CN101386529A - Method for preparing Fe-base compound superconductor - Google Patents
Method for preparing Fe-base compound superconductor Download PDFInfo
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- CN101386529A CN101386529A CNA2008102241789A CN200810224178A CN101386529A CN 101386529 A CN101386529 A CN 101386529A CN A2008102241789 A CNA2008102241789 A CN A2008102241789A CN 200810224178 A CN200810224178 A CN 200810224178A CN 101386529 A CN101386529 A CN 101386529A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a method for preparing an iron-based compound superconductor, which comprises the following steps: (1) evenly mixing raw material powder which is prepared according to a chemical formula of ReMPnO1-xFx, ReM1-xTmxPnO or Ae1-xAxM2Pn2, and filling the raw material powder into a metal tube, tamping the powder completely, and closing two ends of the metal tube; (2) swaging, drawing and rolling the metal tube according to the pass deformation of between 5 and 20 percent; and (3) placing the metal tube which is processed through step 2 in a high-temperature heating furnace, vacuumizing until the pressure is between 10<-2> and 10<-5> Pa at room temperature, introducing argon into the metal tube, insulating the metal tube for 5 to 100 hours at a temperature of between 700 and 1,500 DEG C, and peeling the metal sleeve to obtain the iron-based compound novel superconductor after the high-temperature furnace is cooled to room temperature. Compared with the prior method for preparing quartz glass in two steps, the method has the advantages of effective bursting prevention, safety and reliability, one-step completion for sintering process, simple process and high production efficiency; and the prepared iron-based compound has high density and excellent superconductive performance.
Description
Technical field
The present invention relates to a kind of preparation method of Fe-base compound superconducting material.
Background technology
The Fe-base compound superconducting material is a kind of compound superconductive of finding recently.The Kamihara Y.et al. report that is Japan has at first been found new high-temperature superconductor LaO
1-xF
xFeAs (x=0.05-0.12), its transition temperature are 26K[Iron-basedlayered superconductor LaO
1-xF
xFeAs (x=0.05-0.12) with T
c=26 K.J.Am.Chem.Sco.130,3296-3297 (2008)], use other rare earth elements (Ce, Pr, Nd, Sm, Gd) that La is replaced subsequently, its the highest superconducting transition temperature has reached 55K, this is the novel high temperature superconducting materia that copper removal oxygen compound high temperature superconducting materia first kind of critical transition temperature in addition surpasses 40K, and this performance and superconduction mechanism for the researching high-temperature superconducting material provides more opportunity.In addition, Theoretical Calculation shows the upper critical field of Fe-base compound superconducting material and irreversible all very high, and has bigger coherence length, these show that fully the Fe-base compound superconducting material has good application prospects, so the preparation of Fe-base compound superconducting material is subjected to international extensive concern.Preparation about the Fe-base compound superconducting material mainly is silica glass method preparation in two steps at present, process complexity and cost are higher, what is more important is owing to contain poisonous element, and silica tube explosion easily in the process of heating, these all exist serious potential safety hazard.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art adopting quartz glass pipe, propose a kind of preparation method of new Fe-base compound high-temperature superconductor.
The present invention selects metal tube for use, comprises pure metal pipe, composite metal pipe or compo pipe.Making material chosen from Fe, copper, soft steel, stainless steel, chromium, vanadium, manganese, titanium, zirconium, molybdenum, nickel, niobium, tungsten, hafnium or the tantalum of metal tube, composite metal pipe or compo pipe.
Concrete preparation process of the present invention is:
(1) will be according to ReMPnO
1-xF
xOr ReM
1-xTm
xPnO or Ae
1-xA
xM
2Pn
2In the raw material powder of a kind of chemical formula preparation mix after, the metal tube of packing into, fully compacting, the two ends of closed metal pipe then;
(2) with metal tube according to certain pass deformation (5%-20%) swage, drawing, operation such as rolling processing;
(3) will place high-temperature heater through the metal tube of step 2 processing gained, under room temperature, be evacuated to 10
-2-10
-5Handkerchief charges into argon gas afterwards, is incubated 5-100 hour then under 700-1500 ℃ temperature, treats that at last High Temperature Furnaces Heating Apparatus is cooled to room temperature, and strip off metal jacket obtains Fe-base compound new superconductive body.
Described chemical formula ReMPnO
1-xF
x, ReM
1-xTm
xPnO or Ae
1-xA
xM
2Pn
2: Re is one or more elements that are selected among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, the Y; M is a kind of element that is selected among Fe, Co, Ni, the Ru; Tm is a kind of element among Co, Ni, Mn, the Zn; Pn is a kind of element among As, P, the Sb; Ae is a kind of element among Ca, Sr, Ba, the Eu; A is a kind of element among Li, Na, K, Rb, the Cs; X=0-0.50;
Preparing Fe-base compound new superconductive body with the silica glass method of fractional steps that adopts usually now compares, advantage of the present invention is, at first adopt metal tube to prepare superconductor, the fusing point of metal is higher, can under higher temperature, carry out solid state reaction, thus the softening problem when avoiding the long-time heat of quartz glass tube.Secondly, metal tube mostly has good processing characteristics, helps initial raw material powder is fully broken, compacting in the course of processing, makes the Fe-base compound grain refining of final formation, the crystal grain connectivity of efficient hardening Fe-base compound, thus the density of superconductor improved.Once more, novel Fe-base compound superconductor comprises deleterious phosphorus family element, and the general evaporating point of phosphorus family element is very low, if adopting quartz glass control when being equipped with when high temperature sintering because in the pipe vapour pressure very high, occur Glass tubing explosion phenomenon easily, cause and wound and consequence such as toxic gas leakage.And adopt metal tube can avoid above problem fully, safe and reliable.In addition, the present invention can realize the disposable Fast Sintering of Fe-base compound superconductor, and is convenient and simple and effective, and the preparation time of having avoided the present substep sintering method that generally adopts to bring is long, and cost is than problems such as height.
Embodiment:
The concrete preparation process of the present invention is:
(1) will be according to ReMPnO
1-xF
xOr ReM
1-xTm
xPnO or Ae
1-xA
xM
2Pn
2In the raw material powder of a kind of chemical formula preparation mix after, the metal tube of packing into, fully compacting, the two ends of closed metal pipe then;
(2) with metal tube according to certain pass deformation (5%-20%) swage, drawing, operation such as rolling processing;
(3) will place high-temperature heater through the metal tube of step 2 processing gained, under room temperature, be evacuated to 10
-2-10
-5Handkerchief charges into argon gas afterwards, is incubated 5-100 hour then under 700-1500 ℃ temperature, treats that at last High Temperature Furnaces Heating Apparatus is cooled to room temperature, and strip off metal jacket obtains Fe-base compound new superconductive body.
Above-described chemical formula ReMPnO
1-xF
x, ReM
1-xTm
xPnO or Ae
1-xA
xM
2Pn
2: Re is one or more elements that are selected among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, the Y; M is a kind of element that is selected among Fe, Co, Ni, the Ru; Tm is a kind of element among Co, Ni, Mn, the Zn; Pn is a kind of element among As, P, the Sb; Ae is a kind of element among Ca, Sr, Ba, the Eu; A is a kind of element among Li, Na, K, Rb, the Cs; X=0-0.50;
Embodiment 1
At first according to chemical formula LaO
0.9F
0.1The La of weighing shown in FeAs powder 2.35g, Fe powder 0.39g, Fe
2O
3Powder 0.84g, LaF
3Powder 0.11g, As powder 1.31g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, the powder after mixing is packed in the long iron pipe of 10cm into iron pipe internal diameter 5mm, external diameter 8mm makes powder reach substantial, tight in iron pipe, seals the iron pipe two ends then.Then this iron pipe that mixed powder is housed is swaged to 4mm by 8% pass deformation.Iron pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-2Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 40 hours then, be cooled to room temperature with annealing furnace at last, just make the LaO that superconducting transition temperature is 26K
0.9F
0.1The FeAs superconductor.
Embodiment 2
At first according to chemical formula Eu
0.7Na
0.3Fe
2As
2Shown in weighing Eu powder 0.71g, Fe powder 0.74g, As powder 1.00g and Na fritter 0.05g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long niobium pipe of 5cm, bore 10mm, external diameter 12mm makes powder reach substantial, tight in the niobium pipe, seals niobium pipe two ends then.Then this niobium pipe that mixed powder is housed is drawn to 6mm by 8% pass deformation, the niobium pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, slowly be warming up to 850 ℃ of insulations 35 hours then, be cooled to room temperature with stove at last, just make the Eu that transition temperature is 35K
0.7Na
0.3Fe
2As
2Superconductor.
Embodiment 3
At first according to the powder of weighing Ce shown in chemical formula CeOFeAs 2.77g, Fe powder 0.51g, Fe
2O
3Powder 0.93g, As powder 1.56g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long stainless steel tube of 6cm into bore 8mm, external diameter 12mm, make powder in stainless steel tube, reach substantial, tight, seal the stainless steel tube two ends then.Then this stainless steel tube that mixed powder is housed is swaged to 3mm by 5% pass deformation, the stainless steel tube after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-4Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1150 ℃ of insulations 50 hours then, be cooled to room temperature with stove at last, just make the CeOFeAs superconductor.
Embodiment 4
At first according to chemical formula Ba
0.5K
0.5Fe
2As
2Shown in weighing Ba powder 1.28g, Fe powder 2.08g, As powder 2.78g and K fritter 0.36g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long zirconium pipe of 5cm, bore 10mm, external diameter 12mm makes powder reach substantial, tight in the zirconium pipe, seals zirconium pipe two ends then.Then this zirconium pipe that mixed powder is housed is swaged to 6mm by 10% pass deformation, the zirconium pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-5Charge into high-purity argon gas after the vacuum tightness of handkerchief, slowly be warming up to 850 ℃ of insulations 35 hours then, be cooled to room temperature with stove at last, just make the Ba that transition temperature is 38K
0.5K
0.5Fe
2As
2Superconductor.
Embodiment 5
At first according to chemical formula SmO
0.7F
0.3The Sm of weighing shown in FeAs powder 5.45g, Fe powder 1.20g, Fe
2O
3Powder 1.50g, SmF
3Powder 0.83g, As powder 3.02g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, the powder after mixing is packed in the long nickel pipe of 8cm into bore 16mm, external diameter 20mm makes powder reach substantial, tight in the nickel pipe, seals nickel pipe two ends then.Then this nickel pipe that mixed powder is housed is swaged to 5mm by 20% pass deformation, the nickel pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1160 ℃ of insulations 40 hours then, be cooled to room temperature with stove at last, just make SmO
0.7F
0.3The FeAs superconductor, superconducting transition temperature is not less than 50K after measured, and upper critical field is up to 120T (T=0K).
Embodiment 6
At first according to chemical formula NdO
0.89F
0.11The Nd of weighing shown in NiAs powder 1.91g, Ni powder 0.31g, NiO powder 0.65g, NdF
3Powder 0.10g, As powder 1.03g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long niobium zirconium alloy pipe of 10cm into bore 3mm, external diameter 5mm, make powder in the nb-zr tube compo pipe, reach substantial, tight, seal the nb-zr tube two ends then.Then this nb-zr tube compo pipe that mixed powder is housed is swaged to 4mm by 5% pass deformation, the nb-zr tube compo pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1300 ℃ of insulations 60 hours then, be cooled to room temperature with stove at last, just make NdO
0.89F
0.11The NiAs superconductor.
Embodiment 7
At first according to chemical formula CaFe
2As
2Shown in weighing Ca powder 0.34g, Fe powder 1.91g, As powder 2.56g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long hafnium pipe of 5cm, bore 10mm, external diameter 12mm makes powder reach substantial, tight in pipe, seals two ends then.Then this hafnium pipe that mixed powder is housed is swaged by 12% pass deformation and be drawn to 6mm, the hafnium pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, slowly be warming up to 850 ℃ of insulations 35 hours then, be cooled to room temperature with stove at last, just make CaFe
2As
2Superconductor.
Embodiment 8
At first according to chemical formula PrO
0.89F
0.11The Pr of weighing shown in CoAs powder 4.89g, Co powder 0.72g, Co
2O
3Powder 1.64g, FeF
3Powder 0.14g, As powder 2.60g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, the powder after mixing is packed in the long vanadium pipe of 10cm into bore 10mm, external diameter 13mm makes powder reach substantial, tight in the vanadium pipe, seals vanadium pipe two ends then.Then this vanadium pipe that mixed powder is housed is proceeded to 8mm by 15% pass deformation, then the thick metal strip of the rolling 4mm of 8% pass deformation.Metal strip after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-4Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 40 hours then, be cooled to room temperature with stove at last, just make the PrO that superconducting transition temperature is not less than 45K
0.89F
0.11The CoAs superconductor.
Embodiment 9
At first according to chemical formula GdO
0.83F
0.17The Gd of weighing shown in FeAs powder 3.90g, Fe powder 0.66g, Fe
2O
3Powder 1.16g, GdF
3Powder 0.32g, As powder 1.97g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, the powder after mixing is packed in the long aluminum pipe of 15cm into bore 6mm, external diameter 9mm makes powder reach substantial, tight in the molybdenum pipe, seals molybdenum pipe two ends then.Then this molybdenum pipe that mixed powder is housed is drawn to 4mm by 8% pass deformation, the molybdenum pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-2Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 50 hours then, be cooled to room temperature with stove at last, just make GdO
0.83F
0.17FeAs new superconductive body.
Embodiment 10
At first according to chemical formula TbO
0.95F
0.05The Tb of weighing shown in RuAs powder 3.12g, Ru powder 0.38g, RuO
2Powder 0.99g, TbF
3Powder 0.04g, As powder 1.47g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, the powder after mixing is packed in the long tungsten pipe of 10cm into bore 4mm, external diameter 7mm makes powder reach substantial, tight in the tungsten pipe, seals tungsten pipe two ends then.Then this tungsten pipe that mixed powder is housed is swaged to 4mm by 5% pass deformation, the tungsten pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-5Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1500 ℃ of insulations 80 hours then, be cooled to room temperature with stove at last, just make TbO
0.95F
0.05RuAs new superconductive body.
Embodiment 11
At first according to chemical formula SmFe
0.85Co
0.15The Sm of weighing shown in AsO powder 6.06g, Fe powder 0.75g, Co
2O
3Powder 0.50g, Fe
2O
3Powder 1.66g, As powder 3.02g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, the powder after mixing is packed in the long tantalum pipe of 8cm into bore 12mm, external diameter 15mm makes powder reach substantial, tight in the tantalum pipe, seals two ends then.Then this tantalum pipe that mixed powder is housed is drawn to 10mm by 5% pass deformation, rolling by 5% pass deformation then is metal strip behind the 5mm.Metal strip after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into argon gas after the vacuum tightness of handkerchief, be warming up to 1160 ℃ of insulations 40 hours then, be cooled to room temperature with stove at last, just make SmFe
0.85Co
0.15The AsO superconductor, superconducting transition temperature is 15K after measured.
Embodiment 12
At first according to chemical formula D yFe
0.95Ni
0.05The Dy of weighing shown in AsO powder 4.72g, Fe powder 0.96g, Fe
2O
3Powder 1.20g, Ni powder 0.91g, As powder 2.42g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long titanium pipe of 12cm, bore 8mm, external diameter 11mm makes powder reach substantial, tight in the titanium pipe, seals titanium pipe two ends then.Then this titanium pipe that mixed powder is housed is swaged to 4mm by 12% pass deformation, the titanium pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1300 ℃ of insulations 60 hours then, be cooled to room temperature with stove at last, just make DyFe
0.95Ni
0.05The AsO superconductor.
Embodiment 13
At first according to chemical formula HoO
0.5F
0.5The Ho of weighing shown in FeAs powder 3.01g, Fe powder 0.46g, Fe
2O
3Powder 0.67g, HoF
3Powder 0.31g, As powder 1.44g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long Low Carbon Steel Pipe of 9cm into bore 6mm, external diameter 8mm, make powder in Low Carbon Steel Pipe, reach substantial, tight, seal the Low Carbon Steel Pipe two ends then.And with the Low Carbon Steel Pipe copper pipe of packing into, the copper pipe internal diameter is 8.2mm, and external diameter is 10mm, then this copper pipe that mixed powder is housed is swaged to 4mm by 8% pass deformation, metal tube after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-5Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1050 ℃ of insulations 55 hours then, be cooled to room temperature with stove at last, just make HoO
0.5F
0.5FeAs new superconductive body.
Embodiment 14
At first according to chemical formula Sr
0.5Rb
0.5Fe
2As
2Shown in weighing Sr powder 0.67g, Fe powder 1.72g, the fritter 0.30g of As powder 2.31g and Rb, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long copper pipe of 6cm, bore 6mm, external diameter 8mm makes powder reach substantial, tight in copper pipe, seals the copper pipe two ends then.Then this copper pipe that mixed powder is housed is swaged to 5mm by 5% pass deformation, the copper pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 700 ℃ of insulations 55 hours then, be cooled to room temperature with stove at last, just make Sr
0.5Rb
0.5Fe
2As
2The new superconductive body.
Embodiment 15
At first according to chemical formula YbFe
0.5Zn
0.5The Yb of weighing shown in AsO powder 2.57g, Fe powder 0.28g, Fe
2O
3Powder 0.71g, Zn powder 0.28g, As powder 1.17g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long chromium pipe of 5cm, bore 6mm, external diameter 8mm makes powder reach substantial, tight in the chromium pipe, seals chromium pipe two ends then.Then this chromium pipe that mixed powder is housed is swaged to 4mm by 10% pass deformation, the metal tube after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 55 hours then, be cooled to room temperature with stove at last, just make YbFe
0.5Zn
0.5AsO new superconductive body.
Embodiment 16
At first according to chemical formula La
0.5Sm
0.5O
0.85F
0.15The Sm of weighing shown in FeAs powder 1.85g, La powder 1.90g, Fe powder 0.66g, Fe
2O
3Powder 1.24g, SmF
3Powder 0.28g, As powder 2.05g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, the powder after mixing is packed in the long manganese pipe of 10cm into bore 6mm, external diameter 8mm makes powder reach substantial, tight in the manganese pipe, seals manganese pipe two ends then.Then this manganese pipe that mixed powder is housed is drawn to 4mm by 15% pass deformation, the manganese pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1150 ℃ of insulations 100 hours then, be cooled to room temperature with stove at last, just make La
0.5Sm
0.5O
0.85F
0.15FeAs new superconductive body.
Embodiment 17
At first according to chemical formula ErO
0.5F
0.5The Er of weighing shown in FeP powder 2.36g, Fe powder 0.39g, Fe
2O
3Powder 0.84g, ErF
3Powder 0.12g, P powder 1.31g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long ferrochrome exothermic pipe of 10cm into bore 5mm, external diameter 8mm, make powder in the siderochrome pipe, reach substantial, tight, seal the compo pipe two ends then.Then this ferrochrome exothermic pipe that mixed powder is housed is swaged to 4mm by 8% pass deformation.Compo pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-2Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 40 hours then, be cooled to room temperature with annealing furnace at last, just make ErO
0.5F
0.5The FeP superconductor.
Embodiment 18
At first according to chemical formula Eu
0.6Na
0.4Fe
2As
2Shown in weighing Eu powder 0.60g, Fe powder 0.74g, As powder 1.00g and Na fritter 0.06g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long ferromolybdenum pipe of 5cm, bore 10mm, external diameter 12mm makes powder reach substantial, tight in pipe, seals iron molybdenum pipe two ends then.Then this iron molybdenum pipe that mixed powder is housed is drawn to 6mm by 8% pass deformation, the iron molybdenum pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, slowly be warming up to 850 ℃ of insulations 35 hours then, be cooled to room temperature with stove at last, just make the Eu that transition temperature is 35K
0.6Na
0.4Fe
2As
2Superconductor.
Embodiment 19
At first according to chemical formula TmFe
0.8Mn
0.2The Tm of weighing shown in AsO powder 2.77g, Fe powder 0.51g, Fe
2O
3Powder 0.93g, Mn powder 0.22g, As powder 1.56g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long ferrotungsten pipe of 6cm, bore 8mm, external diameter 12mm makes powder reach substantial, tight in the ferrotungsten pipe, seals ferrotungsten pipe two ends then.Then this ferrotungsten pipe that mixed powder is housed is swaged to 3mm by 5% pass deformation, the ferrotungsten pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-4Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1150 ℃ of insulations 50 hours then, be cooled to room temperature with stove at last, just make TmFe
0.8Mn
0.2The AsO superconductor.
Embodiment 20
At first according to chemical formula Ba
0.9K
0.1Fe
2As
2Shown in weighing Ba powder 1.28g, Fe powder 2.08g, As powder 2.78g and K fritter 0.36g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long iron-nickel alloy pipe of 5cm, bore 10mm, external diameter 12mm makes powder reach substantial, tight in iron-nickel alloy pipe, seals the iron-nickel alloy pipe two ends then.Then this iron-nickel alloy pipe that mixed powder is housed is swaged to 6mm by 10% pass deformation, the iron-nickel alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-5Charge into high-purity argon gas after the vacuum tightness of handkerchief, slowly be warming up to 850 ℃ of insulations 35 hours then, be cooled to room temperature with stove at last, just make Ba
0.9K
0.1Fe
2As
2Superconductor.
Embodiment 21
At first according to chemical formula LuO
0.7F
0.3The Lu of weighing shown in FeSb powder 5.45g, Fe powder 1.20g, Fe
2O
3Powder 1.50g, LuF
3Powder 0.83g, Sb powder 3.02g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long ferrovanadium pipe of 8cm into bore 16mm, external diameter 20mm, make powder in the ferrovanadium pipe, reach substantial, tight, seal ferrovanadium pipe two ends then.Then this ferrovanadium pipe that mixed powder is housed is swaged to 5mm by 20% pass deformation, the ferrovanadium pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1160 ℃ of insulations 40 hours then, be cooled to room temperature with stove at last, just make LuO
0.7F
0.3The FeSb superconductor.
Embodiment 22
At first according to chemical formula YO
0.5F
0.5The Nd of weighing shown in FeAs powder 1.91g, Fe powder 0.31g, Fe
2O
3Powder 0.65g, YF
3Powder 0.30g, As powder 1.03g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long ferroniobium pipe of 10cm into bore 3mm, external diameter 5mm, make powder in the ferroniobium pipe, reach substantial, tight, seal ferroniobium pipe two ends then.Then this ferroniobium pipe that mixed powder is housed is swaged to 4mm by 5% pass deformation, the ferroniobium pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1300 ℃ of insulations 60 hours then, be cooled to room temperature with stove at last, just make YO
0.5F
0.5The FeAs superconductor.
Embodiment 23
At first according to chemical formula Ca
0.5Li
0.5Fe
2As
2Shown in weighing Ca powder 0.34g, Fe powder 1.91g, As powder 2.56g and Li fritter 0.20g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long Ferro Manganese pipe of 5cm, bore 10mm, external diameter 12mm makes powder reach substantial, tight in the Ferro Manganese pipe, seals Ferro Manganese pipe two ends then.Then this Ferro Manganese pipe that mixed powder is housed is swaged by 12% pass deformation and be drawn to 6mm, the Ferro Manganese pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, slowly be warming up to 850 ℃ of insulations 35 hours then, be cooled to room temperature with stove at last, just make the Ca that transition temperature is 20K
0.5Li
0.5Fe
2As
2Superconductor.
Embodiment 24
At first according to chemical formula La
0.5Pr
0.5O
0.89F
0.11The La of weighing shown in FeAs powder 2.44g, Pr powder 2.45g, Fe powder 0.72g, Fe
2O
3Powder 1.64g, FeF
3Powder 0.14g, As powder 2.60g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long ferrotianium pipe of 10cm into bore 10mm, external diameter 13mm, make powder in the ferrotianium pipe, reach substantial, tight, seal ferrotianium pipe two ends then.Then this ferrotianium pipe that mixed powder is housed is proceeded to 8mm by 15% pass deformation, then the thick metal strip of the rolling 4mm of 8% pass deformation.Metal strip after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-4Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 40 hours then, be cooled to room temperature with stove at last, just make the La that superconducting transition temperature is not less than 45K
0.5Pr
0.5O
0.89F
0.11The FeAs superconductor.
Embodiment 25
At first according to chemical formula La
0.5Gd
0.5O
0.83F
0.17The La of weighing shown in FeAs powder 2.10g, Gd powder 1.80g, Fe powder 0.66g, Fe
2O
3Powder 1.16g, GdF
3Powder 0.32g, As powder 1.97g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long ferrozirconium pipe of 15cm into bore 6mm, external diameter 9mm, make powder in the ferrozirconium pipe, reach substantial, tight, seal ferrozirconium pipe two ends then.Then this ferrozirconium pipe that mixed powder is housed is drawn to 4mm by 8% pass deformation, the ferrozirconium pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-2Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 50 hours then, be cooled to room temperature with stove at last, just make La
0.5Gd
0.5O
0.83F
0.17FeAs new superconductive body.
Embodiment 26
At first according to chemical formula La
0.5Tb
0.5O
0.95F
0.05The La of weighing shown in FeAs powder 1.52g, Tb powder 1.60g, Fe powder 0.38g, Fe
2O
3Powder 0.99g, FeF
3Powder 0.04g, As powder 1.47g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long iron tantalum alloy pipe of 10cm into bore 4mm, external diameter 7mm, make powder in iron tantalum alloy pipe, reach substantial, tight, seal iron tantalum alloy pipe two ends then.Then this iron tantalum alloy pipe that mixed powder is housed is swaged to 4mm by 5% pass deformation, the iron tantalum alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-5Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1500 ℃ of insulations 80 hours then, be cooled to room temperature with stove at last, just make La
0.5Tb
0.5O
0.95F
0.05FeAs new superconductive body.
Embodiment 27
At first according to chemical formula SmFe
0.8Zn
0.2The Sm of weighing shown in AsO powder 6.06g, Fe powder 0.75g, ZnO powder 0.58g, Fe
2O
3Powder 1.62g, As powder 3.02g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long iron hafnium alloy pipe of 8cm into bore 12mm, external diameter 15mm, make powder in iron hafnium alloy pipe, reach substantial, tight, seal iron hafnium alloy pipe two ends then.Then this iron hafnium alloy pipe that mixed powder is housed is drawn to 10mm by 5% pass deformation, rolling by 5% pass deformation then is metal strip behind the 5mm.Metal strip after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into argon gas after the vacuum tightness of handkerchief, be warming up to 1160 ℃ of insulations 40 hours then, be cooled to room temperature with stove at last, just make SmFe
0.8Zn
0.2The AsO superconductor.
Embodiment 28
At first according to chemical formula La
0.5Dy
0.5O
0.7F
0.3The La of weighing shown in FeAs powder 2.30g, Dy powder 2.32g, Fe powder 0.96g, Fe
2O
3Powder 1.20g, DyF
3Powder 0.71g, As powder 2.42g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long nickel tungsten pipe of 12cm into bore 8mm, external diameter 11mm, make powder in the nickel tungsten pipe, reach substantial, tight, seal nickel tungsten pipe two ends then.Then this nickel tungsten pipe that mixed powder is housed is swaged to 4mm by 12% pass deformation, the nickel tungsten pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1300 ℃ of insulations 60 hours then, be cooled to room temperature with stove at last, just make La
0.5Dy
0.5O
0.7F
0.3The FeAs superconductor.
Embodiment 29
At first according to chemical formula La
0.7Ho
0.3O
0.85F
0.15The La of weighing shown in FeAs powder 1.81g, Ho powder 1.21g, Fe powder 0.46g, Fe
2O
3Powder 0.87g, HoF
3Powder 0.21g, As powder 1.44g, and place the argon atmospher glove box to grind this powder, make it abundant
Uniform mixing is packed the powder after mixing in the long nickel-molybdenum alloy pipe of 9cm into, bore 6mm, and external diameter 8mm makes powder reach substantial, tight in the nickel-molybdenum alloy pipe, seals nickel-molybdenum alloy pipe two ends then.And with the nickel-molybdenum alloy pipe niobium pipe of packing into, the niobium bore is 8.2mm, and external diameter is 10mm, then this niobium pipe that mixed powder is housed is swaged to 4mm by 8% pass deformation, metal tube after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-5Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1050 ℃ of insulations 55 hours then, be cooled to room temperature with stove at last, just make La
0.7Ho
0.3O
0.85F
0.15FeAs new superconductive body.
Embodiment 30
At first according to chemical formula Sr
0.6Cs
0.4Fe
2As
2Shown in weighing Sr powder 0.67g, Fe powder 1.72g, the fritter 0.28g of As powder 2.31g and Cs, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long nickel hafnium alloy pipe of 6cm, bore 6mm, external diameter 8mm makes powder reach substantial, tight in nickel hafnium alloy pipe, seals nickel hafnium alloy pipe two ends then.Then this nickel hafnium alloy pipe that mixed powder is housed is swaged to 5mm by 5% pass deformation, the nickel hafnium alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 700 ℃ of insulations 55 hours then, be cooled to room temperature with stove at last, just make Sr
0.6Cs
0.4Fe
2As
2The new superconductive body.
Embodiment 31
At first according to chemical formula La
0.8Yb
0.2The La of weighing shown in OFeAs powder 1.85g, Yb powder 0.82g, Fe powder 0.38g, Fe
2O
3Powder 0.71g, As powder 1.17g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, the powder after mixing is packed in the long Ni-Ti alloy pipe of 5cm into bore 6mm, external diameter 8mm makes powder reach substantial, tight in pipe, then the sealed tube two ends.Then this Ni-Ti alloy pipe that mixed powder is housed is swaged to 4mm by 10% pass deformation, the Ni-Ti alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 55 hours then, be cooled to room temperature with stove at last, just make La
0.8Yb
0.2OFeAs new superconductive body.
Embodiment 32
At first according to chemical formula La
0.5Ce
0.5O
0.85F
0.15The Ce of weighing shown in FeAs powder 1.85g, La powder 1.90g, Fe powder 0.66g, Fe
2O
3Powder 1.24g, LaF
3Powder 0.28g, As powder 2.05g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long ickel-niobium alloy pipe of 10cm into bore 6mm, external diameter gmm, make powder in the ickel-niobium alloy pipe, reach substantial, tight, then the sealed tube two ends.Then this ickel-niobium alloy pipe that mixed powder is housed is drawn to 4mm by 15% pass deformation, the ickel-niobium alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1150 ℃ of insulations 100 hours then, be cooled to room temperature with stove at last, just make La
0.5Ce
0.5O
0.85F
0.15FeAs new superconductive body.
Embodiment 33
At first according to chemical formula Sm
0.5Ce
0.5O
0.9F
0.1The Sm of weighing shown in FeAs powder 1.15g, Ce powder 1.20g, Fe powder 0.39g, Fe
2O
3Powder 0.84g, SmF
3Powder 0.11g, As powder 1.31g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long nickel tantalum alloy pipe of 10cm into bore 5mm, external diameter 8mm, make powder in the nickel tantalum alloy pipe, reach substantial, tight, seal nickel tantalum alloy pipe two ends then.Then this nickel tantalum alloy pipe that mixed powder is housed is swaged to 4mm by 8% pass deformation.Nickel tantalum alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-2Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 40 hours then, be cooled to room temperature with annealing furnace at last, just make the Sm that superconducting transition temperature is 26K
0.5Ce
0.5O
0.9F
0.1The FeAs superconductor.
Embodiment 34
At first according to chemical formula Eu
0.7K
0.3Fe
2As
2Shown in weighing Eu powder 0.71g, Fe powder 0.74g, As powder 1.00g and K fritter 0.05g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long nickel-vanadium alloy pipe of 5cm, bore 10mm, external diameter 12mm makes powder reach substantial, tight in the nickel-vanadium alloy pipe, seals nickel-vanadium alloy pipe two ends then.Then this nickel-vanadium alloy pipe that mixed powder is housed is drawn to 6mm by 8% pass deformation, the nickel-vanadium alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, slowly be warming up to 850 ℃ of insulations 35 hours then, be cooled to room temperature with stove at last, just make the Eu that transition temperature is 35K
0.7K
0.3Fe
2As
2Superconductor.
Embodiment 35
At first according to chemical formula Pr
0.5Ce
0.5O
0.84F
0.16The Ce of weighing shown in FeAs powder 1.41g, Pr powder 1.38g, Fe powder 0.51g, Fe
2O
3Powder 0.93g, CeF
3Powder 0.22g, As powder 1.56g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long Zirconium-nickel alloy pipe of 6cm into bore 8mm, external diameter 12mm, make powder in the Zirconium-nickel alloy pipe, reach substantial, tight, seal Zirconium-nickel alloy pipe two ends then.Then this Zirconium-nickel alloy pipe that mixed powder is housed is swaged to 3mm by 5% pass deformation, the Zirconium-nickel alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-4Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1150 ℃ of insulations 50 hours then, be cooled to room temperature with stove at last, just make Pr
0.5Ce
0.5O
84F
0.16The FeAs superconductor.
Embodiment 36
At first according to chemical formula Ba
0.7K
0.3Fe
2As
2Shown in weighing Ba powder 1.38g, Fe powder 2.08g, As powder 2.78g and K fritter 0.26g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long Magno pipe of 5cm, bore 10mm, external diameter 12mm makes powder reach substantial, tight in the Magno pipe, seals Magno pipe two ends then.Then this Magno pipe that mixed powder is housed is swaged to 6mm by 10% pass deformation, the Magno pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-5Charge into high-purity argon gas after the vacuum tightness of handkerchief, slowly be warming up to 850 ℃ of insulations 35 hours then, be cooled to room temperature with stove at last, just make the Ba that transition temperature is 38K
0.7K
0.3Fe
2As
2Superconductor.
Embodiment 37
At first according to chemical formula Sm
0.5Pr
0.5O
0.7F
0.3The Sm of weighing shown in FeAs powder 2.82g, Pr powder 2.65g, Fe powder 1.20g, Fe
2O
3Powder 1.50g, SmF
3Powder 0.83g, As powder 3.02g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long nichrome pipe of 8cm into bore 16mm, external diameter 20mm, make powder in pipe, reach substantial, tight, seal nichrome pipe two ends then.Then this nichrome pipe that mixed powder is housed is swaged to 5mm by 20% pass deformation, the nichrome pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1160 ℃ of insulations 40 hours then, be cooled to room temperature with stove at last, just make Sm
0.5Pr
0.5O
0.7F
0.3The FeAs superconductor.
Embodiment 38
At first according to chemical formula Sm
0.2Nd
0.8O
0.89F
0.11The Sm of weighing shown in FeAs powder 0.52g, Nd powder 1.46g, Fe powder 0.31g, Fe
2O
3Powder 0.65g, NdF
3Powder 0.10g, As powder 1.03g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long titanium-zirconium alloy pipe of 10cm into bore 3mm, external diameter 5mm, make powder in titanium zirconium pipe compo pipe, reach substantial, tight, seal titanium zirconium pipe two ends then.Then this titanium zirconium pipe compo pipe that mixed powder is housed is swaged to 4mm by 5% pass deformation, the titanium zirconium pipe compo pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1300 ℃ of insulations 60 hours then, be cooled to room temperature with stove at last, just make Sm
0.2Nd
0.8O
0.89F
0.11The FeAs superconductor.
Embodiment 39
At first according to chemical formula Ca
0.6Na
0.4Fe
2As
2Shown in weighing Ca powder 0.34g, Fe powder 1.91g, As powder 2.56g and Na fritter 0.18g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long titanium vanadium alloy pipe of 5cm, bore 10mm, external diameter 12mm makes powder reach substantial, tight in the titanium vanadium alloy pipe, seals titanium vanadium alloy pipe two ends then.Then this titanium vanadium alloy pipe that mixed powder is housed is swaged by 12% pass deformation and be drawn to 6mm, the titanium vanadium alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, slowly be warming up to 850 ℃ of insulations 35 hours then, be cooled to room temperature with stove at last, just make the Ca that transition temperature is 20K
0.6Na
0.4Fe
2As
2Superconductor.
Embodiment 40
At first according to chemical formula Pr
0.7Ho
0.3O
0.89F
0.11The Pr of weighing shown in FeAs powder 3.60g, Ho powder 1.29g, Fe powder 0.72g, Fe
2O
3Powder 1.64g, FeF
3Powder 0.14g, As powder 2.60g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long titanium maxter alloy pipe of 10cm into bore 10mm, external diameter 13mm, make powder in pipe, reach substantial, tight, seal titanium maxter alloy pipe two ends then.Then this titanium maxter alloy pipe that mixed powder is housed is proceeded to 8mm by 15% pass deformation, then the thick metal strip of the rolling 4mm of 8% pass deformation.Metal strip after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-4Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 40 hours then, be cooled to room temperature with stove at last, just make Pr
0.7Ho
0.3O
0.89F
0.11The FeAs superconductor.
Embodiment 41
At first according to chemical formula Sm
0.6Gd
0.4O
0.83F
0.17The Sm of weighing shown in FeAs powder 2.30g, Gd powder 1.60g, Fe powder 0.66g, Fe
2O
3Powder 1.16g, GdF
3Powder 0.32g, As powder 1.97g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long titanium manganese alloy pipe of 15cm into bore 6mm, external diameter 9mm, make powder in titanium manganese alloy pipe, reach substantial, tight, seal titanium manganese alloy pipe two ends then.Then this titanium manganese alloy pipe that mixed powder is housed is drawn to 4mm by 8% pass deformation, the titanium manganese alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-2Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 50 hours then, be cooled to room temperature with stove at last, just make Sm
0.6Gd
0.4O
0.83F
0.17FeAs new superconductive body.
Embodiment 42
At first according to chemical formula Sm
0.5Tb
0.5O
0.95F
0.05The Sm of weighing shown in FeAs powder 1.60g, Tb powder 1.52g, Fe powder 0.38g, Fe
2O
3Powder 0.99g, FeF
3Powder 0.04g, As powder 1.47g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long titanium chrome alloy pipe of 10cm into bore 4mm, external diameter 7mm, make powder in pipe, reach substantial, tight, seal titanium chrome alloy pipe two ends then.Then this titanium chrome alloy pipe that mixed powder is housed is swaged to 4mm by 5% pass deformation, the titanium chrome alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-5Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1500 ℃ of insulations 80 hours then, be cooled to room temperature with stove at last, just make Sm
0.5Tb
0.5O
0.95F
0.05FeAs new superconductive body.
Embodiment 43
At first according to chemical formula SmFe
0.9Co
0.1The Sm of weighing shown in AsO powder 6.06g, Fe powder 0.75g, Co
2O
3Powder 0.45g, Fe
2O
3Powder 1.66g, As powder 3.02g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long titanium-tungsten alloy pipe of 8cm into bore 12mm, external diameter 15mm, make powder in pipe, reach substantial, tight, seal titanium-tungsten alloy pipe two ends then.Then this titanium-tungsten alloy pipe that mixed powder is housed is drawn to 10mm by 5% pass deformation, rolling by 5% pass deformation then is metal strip behind the 5mm.Metal strip after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into argon gas after the vacuum tightness of handkerchief, be warming up to 1160 ℃ of insulations 40 hours then, be cooled to room temperature with stove at last, just make SmFe
0.9Co
0.1The AsO superconductor, superconducting transition temperature is 15K after measured.
Embodiment 44
At first according to chemical formula Sm
0.5Dy
0.5O
0.7F
0.3The Sm of weighing shown in FeAs powder 2.32g, Dy powder 2.40g, Fe powder 0.96g, Fe
2O
3Powder 1.20g, DyF
3Powder 0.71g, As powder 2.42g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long titanium niobium alloy pipe of 12cm into bore 8mm, external diameter 11mm, make powder in pipe, reach substantial, tight, seal titanium niobium alloy pipe two ends then.Then this titanium niobium alloy pipe that mixed powder is housed is swaged to 4mm by 12% pass deformation, the titanium niobium alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1300 ℃ of insulations 60 hours then, be cooled to room temperature with stove at last, just make Sm
0.5Dy
0.5O
0.7F
0.3The FeAs superconductor.
Embodiment 45
At first according to chemical formula Er
0.5Ho
0.5O
0.85F
0.15The Er of weighing shown in FeAs powder 1.50g, Ho powder 1.51g, Fe powder 0.46g, Fe
2O
3Powder 0.87g, HoF
3Powder 0.21g, As powder 1.44g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long niobium tungstenalloy pipe of 9cm into bore 6mm, external diameter 8mm, make powder in pipe, reach substantial, tight, seal niobium tungstenalloy pipe two ends then.And with the niobium tungstenalloy pipe titanium pipe of packing into, the titanium bore is 8.2mm, and external diameter is 10mm, then this titanium pipe that mixed powder is housed is swaged to 4mm by 8% pass deformation, metal tube after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-5Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1050 ℃ of insulations 55 hours then, be cooled to room temperature with stove at last, just make Er
0.5Ho
0.5O
0.85F
0.15FeAs new superconductive body.
Embodiment 46
At first according to chemical formula Sr
0.5Na
0.5Fe
2As
2Shown in weighing Sr powder 0.67g, Fe powder 1.72g, the fritter 0.30g of As powder 2.31g and Na, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long niobium molybdenum alloy pipe of 6cm, bore 6mm, external diameter 8mm makes powder reach substantial, tight in pipe, seals niobium molybdenum alloy pipe two ends then.Then this niobium molybdenum alloy pipe that mixed powder is housed is swaged to 5mm by 5% pass deformation, the niobium molybdenum alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 700 ℃ of insulations 55 hours then, be cooled to room temperature with stove at last, just make Sr
0.5Na
0.5Fe
2As
2The new superconductive body.
Embodiment 47
At first according to chemical formula Sm
0.5Yb
0.5O
0.85F
0.15The Sm of weighing shown in FeAs powder 1.25g, Yb powder 1.37g, Fe powder 0.38g, Fe
2O
3Powder 0.71g, YbF
3Powder 0.18g, As powder 1.17g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long zirconium molybdenum alloy pipe of 5cm into bore 6mm, external diameter 8mm, make powder in pipe, reach substantial, tight, seal zirconium molybdenum alloy pipe two ends then.Then this zirconium molybdenum alloy pipe that mixed powder is housed is swaged to 4mm by 10% pass deformation, the metal tube after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 55 hours then, be cooled to room temperature with stove at last, just make Sm
0.5Yb
0.5O
0.85F
0.15FeAs new superconductive body.
Embodiment 48
At first according to chemical formula La
0.5Sm
0.4Ce
0.1O
0.85F
0.15The Sm of weighing shown in FeAs powder 1.85g, La powder 1.90g, Ce powder 0.04g, Fe powder 0.66g, Fe
2O
3Powder 1.24g, SmF
3Powder 0.28g, As powder 2.05g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long zirconium tungstenalloy pipe of 10cm into bore 6mm, external diameter 8mm, make powder in pipe, reach substantial, tight, seal zirconium tungstenalloy pipe two ends then.Then this zirconium tungstenalloy pipe that mixed powder is housed is drawn to 4mm by 15% pass deformation, the zirconium tungstenalloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1150 ℃ of insulations 100 hours then, be cooled to room temperature with stove at last, just make La
0.5Sm
0.4Ce
0.1O
0.85F
0.15FeAs new superconductive body.
Embodiment 49
At first according to chemical formula La
0.6Sm
0.2Gd
0.2O
0.9F
0.1The La of weighing shown in FeAs powder 1.35g, Sm powder 0.45g, Gd powder 0.55g, Fe powder 0.39g, Fe
2O
3Powder 0.84g, LaF
3Powder 0.11g, As powder 1.31g, and place the argon atmospher glove box to grind this powder, make its full and uniform mixing, powder after mixing is packed in the long hafnium tantalum alloy pipe of 10cm into bore 5mm, external diameter 8mm, make powder in hafnium tantalum alloy pipe, reach substantial, tight, seal hafnium tantalum alloy pipe two ends then.Then this hafnium tantalum alloy pipe that mixed powder is housed is swaged to 4mm by 8% pass deformation.Hafnium tantalum alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-2Charge into high-purity argon gas after the vacuum tightness of handkerchief, be warming up to 1200 ℃ of insulations 40 hours then, be cooled to room temperature with annealing furnace at last, just make La
0.6Sm
0.2Gd
0.2O
0.9F
0.1The FeAs superconductor.
Embodiment 50
At first according to chemical formula Eu
0.8Na
0.2Fe
2As
2Shown in weighing Eu powder 0.71g, Fe powder 0.74g, As powder 1.00g and Na fritter 0.03g, and place the argon atmospher glove box to grind this powder, and make its full and uniform mixing, the powder after mixing is packed in the long chrome-manganese alloy pipe of 5cm, bore 10mm, external diameter 12mm makes powder reach substantial, tight in pipe, seals chrome-manganese alloy pipe two ends then.Then this chrome-manganese alloy pipe that mixed powder is housed is drawn to 6mm by 8% pass deformation, the chrome-manganese alloy pipe after the processing is placed high-temperature heater, under room temperature, vacuumize, wait to reach 10
-3Charge into high-purity argon gas after the vacuum tightness of handkerchief, slowly be warming up to 850 ℃ of insulations 35 hours then, be cooled to room temperature with stove at last, just make Eu
0.8Na
0.2Fe
2As
2Superconductor.
Above embodiment illustrate use this technology can the good superconductor of processability, for the mechanism research and the practical application of Fe-base compound superconducting material provides material foundation.
Claims (3)
1. the preparation method of a Fe-base compound superconductor is characterized in that this preparation method may further comprise the steps:
(1) will be according to ReMPnO
1-xF
xOr ReM
1-xTm
xPnO or Ae
1-xA
xM
2Pn
2In the raw material powder of a kind of chemical formula preparation mix after, the metal tube of packing into, fully compacting, the two ends of closed metal pipe then;
(2) with metal tube according to the pass deformation of 5%-20% swage, drawing, rolling processing;
(3) will place high-temperature heater through the metal tube of step 2 processing gained, under room temperature, be evacuated to 10
-2-10
-5Handkerchief charges into argon gas afterwards, is incubated 5-100 hour then under 700-1500 ℃ temperature, treats that at last High Temperature Furnaces Heating Apparatus is cooled to room temperature, and strip off metal jacket obtains Fe-base compound new superconductive body.
2. the preparation method of a kind of Fe-base compound superconductor according to claim 1 is characterized in that: described chemical formula ReMPnO
1-xF
x, ReM
1-xTm
xPnO or Ae
1-xA
xM
2Pn
2: Re is one or more elements that are selected among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, the Y; M is a kind of element that is selected among Fe, Co, Ni, the Ru; Tm is a kind of element among Co, Ni, Mn, the Zn; Pn is a kind of element among As, P, the Sb; Ae is a kind of element among Ca, Sr, Ba, the Eu; A is a kind of element among Li, Na, K, Rb, the Cs; X=0-0.50.
3. the preparation method of a kind of Fe-base compound superconductor according to claim 1, it is characterized in that: described metal tube is pure metal pipe or composite metal pipe or compo pipe, making material chosen from Fe, copper, soft steel, stainless steel, chromium, vanadium, manganese, titanium, zirconium, molybdenum, nickel, niobium, tungsten, hafnium or the tantalum of described metal tube or composite metal pipe or compo pipe.
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