锈钢模具中，将不锈钢模具密封后从手套箱中取出，然后将不锈钢模具置于压片机上，在压片机的压力为9MPa的条件下将经高能球磨处理后的混合粉体压制处理20min，得到Fe(Se,Te)坯体；Step 3. In a glove box filled with inert gas, take the mixed powder processed by high-energy ball milling in step 2 out of the vacuum ball mill tank and put it into a stainless steel mold. After sealing the stainless steel mold, take it out of the glove box, and then put The stainless steel mold is placed on the tablet press, and under the condition that the pressure of the tablet press is 9MPa, the mixed powder processed by high-energy ball milling is pressed for 20 minutes to obtain a Fe(Se,Te) green body;
步骤四、在充满惰性气体的手套箱中，将步骤三中所述Fe(Se,Te)坯体从不锈钢模具中取出置于石英管中，将石英管密封后从手套箱中取出，然后将石英管置于烧结炉中，在烧结炉的温度为700℃条件下对Fe(Se,Te)坯体烧结处理8h，再以20℃/h的降温速率降至室温，得到Fe(Se,Te)超导材料；所述烧结处理在真空气氛中进行。Step 4. In a glove box full of inert gas, the Fe(Se, Te) body described in step 3 is taken out from the stainless steel mold and placed in a quartz tube, and the quartz tube is sealed and taken out of the glove box, and then The quartz tube was placed in a sintering furnace, and the Fe(Se, Te) blank was sintered for 8 hours at a temperature of 700 °C in the sintering furnace, and then cooled to room temperature at a rate of 20 °C/h to obtain Fe(Se, Te ) superconducting material; the sintering process is carried out in a vacuum atmosphere.
由图5可看出，本实施例制备的Fe(Se,Te)为四方相Fe(Se,Te)结构，无杂相，本实施例制备的Fe(Se,Te)超导材料的超导转变温度(Tc)为10.1K，密度为5.61g/cm3，具有高密度以及良好的超导性能。It can be seen from Figure 5 that the Fe(Se, Te) prepared in this example has a tetragonal phase Fe(Se, Te) structure without impurity phases, and the superconductivity of the Fe(Se, Te) superconducting material prepared in this example is The transition temperature (Tc) is 10.1K, the density is 5.61g/cm 3 , and it has high density and good superconducting properties.
实施例3Example 3
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、在充满惰性气体的手套箱中，将混合粉体置于真空球磨罐中，然后将真空球磨罐密封后取出；所述混合粉体由摩尔比为1.0:0.3:0.7的铁粉、硒粉和碲粉混合而成；所述铁粉为还原铁粉，所述铁粉的质量纯度不低于99％，所述硒粉的质量纯度不低于99％，所述碲粉的质量纯度不低于99％；Step 1. In a glove box filled with an inert gas, place the mixed powder in a vacuum ball mill jar, then seal the vacuum ball mill jar and take it out; the mixed powder is composed of iron powder with a molar ratio of 1.0:0.3:0.7, Selenium powder and tellurium powder are mixed; the iron powder is reduced iron powder, the mass purity of the iron powder is not less than 99%, the mass purity of the selenium powder is not less than 99%, and the mass purity of the tellurium powder is Purity not less than 99%;
步骤二、将步骤一中装有混合粉体的真空球磨罐置于高能球磨机中进行高能球磨处理，具体过程为：Step 2. Place the vacuum ball milling tank containing the mixed powder in step 1 in a high-energy ball mill for high-energy ball milling. The specific process is:
步骤201、在高能球磨机的转速为1500r/min的条件下将混合粉体高能球磨处理30min，然后将真空球磨罐取出后浸泡于液氮中冷却；所述高能球磨处理的过程中混合粉体的温度不高于60℃，所述高能球磨处理的球料比为1:10；Step 201: Under the condition that the rotating speed of the high-energy ball mill is 1500r/min, the mixed powder is subjected to high-energy ball milling treatment for 30 minutes, and then the vacuum ball mill tank is taken out and soaked in liquid nitrogen for cooling; during the process of the high-energy ball milling process, the mixed powder The temperature is not higher than 60°C, and the ball-to-material ratio of the high-energy ball milling treatment is 1:10;
步骤202、重复步骤201,直至将混合粉体累计高能球磨处理8h；Step 202, repeating step 201 until the mixed powder is accumulatively treated by high-energy ball milling for 8 hours;
步骤三、在充满惰性气体的手套箱中，将步骤二中经高能球磨处理后的混合粉体从真空球磨罐中取出放入不锈钢模具中，将不锈钢模具密封后从手套箱中取出，然后将不锈钢模具置于压片机上，在压片机的压力为10MPa的条件下将经高能球磨处理后的混合粉体压制处理30min，得到Fe(Se,Te)坯体；Step 3. In a glove box filled with inert gas, take the mixed powder processed by high-energy ball milling in step 2 out of the vacuum ball mill tank and put it into a stainless steel mold. After sealing the stainless steel mold, take it out of the glove box, and then put The stainless steel mold is placed on the tablet press, and the mixed powder after the high-energy ball milling treatment is pressed for 30 minutes under the condition that the pressure of the tablet press is 10MPa, to obtain the Fe(Se,Te) green body;
步骤四、在充满惰性气体的手套箱中，将步骤三中所述Fe(Se,Te)坯体从不锈钢模具中取出置于石英管中，将石英管密封后从手套箱中取出，然后将石英管置于烧结炉中，在烧结炉的温度为600℃条件下对Fe(Se,Te)坯体烧结处理10h，再以15℃/h的降温速率降至室温，得到Fe(Se,Te)超导材料；所述烧结处理在氩气气氛中进行。Step 4. In a glove box full of inert gas, the Fe(Se, Te) body described in step 3 is taken out from the stainless steel mold and placed in a quartz tube, and the quartz tube is sealed and taken out of the glove box, and then The quartz tube was placed in a sintering furnace, and the Fe(Se, Te) green body was sintered for 10 h at a temperature of 600 °C in the sintering furnace, and then cooled to room temperature at a cooling rate of 15 °C/h to obtain Fe(Se, Te ) superconducting material; the sintering treatment is carried out in an argon atmosphere.
本实施例制备的Fe(Se,Te)主相为四方相Fe(Se,Te)结构，并且四方相Fe(Se,Te)的含量达到90vol％，本实施例制备的Fe(Se,Te)超导材料的超导转变温度(Tc)为10.5K，密度为5.65g/cm3，具有高密度以及良好的超导性能。The main phase of Fe(Se, Te) prepared in this example is a tetragonal phase Fe(Se, Te) structure, and the content of tetragonal phase Fe(Se, Te) reaches 90vol%. The Fe(Se, Te) prepared in this example The superconducting transition temperature (Tc) of the superconducting material is 10.5K, the density is 5.65g/cm 3 , and has high density and good superconducting performance.
实施例4Example 4
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、在充满惰性气体的手套箱中，将混合粉体置于真空球磨罐中，然后将真空球磨罐密封后取出；所述混合粉体由摩尔比为1.4:0.6:0.4的铁粉、硒粉和碲粉混合而成；所述铁粉为还原铁粉，所述铁粉的质量纯度不低于99％，所述硒粉的质量纯度不低于99％，所述碲粉的质量纯度不低于99％；Step 1. In a glove box filled with an inert gas, place the mixed powder in a vacuum ball mill jar, then seal the vacuum ball mill jar and take it out; the mixed powder is composed of iron powder with a molar ratio of 1.4:0.6:0.4, Selenium powder and tellurium powder are mixed; the iron powder is reduced iron powder, the mass purity of the iron powder is not less than 99%, the mass purity of the selenium powder is not less than 99%, and the mass purity of the tellurium powder is Purity not less than 99%;
步骤二、将步骤一中装有混合粉体的真空球磨罐置于高能球磨机中进行高能球磨处理，具体过程为：Step 2. Place the vacuum ball milling tank containing the mixed powder in step 1 in a high-energy ball mill for high-energy ball milling. The specific process is:
步骤201、在高能球磨机的转速为1700r/min的条件下将混合粉体高能球磨处理20min，然后将真空球磨罐取出后浸泡于液氮中冷却；所述高能球磨处理的过程中混合粉体的温度不高于60℃，所述高能球磨处理的球料比为1:3；Step 201: Under the condition that the speed of the high-energy ball mill is 1700r/min, the mixed powder is subjected to high-energy ball milling for 20 minutes, and then the vacuum ball mill tank is taken out and soaked in liquid nitrogen to cool; during the high-energy ball milling process, the mixed powder The temperature is not higher than 60°C, and the ball-to-material ratio of the high-energy ball milling treatment is 1:3;
步骤202、重复步骤201,直至将混合粉体累计高能球磨处理6h；Step 202, repeating step 201 until the mixed powder is accumulatively treated by high-energy ball milling for 6 hours;
步骤三、在充满惰性气体的手套箱中，将步骤二中经高能球磨处理后的混合粉体从真空球磨罐中取出放入不锈钢模具中，将不锈钢模具密封后从手套箱中取出，然后将不锈钢模具置于压片机上，在压片机的压力为8MPa的条件下将经高能球磨处理后的混合粉体压制处理10min，得到Fe(Se,Te)坯体；Step 3. In a glove box filled with inert gas, take the mixed powder processed by high-energy ball milling in step 2 out of the vacuum ball mill tank and put it into a stainless steel mold. After sealing the stainless steel mold, take it out of the glove box, and then put The stainless steel mold is placed on the tablet press, and under the condition that the pressure of the tablet press is 8MPa, the mixed powder after the high-energy ball milling treatment is pressed for 10 minutes to obtain the Fe(Se,Te) green body;
步骤四、在充满惰性气体的手套箱中，将步骤三中所述Fe(Se,Te)坯体从不锈钢模具中取出置于石英管中，将石英管密封后从手套箱中取出，然后将石英管置于烧结炉中，在烧结炉的温度为500℃条件下对Fe(Se,Te)坯体烧结处理25h，再以15℃/h的降温速率降至室温，得到Fe(Se,Te)超导材料；所述烧结处理在氩气气氛中进行。Step 4. In a glove box full of inert gas, the Fe(Se, Te) body described in step 3 is taken out from the stainless steel mold and placed in a quartz tube, and the quartz tube is sealed and taken out of the glove box, and then The quartz tube was placed in a sintering furnace, and the Fe(Se, Te) green body was sintered for 25 hours at a temperature of 500 °C in the sintering furnace, and then cooled to room temperature at a cooling rate of 15 °C/h to obtain Fe(Se, Te) ) superconducting material; the sintering treatment is carried out in an argon atmosphere.
本实施例制备的Fe(Se,Te)主相为四方相Fe(Se,Te)结构，并且四方相Fe(Se,Te)的含量达到95vol％，本实施例制备的Fe(Se,Te)超导材料的超导转变温度(Tc)为9.2K，密度为5.63g/cm3，具有高密度以及良好的超导性能。The Fe(Se, Te) main phase prepared in this example is a tetragonal phase Fe(Se, Te) structure, and the content of the tetragonal phase Fe(Se, Te) reaches 95vol%. The Fe(Se, Te) prepared in this example The superconducting transition temperature (Tc) of the superconducting material is 9.2K, and the density is 5.63g/cm 3 , which has high density and good superconducting performance.
实施例5Example 5
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、在充满惰性气体的手套箱中，将混合粉体置于真空球磨罐中，然后将真空球磨罐密封后取出；所述混合粉体由摩尔比为0.9:0.4:0.6的铁粉、硒粉和碲粉混合而成；所述铁粉为还原铁粉，所述铁粉的质量纯度不低于99％，所述硒粉的质量纯度不低于99％，所述碲粉的质量纯度不低于99％；Step 1. In a glove box filled with an inert gas, place the mixed powder in a vacuum ball mill jar, then seal the vacuum ball mill jar and take it out; the mixed powder is composed of iron powder with a molar ratio of 0.9:0.4:0.6, Selenium powder and tellurium powder are mixed; the iron powder is reduced iron powder, the mass purity of the iron powder is not less than 99%, the mass purity of the selenium powder is not less than 99%, and the mass purity of the tellurium powder is Purity not less than 99%;
步骤二、将步骤一中装有混合粉体的真空球磨罐置于高能球磨机中进行高能球磨处理，具体过程为：Step 2. Place the vacuum ball milling tank containing the mixed powder in step 1 in a high-energy ball mill for high-energy ball milling. The specific process is:
步骤201、在高能球磨机的转速为2000r/min的条件下将混合粉体高能球磨处理5min，然后将真空球磨罐取出后浸泡于液氮中冷却；所述高能球磨处理的过程中混合粉体的温度不高于60℃，所述高能球磨处理的球料比为1:4；Step 201: Under the condition that the rotating speed of the high-energy ball mill is 2000r/min, the mixed powder is subjected to high-energy ball milling for 5 minutes, and then the vacuum ball mill tank is taken out and soaked in liquid nitrogen to cool; during the process of the high-energy ball milling, the mixed powder The temperature is not higher than 60°C, and the ball-to-material ratio of the high-energy ball milling treatment is 1:4;
步骤202、重复步骤201,直至将混合粉体累计高能球磨处理0.5h；Step 202, repeating step 201 until the mixed powder is accumulatively treated by high-energy ball milling for 0.5 h;
步骤三、在充满惰性气体的手套箱中，将步骤二中经高能球磨处理后的混合粉体从真空球磨罐中取出放入不锈钢模具中，将不锈钢模具密封后从手套箱中取出，然后将不锈钢模具置于压片机上，在压片机的压力为9MPa的条件下将经高能球磨处理后的混合粉体压制处理2min，得到Fe(Se,Te)坯体；Step 3. In a glove box filled with inert gas, take the mixed powder processed by high-energy ball milling in step 2 out of the vacuum ball mill tank and put it into a stainless steel mold. After sealing the stainless steel mold, take it out of the glove box, and then put The stainless steel mold is placed on the tablet press, and the mixed powder after the high-energy ball milling treatment is pressed for 2 minutes under the condition that the pressure of the tablet press is 9MPa, to obtain a Fe(Se,Te) green body;
步骤四、在充满惰性气体的手套箱中，将步骤三中所述Fe(Se,Te)坯体从不锈钢模具中取出置于石英管中，将石英管密封后从手套箱中取出，然后将石英管置于烧结炉中，在烧结炉的温度为650℃条件下对Fe(Se,Te)坯体烧结处理16h，再以16℃/h的降温速率降至室温，得到Fe(Se,Te)超导材料；所述烧结处理在氩气气氛中进行。Step 4. In a glove box full of inert gas, the Fe(Se, Te) body described in step 3 is taken out from the stainless steel mold and placed in a quartz tube, and the quartz tube is sealed and taken out of the glove box, and then The quartz tube was placed in a sintering furnace, and the Fe(Se, Te) green body was sintered for 16 hours at a temperature of 650 °C in the sintering furnace, and then cooled to room temperature at a cooling rate of 16 °C/h to obtain Fe(Se, Te ) superconducting material; the sintering treatment is carried out in an argon atmosphere.
本实施例制备的Fe(Se,Te)主相为四方相Fe(Se,Te)结构，并且四方相Fe(Se,Te)的含量达到90vol％，本实施例制备的Fe(Se,Te)超导材料的超导转变温度(Tc)为8.1K，密度为5.02g/cm3，具有高密度以及良好的超导性能。The main phase of Fe(Se, Te) prepared in this example is a tetragonal phase Fe(Se, Te) structure, and the content of tetragonal phase Fe(Se, Te) reaches 90vol%. The Fe(Se, Te) prepared in this example The superconducting transition temperature (Tc) of the superconducting material is 8.1K, the density is 5.02g/cm 3 , and it has high density and good superconducting performance.
实施例6Example 6
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、在充满惰性气体的手套箱中，将混合粉体置于真空球磨罐中，然后将真空球磨罐密封后取出；所述混合粉体由摩尔比为1.1:0.2:0.8的铁粉、硒粉和碲粉混合而成；所述铁粉为还原铁粉，所述铁粉的质量纯度不低于99％，所述硒粉的质量纯度不低于99％，所述碲粉的质量纯度不低于99％；Step 1. In a glove box filled with an inert gas, place the mixed powder in a vacuum ball mill jar, then seal the vacuum ball mill jar and take it out; the mixed powder is composed of iron powder with a molar ratio of 1.1:0.2:0.8, Selenium powder and tellurium powder are mixed; the iron powder is reduced iron powder, the mass purity of the iron powder is not less than 99%, the mass purity of the selenium powder is not less than 99%, and the mass purity of the tellurium powder is Purity not less than 99%;
步骤二、将步骤一中装有混合粉体的真空球磨罐置于高能球磨机中进行高能球磨处理，具体过程为：Step 2. Place the vacuum ball milling tank containing the mixed powder in step 1 in a high-energy ball mill for high-energy ball milling. The specific process is:
步骤201、在高能球磨机的转速为1600r/min的条件下将混合粉体高能球磨处理25min，然后将真空球磨罐取出后浸泡于液氮中冷却；所述高能球磨处理的过程中混合粉体的温度不高于60℃，所述高能球磨处理的球料比为1:20；Step 201: Under the condition that the speed of the high-energy ball mill is 1600r/min, the mixed powder is subjected to high-energy ball milling for 25 minutes, and then the vacuum ball mill tank is taken out and soaked in liquid nitrogen to cool; during the process of the high-energy ball milling, the The temperature is not higher than 60°C, and the ball-to-material ratio of the high-energy ball milling treatment is 1:20;
步骤202、重复步骤201,直至将混合粉体累计高能球磨处理12h；Step 202, repeating step 201 until the mixed powder is accumulatively treated by high-energy ball milling for 12 hours;
步骤三、在充满惰性气体的手套箱中，将步骤二中经高能球磨处理后的混合粉体从真空球磨罐中取出放入不锈钢模具中，将不锈钢模具密封后从手套箱中取出，然后将不锈钢模具置于压片机上，在压片机的压力为5MPa的条件下将经高能球磨处理后的混合粉体压制处理15min，得到Fe(Se,Te)坯体；Step 3. In a glove box filled with inert gas, take the mixed powder processed by high-energy ball milling in step 2 out of the vacuum ball mill tank and put it into a stainless steel mold. After sealing the stainless steel mold, take it out of the glove box, and then put The stainless steel mold is placed on the tablet press, and under the condition that the pressure of the tablet press is 5MPa, the mixed powder after the high-energy ball milling treatment is pressed for 15 minutes to obtain the Fe(Se,Te) green body;
步骤四、在充满惰性气体的手套箱中，将步骤三中所述Fe(Se,Te)坯体从不锈钢模具中取出置于石英管中，将石英管密封后从手套箱中取出，然后将石英管置于烧结炉中，在烧结炉的温度为550℃条件下对Fe(Se,Te)坯体烧结处理20h，再以20℃/h的降温速率降至室温，得到Fe(Se,Te)超导材料；所述烧结处理在氩气气氛中进行。Step 4. In a glove box full of inert gas, the Fe(Se, Te) body described in step 3 is taken out from the stainless steel mold and placed in a quartz tube, and the quartz tube is sealed and taken out of the glove box, and then The quartz tube was placed in a sintering furnace, and the Fe(Se, Te) body was sintered for 20 hours at a temperature of 550 °C in the sintering furnace, and then cooled to room temperature at a rate of 20 °C/h to obtain Fe(Se, Te ) superconducting material; the sintering treatment is carried out in an argon atmosphere.
本实施例制备的Fe(Se,Te)主相为四方相Fe(Se,Te)结构，并且四方相Fe(Se,Te)的含量达到92vol％，本实施例制备的Fe(Se,Te)超导材料的超导转变温度(Tc)为10.8K，密度为5.66g/cm3，具有高密度以及良好的超导性能。The Fe(Se, Te) main phase prepared in this example is a tetragonal phase Fe(Se, Te) structure, and the content of the tetragonal phase Fe(Se, Te) reaches 92vol%. The Fe(Se, Te) prepared in this example The superconducting transition temperature (Tc) of the superconducting material is 10.8K, the density is 5.66g/cm 3 , and has high density and good superconducting performance.
实施例7Example 7
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、在充满惰性气体的手套箱中，将混合粉体置于真空球磨罐中，然后将真空球磨罐密封后取出；所述混合粉体由摩尔比为1.0:0.8:0.2的铁粉、硒粉和碲粉混合而成；所述铁粉为还原铁粉，所述铁粉的质量纯度不低于99％，所述硒粉的质量纯度不低于99％，所述碲粉的质量纯度不低于99％；Step 1. In a glove box filled with an inert gas, place the mixed powder in a vacuum ball mill jar, then seal the vacuum ball mill jar and take it out; the mixed powder is composed of iron powder with a molar ratio of 1.0:0.8:0.2, Selenium powder and tellurium powder are mixed; the iron powder is reduced iron powder, the mass purity of the iron powder is not less than 99%, the mass purity of the selenium powder is not less than 99%, and the mass purity of the tellurium powder is Purity not less than 99%;
步骤二、将步骤一中装有混合粉体的真空球磨罐置于高能球磨机中进行高能球磨处理，具体过程为：Step 2. Place the vacuum ball milling tank containing the mixed powder in step 1 in a high-energy ball mill for high-energy ball milling. The specific process is:
步骤201、在高能球磨机的转速为1650r/min的条件下将混合粉体高能球磨处理15min，然后将真空球磨罐取出后浸泡于液氮中冷却；所述高能球磨处理的过程中混合粉体的温度不高于60℃，所述高能球磨处理的球料比为1:1；Step 201: Under the condition that the speed of the high-energy ball mill is 1650r/min, the mixed powder is subjected to high-energy ball milling for 15 minutes, and then the vacuum ball mill tank is taken out and soaked in liquid nitrogen to cool; during the process of the high-energy ball milling, the The temperature is not higher than 60°C, and the ball-to-material ratio of the high-energy ball milling treatment is 1:1;
步骤202、重复步骤201,直至将混合粉体累计高能球磨处理10h；Step 202, repeating step 201 until the mixed powder is accumulatively treated by high-energy ball milling for 10 hours;
步骤三、在充满惰性气体的手套箱中，将步骤二中经高能球磨处理后的混合粉体从真空球磨罐中取出放入不锈钢模具中，将不锈钢模具密封后从手套箱中取出，然后将不锈钢模具置于压片机上，在压片机的压力为6MPa的条件下将经高能球磨处理后的混合粉体压制处理25min，得到Fe(Se,Te)坯体；Step 3. In a glove box filled with inert gas, take the mixed powder processed by high-energy ball milling in step 2 out of the vacuum ball mill tank and put it into a stainless steel mold. After sealing the stainless steel mold, take it out of the glove box, and then put The stainless steel mold is placed on the tablet press, and under the condition that the pressure of the tablet press is 6MPa, the mixed powder processed by high-energy ball milling is pressed for 25 minutes to obtain the Fe(Se,Te) green body;
步骤四、在充满惰性气体的手套箱中，将步骤三中所述Fe(Se,Te)坯体从不锈钢模具中取出置于石英管中，将石英管密封后从手套箱中取出，然后将石英管置于烧结炉中，在烧结炉的温度为680℃条件下对Fe(Se,Te)坯体烧结处理13h，再以25℃/h的降温速率降至室温，得到Fe(Se,Te)超导材料；所述烧结处理在氩气气氛中进行。Step 4. In a glove box full of inert gas, the Fe(Se, Te) body described in step 3 is taken out from the stainless steel mold and placed in a quartz tube, and the quartz tube is sealed and taken out of the glove box, and then The quartz tube was placed in a sintering furnace, and the Fe(Se, Te) blank was sintered for 13 hours at a temperature of 680 °C in the sintering furnace, and then cooled to room temperature at a cooling rate of 25 °C/h to obtain Fe(Se, Te ) superconducting material; the sintering treatment is carried out in an argon atmosphere.
本实施例制备的Fe(Se,Te)主相为四方相Fe(Se,Te)结构，并且四方相Fe(Se,Te)的含量达到93vol％，本实施例制备的Fe(Se,Te)超导材料的超导转变温度(Tc)为9.8K，密度为5.54g/cm3，具有高密度以及良好的超导性能。The main phase of Fe(Se, Te) prepared in this example is a tetragonal phase Fe(Se, Te) structure, and the content of tetragonal phase Fe(Se, Te) reaches 93vol%. The Fe(Se, Te) prepared in this example The superconducting transition temperature (Tc) of the superconducting material is 9.8K, and the density is 5.54g/cm 3 , which has high density and good superconducting performance.
实施例8Example 8
本实施例包括以下步骤：This embodiment includes the following steps:
步骤一、在充满惰性气体的手套箱中，将混合粉体置于真空球磨罐中，然后将真空球磨罐密封后取出；所述混合粉体由摩尔比为1.2:0.7:0.3的铁粉、硒粉和碲粉混合而成；所述铁粉为还原铁粉，所述铁粉的质量纯度不低于99％，所述硒粉的质量纯度不低于99％，所述碲粉的质量纯度不低于99％；Step 1. In a glove box filled with an inert gas, place the mixed powder in a vacuum ball mill jar, then seal the vacuum ball mill jar and take it out; the mixed powder is composed of iron powder with a molar ratio of 1.2:0.7:0.3, Selenium powder and tellurium powder are mixed; the iron powder is reduced iron powder, the mass purity of the iron powder is not less than 99%, the mass purity of the selenium powder is not less than 99%, and the mass purity of the tellurium powder is Purity not less than 99%;
步骤二、将步骤一中装有混合粉体的真空球磨罐置于高能球磨机中进行高能球磨处理，具体过程为：Step 2. Place the vacuum ball milling tank containing the mixed powder in step 1 in a high-energy ball mill for high-energy ball milling. The specific process is:
步骤201、在高能球磨机的转速为2000r/min的条件下将混合粉体高能球磨处理10min，然后将真空球磨罐取出后浸泡于液氮中冷却；所述高能球磨处理的过程中混合粉体的温度不高于60℃，所述高能球磨处理的球料比为1:4.5；Step 201: Under the condition that the rotating speed of the high-energy ball mill is 2000r/min, the mixed powder is subjected to high-energy ball milling for 10 minutes, and then the vacuum ball-milling tank is taken out and soaked in liquid nitrogen to cool; during the process of the high-energy ball milling, the The temperature is not higher than 60°C, and the ball-to-material ratio of the high-energy ball milling treatment is 1:4.5;
步骤202、重复步骤201,直至将混合粉体累计高能球磨处理4h；Step 202, repeating step 201 until the mixed powder is accumulatively treated by high-energy ball milling for 4 hours;
步骤三、在充满惰性气体的手套箱中，将步骤二中经高能球磨处理后的混合粉体从真空球磨罐中取出放入不锈钢模具中，将不锈钢模具密封后从手套箱中取出，然后将不锈钢模具置于压片机上，在压片机的压力为10MPa的条件下将经高能球磨处理后的混合粉体压制处理5min，得到Fe(Se,Te)坯体；Step 3. In a glove box filled with inert gas, take the mixed powder processed by high-energy ball milling in step 2 out of the vacuum ball mill tank and put it into a stainless steel mold. After sealing the stainless steel mold, take it out of the glove box, and then put The stainless steel mold is placed on the tablet press, and the mixed powder after the high-energy ball milling treatment is pressed for 5 minutes under the condition that the pressure of the tablet press is 10 MPa, to obtain a Fe(Se,Te) green body;
步骤四、在充满惰性气体的手套箱中，将步骤三中所述Fe(Se,Te)坯体从不锈钢模具中取出置于石英管中，将石英管密封后从手套箱中取出，然后将石英管置于烧结炉中，在烧结炉的温度为620℃条件下对Fe(Se,Te)坯体烧结处理18h，再以15℃/h的降温速率降至室温，得到Fe(Se,Te)超导材料；所述烧结处理在氩气气氛中进行。Step 4. In a glove box full of inert gas, the Fe(Se, Te) body described in step 3 is taken out from the stainless steel mold and placed in a quartz tube, and the quartz tube is sealed and taken out of the glove box, and then The quartz tube was placed in a sintering furnace, and the Fe(Se, Te) green body was sintered for 18 hours at a temperature of 620 °C in the sintering furnace, and then cooled to room temperature at a cooling rate of 15 °C/h to obtain Fe(Se, Te ) superconducting material; the sintering treatment is carried out in an argon atmosphere.
本实施例制备的Fe(Se,Te)主相为四方相Fe(Se,Te)结构，并且四方相Fe(Se,Te)的含量达到93vol％，本实施例制备的Fe(Se,Te)超导材料的超导转变温度(Tc)为8.9K，密度为5.33g/cm3，具有高密度以及良好的超导性能。The main phase of Fe(Se, Te) prepared in this example is a tetragonal phase Fe(Se, Te) structure, and the content of tetragonal phase Fe(Se, Te) reaches 93vol%. The Fe(Se, Te) prepared in this example The superconducting transition temperature (Tc) of the superconducting material is 8.9K, and the density is 5.33g/cm 3 , which has high density and good superconducting performance.
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制，凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效结构变化，均仍属于本发明技术方案的保护范围内。The above are only preferred embodiments of the present invention, and do not limit the present invention in any way. All simple modifications, changes and equivalent structural changes made to the above embodiments according to the technical essence of the present invention still belong to the technical aspects of the present invention. within the scope of protection of the scheme.
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