A kind of superconducting wire core, made multi-core composite superconducting wire and preparation thereof by this core
Method
Technical field
The invention belongs to superconductor technical field, be specifically related to a kind of superconduction MgB2Compound packet wire material core and by this
The superconduction MgB that core is made2Compound packet wire material and preparation method thereof.
Background technology
Compared with traditional low temperature superconducting material, the superconducting transition temperature of magnesium diboride is 39K, and this temperature surpasses between low temperature
Lead between material and high temperature superconducting materia, i.e. belong to middle temp. superconductive material, be also simultaneously the critical temperature that finds up to now
High metallic compound, compared with the high temperature superconducting materia of perovskite structure, the anisotropy of magnesium diboride is relatively small, with
Time magnesium diboride crystal structure simple, for hexagonal crystal system, and preparation is easier, low cost of manufacture;Furthermore, magnesium diboride has
Having the coherence length more than atomic radius, supercurrent is not limited by crystal boundary Weak link, and this series of advantages makes two boronations
Magnesium is expected to become 21st century the most practical superconductor, can be widely applied to power transmission cable, current limiter, transformator, superconduction
The aspects such as motor, magnetic suspension train, nuclear magnetic resonance device, superconducting antenna.
At present, prepare in the method for MgB 2 superconductor wire material band, powder tube packing technique (Powder-In-Tube,
PIT) being the method being most widely used, the most this method the most easily realizes industrialized production.Powder tube is equipped with two kinds at present
Technique, the first is that power of magnesium diboride is loaded compound canning tube, the second be by a certain percentage by weighed magnesium powder and
Boron powder loads compound canning tube (powder-in-tube method in situ).Owing to second method can repair magnesium and boron in heat treatment process
Crackle during becoming mutually, improves the switching performance of crystalline phase, and other yuan that simultaneously can also adulterate usually introduces pinning center, carries
High magnesium diboride critical current density, so being most widely used.But still have the disadvantage that during pyroreaction,
The Mg melted spreads to B, and owing to the surface activity of B is the lowest, B is difficult to spread to Mg, thus can stay in the position that Mg is original
Pore, causes there is more cavity in magnesium diboride, and compactness is poor, and generally its consistency is about the 55% of theoretical consistency,
The superconductivity of magnesium diboride can be had a negative impact by relatively low consistency.
Summary of the invention
It is an object of the invention to provide a kind of superconducting line core, it is provided that the multi-core composite superconducting wire being made up of this core is
Second goal of the invention of the present invention, it is provided that the preparation method of multi-core composite superconducting wire is the 3rd goal of the invention of the present invention.
The superconduction core compactness of the present invention is good, has higher critical current density.
Based on above-mentioned purpose, the present invention adopts the following technical scheme that: a kind of superconducting line core, by magnesium powder, amorphous boron powder
Making with nanometer carbon crystal, the mol ratio of described magnesium powder and boron powder is 1:(1.9~2), magnesium powder and the gross mass of boron powder and nano-sized carbon
Brilliant mass ratio 1:(0.01~0.1).
The purity of described magnesium powder is 99%, and granularity is 200~300nm;The purity of described amorphous boron powder is 96%~97%,
Granularity is 300~500nm;The crystallite dimension of described nanometer carbon crystal is 2~5nm.
The multi-core composite superconducting wire being made up of described superconducting line core, superconducting line core peripheral hardware is combined canning tube, compound
Canning tube the most successively by the first stainless steel tube barrier layer, the second stainless steel tube barrier layer and copper pipe jacket layer, core and
Compound canning tube constitutes single-core superconducting wire;Single-core superconducting wire is obtained along the inwall ecto-entad uniform close successively arrangement of copper pipe
Multicore composite bushing, the gap of the cross section of multicore composite bushing is filled in copper bar, multicore composite bushing and copper bar and is constituted multicore
Composite superconducting wire.
The preparation method of described multi-core composite superconducting wire, including (one) tubulature, (two) swage, drawing, (three) secondary group
Dress, (four) secondary is swaged, drawing and (five) high temperature sintering process, wherein,
(1) the concretely comprising the following steps of tubulature:
1) first nanometer carbon crystal is joined in methanol and carry out ultrasonic disperse;It is added to boron powder again carry out being mixed to get mixing
Liquid;
2) being heated in vacuum desiccator by mixed liquor, heating process uses ladder heating, concretely comprises the following steps: system is first by room temperature
Rise to 40 DEG C, be incubated 40min;Rise to 80 DEG C again, be incubated 1h;Rising to 100 DEG C afterwards, insulation is until solvent all volatilizees is mixed
Compound A;Programming rate when every time heating up is 5 DEG C/min;
3) mixture A is poured three-dimensional material mixer into, and add magnesium powder carry out batch mixing stirring obtain mixture B, mixing time is
2.5h;
4) mixture B loads compound canning tube, is closed one end of canning tube afterwards, and canning tube is carried out gas pressurized, execute
Adding gas pressure is 0.3MPa~2MPa, and the other end of re-closed canning tube i.e. obtains single and is combined canning tube;
(2) swage, the concretely comprising the following steps of drawing:
5) carry out compound canning tube on swager and drawbench swaging and drawing, by control single pass deformation rate 5%~
Between 15%, obtain the single-core superconducting wire material of diameter phi 5~φ 7mm;
(3) what secondary assembled concretely comprises the following steps:
6) a diameter of φ 5~φ 7mm single-core superconducting wire material sizing is blocked, alignment, by single-core superconducting wire along the inwall of copper pipe
The arrangement of ecto-entad uniform close obtains multicore composite bushing successively;
7) one end of multicore composite bushing is closed, copper bar is filled in the gap of multicore cable cross section, and ensure to cut
Face void area is not more than the 15% of cross-sectional area, and re-closed multicore is combined the canning tube other end;
(4) secondary swage, the concretely comprising the following steps of drawing:
8) multicore after being assembled by secondary is combined canning tube to carry out secondary on swager and drawbench and swages and drawing, controls single
Pass deformation rate, between 5%~15%, obtains the multicore MgB 2 superconductor wire material of compound sheath material;
9) superconduction core is carried out again gas pressurized, supplement mixture B simultaneously, it is ensured that material is full of compound canning tube, applies
Gas pressure is 1MPa~5MPa;
(5) what high temperature sintering processed concretely comprises the following steps:
10) swaged by secondary, the tubular heater under flowing argon shield put into by multi-core superconducting magnesium diboride wire rod after drawing
In, the purity of described argon is not less than 99.9%, and the flow velocity 25~30L/min of argon, heating mode uses staged heating, tool
Body step is: first is that 5~6 DEG C/min is risen to 500~550 DEG C by room temperature with heating rate, is incubated 30min;Again with heating rate
It is that 5~6 DEG C/min is warming up to 600~650 DEG C, is incubated 30min;Afterwards with heating rate be 8~10 DEG C/min be warming up to 750~
850 DEG C, being incubated 1h, finally cool to room temperature with the furnace, rate of cooling is 10~15 DEG C/min.
In step 1), the power of ultrasonic disperse is 0.3~0.6KW, and the time is 10~15min;Add boron powder to mix
Shi Caiyong speed governing motor stirrer, mixing speed is 2000~2100r/min, and mixing time is 25~35min.
Step 2) in all processes of heating and thermal insulation and the whole heating of step 10), cooling procedure entered by computer
Row controls.
Compared with prior art, the beneficial effects of the present invention is:
1, first nanometer carbon crystal is disperseed in toluene, then be stirred mixing with boron powder, owing to nanometer carbon crystal has
High surface activity, the boron of greater particle size will be adhered to by the nanometer carbon crystal of small particle, and now nanometer carbon crystal can be dispersed in
In boron powder, in heat treatment process, the effect adhered to by nanometer carbon crystal due to boron particles surface, strengthen B diffusivity, Mg to
While B diffusion, B also can flow to the gap of Mg, therefore can significantly weaken the porous defect of magnesium diboride, improves it and causes
Density, reaches as high as the 80% of magnesium diboride theory consistency;
2, nanometer carbon crystal is compared with other nano-sized carbon, good dispersion, be difficult to reunite, be easily dispersed in magnesium diboride tissue
In.The crystallite dimension of nanometer carbon crystal is 2~5nm, has a higher surface activity than other nano-sized carbon, and its crystallite dimension with
Closely, under high temperature action, nanometer carbon crystal more easily enters magnesium diboride to the coherence length (5nm) of magnesium diboride
Lattice and crystal boundary, produce more lattice defect, so the quantity at effectively pin center can will increase, thus improve two boronations
Magnesium wire rod is in the critical current density of highfield;
3, according to the reaction mechanism of Mg with B and become phase process, high temperature sintering heat treatment uses trapezoidal mode of heating, simultaneously each
The heating rate of temperature section is different, contributes to the abundant reaction of magnesium and boron, and the magnesium diboride that formation even tissue, consistency are high surpasses
Wire material;
4, single magnesium diboride wire rod arranges along copper pipe inwall ecto-entad uniform close successively, in the gap of core Yu core
Insert and the copper bar of pore cross-section form fit, not only facilitate secondary swage, the uniform force of single core in drawing process,
Also can improve the tensile strength of integrated wire simultaneously.
Accompanying drawing explanation
Effects of Density to multi-core composite superconducting wire when Fig. 1 is nanometer carbon crystal doping difference;
Impact on the critical current density of multi-core composite superconducting wire when Fig. 2 is nanometer carbon crystal doping difference;
Fig. 3 is the structural representation of single-core superconducting wire of the present invention;
Fig. 4 is the structural representation of multi-core composite superconducting wire of the present invention.
Detailed description of the invention
Example below, only for further illustrating the present invention, limits the present invention the most in any form.
Embodiment 1
A kind of superconducting line core, is made up of magnesium powder, amorphous boron powder and nanometer carbon crystal, and the mol ratio of described magnesium powder and boron powder is 1:
2, the gross mass of magnesium powder and boron powder and the mass ratio 1:0.05 of nanometer carbon crystal;The purity of described magnesium powder is 99%, and granularity is 250nm;
The purity of described amorphous boron powder is 96%, and granularity is 400nm;The crystallite dimension of described nanometer carbon crystal is 3nm.
The multi-core composite superconducting wire being made up of described superconducting wire core, as shown in Figure 3 and Figure 4, outside superconducting line core 4
If compound canning tube, compound canning tube is the most successively by the 3, second stainless steel tube barrier layer 2, the first stainless steel tube barrier layer
Forming with copper pipe jacket layer 1, compound canning tube and core 4 constitute single-core superconducting wire;By single-core superconducting wire along the second copper pipe jacket
The inwall ecto-entad uniform close successively arrangement of layer 5 obtains multicore composite bushing, the space of the cross section of multicore composite bushing
Place fills in copper bar 6, multicore composite bushing and copper bar 6 and constitutes multi-core composite superconducting wire.
The preparation method of described multi-core composite superconducting wire, including (one) tubulature, (two) swage, drawing, (three) secondary group
Dress, (four) secondary is swaged, drawing and (five) high temperature sintering process, wherein,
(1) the concretely comprising the following steps of tubulature:
1) first nanometer carbon crystal is joined in methanol and carry out ultrasonic disperse;It is added to boron powder again carry out being mixed to get mixing
Liquid;In step 1), the power of ultrasonic disperse is 0.3KW, and the time is 15min;Adding uses speed governing electronic when boron powder mixes
Agitator, mixing speed is 2100r/min, and mixing time is 25min;
2) being heated in vacuum desiccator by mixed liquor, heating process uses ladder heating, concretely comprises the following steps: system is first by room temperature
Rise to 40 DEG C, be incubated 40min;Rise to 80 DEG C again, be incubated 1h;Rising to 100 DEG C afterwards, insulation is until solvent all volatilizees is mixed
Compound A;Programming rate when every time heating up is 5 DEG C/min;Step 2) in all processes of heating and thermal insulation carried out by computer
Control.
3) mixture A is poured three-dimensional material mixer into, and add magnesium powder carry out batch mixing stirring obtain mixture B, mixing time
For 2.5h;
4) mixture B loads compound canning tube, is closed one end of canning tube afterwards, and canning tube is carried out gas pressurized, execute
Adding gas pressure is 0.3MPa~2MPa, and the other end of re-closed canning tube i.e. obtains single and is combined canning tube;
(2) swage, drawing specially comprises the following steps:
5) carry out compound canning tube on swager and drawbench swaging and drawing, by controlling single pass deformation rate 10%
Between, obtain the single-core superconducting wire material of diameter phi 6mm;
(3) what secondary assembled concretely comprises the following steps:
6) a diameter of φ 6mm single-core superconducting wire material sizing is blocked, alignment, by single-core superconducting wire along copper pipe inwall successively by
Uniform close arrangement obtains multicore composite bushing outside to inside;
7) one end of multicore composite bushing is closed, copper bar is filled in the gap of multicore cable cross section, and ensure to cut
Face void area is not more than the 15% of cross-sectional area, and re-closed multicore is combined the canning tube other end;
(4) secondary swage, the concretely comprising the following steps of drawing:
8) multicore after being assembled by secondary is combined canning tube to carry out secondary on swager and drawbench and swages and drawing, controls single
Pass deformation rate, between 10%, obtains the multicore MgB 2 superconductor wire material of compound sheath material;
9) superconduction core is carried out again gas pressurized, supplement mixture B simultaneously, it is ensured that material is full of compound canning tube, applies
Gas pressure is 2MPa;
(5) what high temperature sintering processed concretely comprises the following steps:
10) swaged by secondary, the tubular heater under flowing argon shield put into by multi-core superconducting magnesium diboride wire rod after drawing
In, the purity of described argon is not less than 99.9%, the flow velocity 25L/min of argon, and heating mode uses staged heating, specifically walks
Suddenly it is: first is that 5 DEG C/min is risen to 500 DEG C by room temperature with heating rate, is incubated 30min;Again with heating rate be 6 DEG C/min heat up
To 600~DEG C, be incubated 30min;It is that 8 DEG C/min is warming up to 750 DEG C with heating rate afterwards, is incubated 1h, finally cools to the furnace
Room temperature, rate of cooling is 10 DEG C/min;The whole heating of step 10), cooling procedure are controlled by computer.
Embodiment 2
A kind of superconducting line core, is made up of magnesium powder, amorphous boron powder and nanometer carbon crystal, and the mol ratio of described magnesium powder and boron powder is 1:
1.9, the gross mass of magnesium powder and boron powder and the mass ratio 1:0.01 of nanometer carbon crystal;The purity of described magnesium powder is 99%, and granularity is
200nm;The purity of described amorphous boron powder is 96%, and granularity is 300nm;The crystallite dimension of described nanometer carbon crystal is 2nm.
The multi-core composite superconducting wire being made up of described superconducting wire core, superconducting line core 4 peripheral hardware is combined canning tube, multiple
Close canning tube the most successively by the 3, second stainless steel tube barrier layer 2, the first stainless steel tube barrier layer and 1 group of copper pipe jacket layer
Becoming, compound canning tube and core 4 constitute single-core superconducting wire;By single-core superconducting wire along the second copper pipe jacket layer 5 inwall successively by
Uniform close arrangement obtains multicore composite bushing outside to inside, and copper bar 6, multicore are filled in the gap of the cross section of multicore composite bushing
Composite bushing and copper bar 6 constitute multi-core composite superconducting wire.
The preparation method of described multi-core composite superconducting wire, including (one) tubulature, (two) swage, drawing, (three) secondary group
Dress, (four) secondary is swaged, drawing and (five) high temperature sintering process, wherein,
(1) the concretely comprising the following steps of tubulature:
1) first nanometer carbon crystal is joined in methanol and carry out ultrasonic disperse;It is added to boron powder again carry out being mixed to get mixing
Liquid;In step 1), the power of ultrasonic disperse is 0.3KW, and the time is 10min;Adding uses speed governing electronic when boron powder mixes
Agitator, mixing speed is 2000r/min, and mixing time is 25min;
2) being heated in vacuum desiccator by mixed liquor, heating process uses ladder heating, concretely comprises the following steps: system is first by room temperature
Rise to 40 DEG C, be incubated 40min;Rise to 80 DEG C again, be incubated 1h;Rising to 100 DEG C afterwards, insulation is until solvent all volatilizees is mixed
Compound A;Programming rate when every time heating up is 5 DEG C/min;Step 2) in all processes of heating and thermal insulation carried out by computer
Control.
3) mixture A is poured three-dimensional material mixer into, and add magnesium powder carry out batch mixing stirring obtain mixture B, mixing time
For 2.5h;
4) mixture B loads compound canning tube, is closed one end of canning tube afterwards, and canning tube is carried out gas pressurized, execute
Adding gas pressure is 0.3MPa, and the other end of re-closed canning tube i.e. obtains single and is combined canning tube;
(2) swage, drawing specially comprises the following steps:
5) carry out compound canning tube on swager and drawbench swaging and drawing, by control single pass deformation rate 5% it
Between, obtain the single-core superconducting wire material of diameter phi 5mm;
(3) what secondary assembled concretely comprises the following steps:
6) a diameter of φ 5mm single-core superconducting wire material sizing is blocked, alignment, by single-core superconducting wire along copper pipe inwall successively by
Uniform close arrangement obtains multicore composite bushing outside to inside;
7) one end of multicore composite bushing is closed, copper bar is filled in the gap of multicore cable cross section, and ensure to cut
Face void area is not more than the 15% of cross-sectional area, and re-closed multicore is combined the canning tube other end;
(4) secondary swage, the concretely comprising the following steps of drawing:
8) multicore after being assembled by secondary is combined canning tube to carry out secondary on swager and drawbench and swages and drawing, controls single
Pass deformation rate, between 5%, obtains the multicore MgB 2 superconductor wire material of compound sheath material;
9) superconduction core is carried out again gas pressurized, supplement mixture B simultaneously, it is ensured that material is full of compound canning tube, applies
Gas pressure is 1MPa;
(5) what high temperature sintering processed concretely comprises the following steps:
10) swaged by secondary, the tubular heater under flowing argon shield put into by multi-core superconducting magnesium diboride wire rod after drawing
In, the purity of described argon is not less than 99.9%, the flow velocity 25L/min of argon, and heating mode uses staged heating, specifically walks
Suddenly it is: first is that 5 DEG C/min is risen to 500 DEG C by room temperature with heating rate, is incubated 30min;Again with heating rate be 5 DEG C/min heat up
To 600 DEG C, it is incubated 30min;It is that 8 DEG C/min is warming up to 750 DEG C with heating rate afterwards, is incubated 1h, finally cools to room with the furnace
Temperature, rate of cooling is 10 DEG C/min;The whole heating of step 10), cooling procedure are controlled by computer.
Embodiment 3
A kind of superconducting line core, is made up of magnesium powder, amorphous boron powder and nanometer carbon crystal, and the mol ratio of described magnesium powder and boron powder is 1:
2), the gross mass of magnesium powder and boron powder and the mass ratio 1:0.1 of nanometer carbon crystal;The purity of described magnesium powder is 99%, and granularity is 300nm;
The purity of described amorphous boron powder is 97%, and granularity is 500nm;The crystallite dimension of described nanometer carbon crystal is 5nm.
The multi-core composite superconducting wire being made up of described superconducting wire core, superconducting line core 4 peripheral hardware is combined canning tube, multiple
Close canning tube the most successively by the 3, second stainless steel tube barrier layer 2, the first stainless steel tube barrier layer and 1 group of copper pipe jacket layer
Becoming, compound canning tube and core 4 constitute single-core superconducting wire;By single-core superconducting wire along the second copper pipe jacket layer 5 inwall successively by
Uniform close arrangement obtains multicore composite bushing outside to inside, and copper bar 6, multicore are filled in the gap of the cross section of multicore composite bushing
Composite bushing and copper bar 6 constitute multi-core composite superconducting wire.
The preparation method of described multi-core composite superconducting wire, including (one) tubulature, (two) swage, drawing, (three) secondary group
Dress, (four) secondary is swaged, drawing and (five) high temperature sintering process, wherein,
(1) the concretely comprising the following steps of tubulature:
1) first nanometer carbon crystal is joined in methanol and carry out ultrasonic disperse;It is added to boron powder again carry out being mixed to get mixing
Liquid;In step 1), the power of ultrasonic disperse is 0.6KW, and the time is 15min;Adding uses speed governing electronic when boron powder mixes
Agitator, mixing speed is 2100r/min, and mixing time is 35min;
2) being heated in vacuum desiccator by mixed liquor, heating process uses ladder heating, concretely comprises the following steps: system is first by room temperature
Rise to 40 DEG C, be incubated 40min;Rise to 80 DEG C again, be incubated 1h;Rising to 100 DEG C afterwards, insulation is until solvent all volatilizees is mixed
Compound A;Programming rate when every time heating up is 5 DEG C/min;Step 2) in all processes of heating and thermal insulation carried out by computer
Control.
3) mixture A is poured three-dimensional material mixer into, and add magnesium powder carry out batch mixing stirring obtain mixture B, mixing time
For 2.5h;
4) mixture B loads compound canning tube, is closed one end of canning tube afterwards, and canning tube is carried out gas pressurized, execute
Adding gas pressure is 2MPa, and the other end of re-closed canning tube i.e. obtains single and is combined canning tube;
(2) swage, drawing specially comprises the following steps:
5) carry out compound canning tube on swager and drawbench swaging and drawing, by controlling single pass deformation rate 15%
Between, obtain the single-core superconducting wire material of diameter phi 7mm;
(3) what secondary assembled concretely comprises the following steps:
6) a diameter of φ 7mm single-core superconducting wire material sizing is blocked, alignment, by single-core superconducting wire along copper pipe inwall successively by
Uniform close arrangement obtains multicore composite bushing outside to inside;
7) one end of multicore composite bushing is closed, copper bar is filled in the gap of multicore cable cross section, and ensure to cut
Face void area is not more than the 15% of cross-sectional area, and re-closed multicore is combined the canning tube other end;
(4) secondary swage, the concretely comprising the following steps of drawing:
8) multicore after being assembled by secondary is combined canning tube to carry out secondary on swager and drawbench and swages and drawing, controls single
Pass deformation rate, between 15%, obtains the multicore MgB 2 superconductor wire material of compound sheath material;
9) superconduction core is carried out again gas pressurized, supplement mixture B simultaneously, it is ensured that material is full of compound canning tube, applies
Gas pressure is 5MPa;
(5) what high temperature sintering processed concretely comprises the following steps:
10) swaged by secondary, the tubular heater under flowing argon shield put into by multi-core superconducting magnesium diboride wire rod after drawing
In, the purity of described argon is not less than 99.9%, the flow velocity 30L/min of argon, and heating mode uses staged heating, specifically walks
Suddenly it is: first is that 6 DEG C/min is risen to 550 DEG C by room temperature with heating rate, is incubated 30min;Again with heating rate be 6 DEG C/min heat up
To 650 DEG C, it is incubated 30min;It is that 10 DEG C/min is warming up to 850 DEG C with heating rate afterwards, is incubated 1h, finally cools to room with the furnace
Temperature, rate of cooling is 15 DEG C/min;The whole heating of step 10), cooling procedure are controlled by computer.
Performance test
Density and critical current to multi-core composite superconducting wire when the present invention also furthermore present nanometer carbon crystal doping difference
The impact of density, result is shown in that shown in Fig. 1 and Fig. 2, (heretofore described doping is actually nanometer carbon crystal and magnesium powder and boron powder
The mass values of gross mass).
It will be seen from figure 1 that along with the difference of nanometer carbon crystal doping, the density of multi-core composite superconducting wire is the most different,
When the doping of nanometer carbon crystal is 0.01~0.1, its density is relatively big, when doping is about 0.05, reaches maximum 2.1g/
cm3, for the 80% of theoretical magnesium diboride density, a certain amount of nanometer carbon crystal that therefore adulterates is for improving single-core superconducting wire or multicore
Complex superconducting line density has significantly effect.
From figure 2 it can be seen that the critical current density of the multi-core composite superconducting wire of nanometer carbon crystal doping is not apparently higher than
The critical current density of the multi-core composite superconducting wire of doping, when doping is 0.05, its critical current density is maximum, at 3T,
Under conditions of 20K, its critical current density is 45000A/cm2, relative to unadulterated multi-core composite superconducting wire, critical current
Density improves 4.5 times.