CN108486418A - A kind of B alloy wire and its preparation process for thermoelectric generator - Google Patents
A kind of B alloy wire and its preparation process for thermoelectric generator Download PDFInfo
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- CN108486418A CN108486418A CN201810383429.1A CN201810383429A CN108486418A CN 108486418 A CN108486418 A CN 108486418A CN 201810383429 A CN201810383429 A CN 201810383429A CN 108486418 A CN108486418 A CN 108486418A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
- B21C37/047—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire of fine wires
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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Abstract
The present invention relates to field of generating equipment, more particularly to a kind of B alloy wire and its preparation process for thermoelectric generator, it solves the problems, such as to generate electricity using combustion gas in the prior art less efficient, its key points of the technical solution are that, a kind of B alloy wire for thermoelectric generator, it is made of nisiloy magnesium alloy, the silicon for being 3.5% 4% including mass fraction, 0.1% 0.5% cobalt, 0.1% 0.3% iron, 0.1% 0.3% magnesium, 0.05% 0.2% yttrium, 0.1% 0.5% niobium, 0.1% 0.5% vanadium, 0.1% 0.25% carbon, remaining is nickel, pass through the stability under the heat resistance and high temperature of raising B alloy wire, improve the fusing-off temperature of B alloy wire；Meanwhile the inoxidizability by improving B alloy wire, it avoids the B alloy wire resistance value brought due to oxidation and increases, it is ensured that the electric conductivity of B alloy wire is good.
Description
Technical field
The present invention relates to field of generating equipment, more particularly to a kind of B alloy wire and its preparation work for thermoelectric generator
Skill.
Background technology
Power generation is to utilize generation power device by water energy, the thermal energy of fossil fuel, nuclear energy and solar energy, wind energy, underground heat
Energy, ocean energy etc. are converted to electric energy.Wherein it is a kind of most commonly used side in the way of the heat energy power-generating of fossil fuel
Formula, and the generating efficiency of existing fossil fuel power is usually relatively low, while also will produce certain pollution.
And fuel gas generation is to utilize one of most stable of generation mode in fossil fuel power, combustion gas hair in the prior art
Motor group is broadly divided into two kinds, and one is combined cycle gas turbines, and one is gas internal-combustion engine, common ground is to turn interior energy
Turn to a kind of power generation mode that kinetic energy is then converted to electric energy.And the conversion between energy each time can all generate certain energy damage
Consumption, and by the generation mode of interior energy → kinetic energy → electric energy, energy conversion twice has been carried out, energy damage twice is also just produced
Consumption, thus common generating efficiency is less than 50%, and cold, heat and electricity three-way electricity generation system is since its is complicated, cost is higher,
Some small-sized power stations are difficult to promote the use of.
For this purpose, in the prior art, having invented thermoelectric generator, without rotatable parts, small, long lifespan utilizes plug shellfish
Gram effect, is directly changed into electric energy, to improve generating efficiency by thermal energy.When in use, by a p-type thermoelement and
One N-shaped thermoelement is connected in hot junction with metallic conductor electrode, and cold terminal electrodes are separately connected in its cold end, is just constituted
One temperature difference monomer is single even.And connect the metallic conductor electrode of p-type thermoelement and N-shaped thermoelement, usually by
It fuses in working under the high temperature conditions, thus inconvenient for use.
Invention content
The object of the present invention is to provide a kind of B alloy wires and its preparation process for thermoelectric generator, it is advantageous that,
High-temperature stability is strong, is not susceptible to fuse.
The present invention above-mentioned technical purpose technical scheme is that：
A kind of B alloy wire for thermoelectric generator is made of nisiloy magnesium alloy, including mass fraction is 3.5%-4%'s
Silicon, the cobalt of 0.1%-0.5%, the iron of 0.1%-0.3%, the magnesium of 0.1%-0.3%, the yttrium of 0.05%-0.2%, 0.1%-
0.5% niobium, the vanadium of 0.1%-0.5%, the carbon of 0.1%-0.25%, remaining is nickel.
Conjunction is improved by the stability under the heat resistance and high temperature of raising B alloy wire by using above-mentioned technical proposal
The fusing-off temperature of spun gold；Meanwhile the inoxidizability by improving B alloy wire, it avoids due to B alloy wire internal oxidation and brings
B alloy wire resistance value increases, it is ensured that the electric conductivity of B alloy wire is good.
It is easy to form silicon magnesium complex oxide film by the way that silicon and magnesium, the surface of alloy is added, relative to common magnesium oxide films,
Consistency bigger, inoxidizability are extremely strong；Meanwhile magnesium forms magnesium silicon binary alloy with silicon, has soft α-magnesium and hard phase silicon, it is wear-resisting
Functional, temperature not will produce the phenomenon that reinforcing is dissolved or assembled after increasing, have good heat resistance.
After iron is added, the toughness of B alloy wire is improved.
After magnesium is added, it is greatly improved the inoxidizability of the B alloy wire for thermoelectric generator, surface forms
Fine and close magnesium oxide films, especially at high operating temperatures, magnesium oxide films thermal stability is good, can prevent the lasting progress of oxidation；Together
When, magnesium has the effect of crystal grain thinning, improves the high-temperature corrosion resistance ability of B alloy wire.
By the way that yttrium is added, accelerates the diffusion of magnesium in alloy, improve the formation speed of magnesium oxide films；Meanwhile in magnesium yttrium oxygen
Change the intersection of film and alloy substrate, the oxide of yttrium is distributed in dendroid to matrix, plays the role of " pinning ", Dispersed precipitate
Yttrium oxide causes vacancy trap effect, to improve oxidation film and matrix combination intensity, to improve alloy
Inoxidizability；At the same time, yttrium magnesium complex oxide film, relative to common magnesium oxide films, inoxidizability is stronger, and stability is more
By force, the stability at high temperature of B alloy wire is improved.
It can play the role of crystal grain thinning by the way that vanadium and carbon, vanadium is added, to improve intensity and toughness, meanwhile, vanadium
Carbide is formd in alloy with carbon, to improve the ability of resistant to hydrogen corrosion.
Preferably, for further including the rich lanthanum for having mass fraction for 0.05%-0.2% in the B alloy wire of thermoelectric generator
Rare earth.
Play the role of crystal grain thinning in the alloy, together by the way that lanthanum rich rare earth is added by using above-mentioned technical proposal
When, lanthanum rich rare earth plays the role of long-acting braiding agent in the alloy, improves the anti-remelting decline ability of alloy.Thus, alloy
Silk during use, remains to keep stable state at high temperature, and the heat for improving the B alloy wire for thermoelectric generator is steady
It is qualitative.
Preferably, for further including the antimony for having mass fraction for 0.1%-0.3% in the B alloy wire of thermoelectric generator.
The heat resistance of B alloy wire is improved, after antimony is added, on the one hand by the way that antimony is added by using above-mentioned technical proposal
It is dissolved into β phases；Another aspect disperse educt has six side D52The Mg of crystal form3Sb2Phase has the advantages that thermal stability is strong, Mg3Sb2
Phase Dispersed precipitate in the matrix of alloy dispersion-strengtherning effect, meanwhile, also compensate for the deficiency of β phases and as α-Mg matrixes
Non-spontaneous forming core substrate, promote transgranular with alloy substrate coherent structural Mg17Sb12Mutually it is precipitated.Mg17Sb12Mutually have tiny
The advantages of continuous uniform is distributed, thus improve the high-temperature behavior of alloy.
And due to containing silicon, the addition of antimony, on the one hand by synthesizing heterogeneous nucleus core Mg in alloy3Sb2, promote tiny
The Mg of Dispersed precipitate2Si particles are formed, and coarse Mg original in alloy is made2Si becomes the graininess Mg of small and dispersed distribution2Si；
On the other hand, alloy substrate tissue has further been refined, creep-resistant property of the alloy between 150-200 DEG C is significantly improved.
Preferably, for further including the copper for having mass fraction for 0.4%-0.8% in the B alloy wire of thermoelectric generator.
By using above-mentioned technical proposal, nickel forms the single phase austenite of high intensity with copper, compares in reductant
Other Ni-based alloys are corrosion-resistant, than nickel and copper more resistant to corrosion in Oxidant faces phosphoric acid, sulfuric acid, hydrochloric acid and organic acid.
The preparation process of a kind of B alloy wire for thermoelectric generator, which is characterized in that include the following steps：
S1, shearing：Raw material are cut into strip and block or spherical；
S2, dispensing：Raw material after shearing are subjected to dispensing in proportion；
S3, melting：Raw material after dispensing are put into vacuum melting furnace and carries out vacuum melting and is cooled and shaped；
S4, it forges：Wire rod after melting is carried out to forge amendment；
S5, working process：Wire rod after forging carries out drawing process and forms finished product；
S6, storage is examined：It tests to the finished product after working process, certified products are stored in storehouse.
By using above-mentioned technical proposal, raw material is cut into fritter by shearing, the proportioning convenient for raw material and melting；It is logical
Cross and forge, the wire rod after cooling and shaping is forged, reduce stomata on wire rod, shrinkage cavity defect, optimize wire rod
Micro-pipe institutional framework.
Preferably, the S5 is specifically included：
A1, it makes annealing treatment for the first time：Wire rod after forging is done and is made annealing treatment for the first time, annealing is moved back for bell-type for the first time
Fire；
A2, first round drawing process：Multiple drawing is gradually drawn to 2.6mm by a diameter of 8.5mm；
A3, first time pickling：Wire rod after first round drawing process is subjected to pickling, removes surface scale and rust；
A4, it makes annealing treatment for second：Second of annealing is done to the wire rod after forging, second of annealing is continuously to move back
Fire；
A5, the second wheel drawing process：Multiple drawing is gradually drawn to 1.37mm by a diameter of 2.6mm and semi-finished product is made；
A6, screening：Product of accomplishing after second wheel drawing process are sieved, other productions are according to circumstances made in underproof product
Product, qualified semi-finished product continue A7；
A7, third round drawing process：Multiple drawing is gradually drawn to 0.53mm by a diameter of 1.37mm and finished product is made；
A8, second of pickling：Semi-finished product qualified after screening are subjected to pickling, remove qualified surface of semi-finished oxide skin and corrosion
Object.
By using above-mentioned technical proposal, by the first annealing, using bell-type annealing, heat is carried out to coiled wire rod
Processing, single heat treatment amount is big, easy to use；It is made annealing treatment by second, using continuous annealing, wire rod high speed passes through at heat
It manages in stove, to make deformed grains in wire rod be re-converted to uniform equi-axed crystal, while eliminating in processing hardening and residual
Stress.
Part wire rod is during the drawing process, it may appear that not the defects of size is not inconsistent or deforms, thus after first round drawing, into
After row screening, these defects can be found in time, and in advance filter out undesirable semi-finished product, by defective work according to reality
Border situation is made other and requires lower product；Qualified product is continued into the second wheel drawing, finished product is made, to significantly
It improves yield rate and reduces the waste of material.
For wire rod after drawing, the remained on surface of wire rod has oxide skin and rust, after pickling twice, by oxide skin and
Rust reacts removing with acid.
Preferably, the S3 specifically comprises the following steps：
B1, first by magnesium and Ni-B alloy at intermediate alloy, intermediate alloy includes the nickel that mass fraction is 60% and mass fraction is
Proportioned magnesium and nickel are added in vacuum melting furnace and carry out melting by 40% magnesium；
B2, after magnesium and nickel fully melt, lanthanum rich rare earth is added, continues melting, at 1500 DEG C after melting 1 minute,
Enter cooling in punching block；
B3, it carries out, to nisiloy magnesium alloy sample detection, the amount that intermediate alloy is added being calculated by the requirement of content of magnesium in formula, and add
Enter remaining nickel；
B4, proportioned intermediate alloy and nickel are put into vacuum melting furnace, heat melting, waits for that intermediate alloy is fully melted with nickel
Afterwards, other small powders are added in vacuum melting furnace.
By using above-mentioned technical proposal, the fusing-off temperature of magnesium is 648 DEG C, and the fusing-off temperature of nickel is 1453 DEG C, magnesium it is close
Degree is 1.74g/cm3, and the density of nickel is 8.9g/cm3, in conventional melting mode, due to the fusing-off temperature of magnesium and nickel, close
Degree difference is larger, during direct melting, needs to improve heating temperature, extends smelting time, meanwhile, easy to produce burning
The phenomenon that damage, segregation, casting yield is relatively low, thus is difficult to realize mutually melting for magnesium and nickel.Especially in the B alloy wire as thermocouple,
Due to nickel in the alloy accounting much larger than magnesium accounting magnesium be added nickel in after, fusing-off temperature difference it is larger, magnesium is difficult to be formed with nickel
Uniform crystal grain, thus cause the B alloy wire quality of output uneven, the property of B alloy wire is uneven, affects thermocouple temperature measurement degree
Accuracy.
By first making the intermediate alloy of magnesium and nickel, nickel and content are more than the content of magnesium, after carrying out vacuum melting, burn out rate
It is relatively low；After lanthanum rich rare earth is added, so that the profit visual angle between nickel solution and magnesium is increased, improve the uniform journey that magnesium is distributed in nickel
Degree, it is therefore prevented that the segregation of magnesium.The magnesium nickel intermediate alloy produced, be evenly distributed disperse, and crystal grain is tiny, thus by intermediate alloy
Addition accelerates mutually molten speed when being mixed with other raw materials, to reduce the scaling loss of magnesium and be unevenly distributed.
Preferably, after waiting for A8, continue
A9, Dehydroepiandrosterone derivative：By melted finished product, finished surface is brushed using high-pressure spray gun.
By using above-mentioned technical proposal, the surface of finished product is brushed using high-pressure spray gun, on the one hand, by wire rod table
The possible remaining oxide skin in face or rust are blown off, and oxide skin and influence of the rust to wire rod performance itself are reduced.
On the other hand, after pickling, oxide skin or rust react with acid and generate hydrogen, and hydrogen partial is attached to the table of wire rod
Face.Although wire rod has good resistant to hydrogen corrosion, due to the Special use purposes of thermocouple, the size of wire rod is required and its
Strictly, thus, a small amount of hydrogen attack of wire surface still results in the minor change in wire size, so as to cause thermocouple
Temperature measurement accuracy declines.Wire surface is brushed by high-pressure spray gun, the hydrogen for being attached to wire surface is blown out, to cut off
The source of diffusible hydrogen, further reduces hydrogen attack, improves the temperature measurement accuracy of the thermocouple made of B alloy wire.
Preferably, when Dehydroepiandrosterone derivative, finished product is positioned in pyroreaction kettle, the gas used in high-pressure spray gun is dioxy
Change carbon.
By using above-mentioned technical proposal, carbon dioxide reacts with hydrogen at high temperature, CO2+H2→CO+H2O, because
And high-pressure spray gun of being more convenient for removes hydrogen.
Preferably, being placed with alkaline drier in pyroreaction kettle.
By using above-mentioned technical proposal, the alkaline drier in pyroreaction kettle on the one hand can be in time by carbon dioxide
The water generated is reacted with hydrogen to absorb, to be conducive to the positive progress that carbon dioxide is reacted with hydrogen, meanwhile, reduce titanium dioxide
Carbon mixes generation carbonic acid molecule with water and is reacted with alkaline drier, to reduce the waste of carbon dioxide；
On the other hand, since alloy itself has good antiacid corrosivity, thus after pickling, part acid may adhere to wire rod
Surface, volatilization may be will produce under high temperature environment, by alkaline drier, the absorbable acid being more than is more than to reduce
Corrosion of the acid to pyroreaction kettle.
In conclusion the invention has the advantages that：
1, by taking turns drawing and screening more, improving yield rate and reducing the waste of material；
2, it by the addition of intermediate alloy, solves the problems, such as that nickel is difficult to mutually melt with magnesium, improves the reliability of B alloy wire；
3, carbon dioxide is brushed to the wire rod after pickling by high-pressure spray gun, reduces the surface hydrogen attack of wire rod；
4, by the stability under the heat resistance and high temperature of raising B alloy wire, the fusing-off temperature of B alloy wire is improved；Meanwhile passing through
The inoxidizability for improving B alloy wire is avoided the B alloy wire resistance value brought due to oxidation and increased, it is ensured that the conduction of B alloy wire
It is functional..
Description of the drawings
Fig. 1 is a kind of structural schematic diagram of pyroreaction kettle；
Fig. 2 is a kind of internal structure schematic diagram of pyroreaction kettle；
Fig. 3 is to brush device and the structural schematic diagram of mounting assembly；
Fig. 4 is the enlarged drawing at A in Fig. 3.
In figure：1, pedestal；11, control panel；2, autoclave body；21, snap ring；3, device is brushed；31, pipe is brushed；311, it brushes
Unit；312, snorkel；313, hole is brushed；32, gas cylinder；33, air pump；4, heating component；5, mounting assembly；51, mounting bracket；
511, support shaft；512, support plate；52, driving motor；53, mounting head；531, mounting hole；532, slot is deformed；533, deformation sheet；
534, non-slip texture；54, binding nut.
Specific implementation mode
Below in conjunction with attached drawing, invention is further described in detail.
The various raw materials used in this patent and source are as follows：
Lanthanum rich rare earth (mass fraction of each component is lanthanum 45%, cerium 15%, praseodymium 18%, neodymium 16%, other rare earth elements 6%) nothing
Xi Shi Fu Tuo metal materials Co., Ltd.
A kind of B alloy wire for thermoelectric generator is made of nisiloy magnesium alloy, is used for the B alloy wire of thermoelectric generator
Including mass fraction be 3.5%-4% silicon, the cobalt of 0.1%-0.5%, the iron of 0.1%-0.3%, the magnesium of 0.1%-0.3%,
The yttrium of 0.05%-0.2%, the niobium of 0.1%-0.5%, the vanadium of 0.1%-0.5%, the carbon of 0.1%-0.25%, 0.2%-0.3%
Antimony, the copper of 0.4%-0.8%, the lanthanum rich rare earth of 0.05%-0.2%, remaining is nickel.
A kind of preparation process of B alloy wire for thermoelectric generator, includes the following steps：
S1, shearing：Raw material are cut into strip and block or spherical；
Nickel is sheared to the strip and block of growth 5-8cm, width 5-8cm, high 20-30cm；It is in 1*1*3cm by cobalt, yttrium, lanthanum rich rare earth shearing
Strip and block.
S2, dispensing：Raw material after shearing are subjected to dispensing in proportion；
S3, melting：Raw material after dispensing are put into and carry out vacuum melting in vacuum melting furnace；
Wherein S3 is specifically included：
B1, first by magnesium and Ni-B alloy at intermediate alloy, intermediate alloy includes the nickel that mass fraction is 60% and mass fraction is
Proportioned magnesium and nickel are added in vacuum melting furnace and carry out melting by 40% magnesium；
B2, after magnesium and nickel fully melt, lanthanum rich rare earth is added, continues melting, at 1500 DEG C after melting 1 minute,
Enter cooling in punching block；
B3, it carries out, to nisiloy magnesium alloy sample detection, the amount that intermediate alloy is added being calculated by the requirement of content of magnesium in formula, and add
Enter remaining nickel；
B4, proportioned intermediate alloy and nickel are put into vacuum melting furnace, heat melting, waits for that intermediate alloy is fully melted with nickel
Afterwards, other small powders are added in vacuum melting furnace.
S4, it forges：Wire rod after melting is carried out to forge amendment, it is desirable that surface is without smooth, impulse- free robustness, without pit；
S5, working process：Wire rod after forging is processed into finished product；
Wherein, S5 is specifically included：
A1, it makes annealing treatment for the first time：Wire rod after forging is done and is made annealing treatment for the first time, annealing is moved back for bell-type for the first time
Fire；
It after wire rod shove charge, first vacuumizes, it is -0.4MPa to be re-filled with argon gas to pressure, and 0.5h is kept the temperature at 400 DEG C, is then risen
Temperature is completed to make annealing treatment for the first time to 1000 DEG C of heat preservation 2.5h, then after being cooled to 400 DEG C of heat preservation 0.5h；
A2, first round drawing process：Multiple drawing is drawn to 8mm by a diameter of 8.5mm, then be drawn to successively 7.5mm, 7mm,
6.5mm, 6mm, 5.5mm, 5mm, 4.5mm, 4mm, 3.5mm, 3mm are drawn to 2.6mm for the last time；
A3, first time pickling：Wire rod after first round drawing process is subjected to pickling, removes surface scale and rust；
A4, it makes annealing treatment for second：Second of annealing is done to the wire rod after forging, second of annealing is continuously to move back
Fire；
It after wire rod shove charge, first vacuumizes, it is that -0.1MPa keeps the temperature 0.5h at 1000 DEG C to be re-filled with argon gas to pressure, is then dropped
Temperature completes second of annealing to 900 DEG C of heat preservation 1.5h after being finally cooled to 600 DEG C of heat preservation 0.5h；
A5, the second wheel drawing process：Multiple drawing is drawn to 2.3mm by a diameter of 2.6mm, then be drawn to successively 2mm,
1.8mm, 1.58mm, 1.48mm are simultaneously finally drawn to 1.37mm semi-finished product are made；
A6, screening：Product of accomplishing after second wheel drawing process are sieved, underproof product continues, qualified semi-finished product
Continue A7；
A7, third round drawing process：Multiple drawing is drawn to 1.18mm by a diameter of 1.37mm, then be drawn to successively 1mm,
0.82mm, 0.65mm are simultaneously finally drawn to 0.53mm finished product are made；
A8, second of pickling：Semi-finished product qualified after screening are subjected to pickling, remove qualified surface of semi-finished oxide skin and corrosion
Object；
A9, Dehydroepiandrosterone derivative：It is placed on melted finished product in pyroreaction kettle, finished surface is carried out using high-pressure spray gun
Brush carbon dioxide.Alkaline drier is placed in pyroreaction kettle.
S6, storage is examined：Dimension control is carried out to the finished product after working process, certified products are stored in storehouse, defective work weight
Newly melt down smelting.
Refer to the attached drawing 1 and attached drawing 2, the pyroreaction kettle used in preparation process, including pedestal 1, autoclave body 2, brush device
3, heating component 4 and the mounting assembly 5 for installing wire rod.Autoclave body 2 is mounted on pedestal 1, and mounting assembly 5 is installed on autoclave body 2
Interior, heating component 4 is installed on the inner peripheral surface of autoclave body 2.The side of pedestal 1 is provided with control panel 11.
Brush device 3 include be installed in autoclave body 2 brush pipe 31, with brush the gas cylinder 32 and be installed on that pipe 31 is connected
Gas cylinder 32 and brush the air pump 33 between pipe 31.The carbon dioxide in gas cylinder 32 is sent into autoclave body by brushing pipe 31 by air pump 33
In 2.
Refer to the attached drawing 3 brushes pipe 31 and is arranged in the turriform of multilayer, if including dried layer annular brush unit 311, it is adjacent to blow
It strokes and is connected by several snorkels 312 between unit 311, snorkel 312 is uniformly distributed along unit 311 is brushed.Brush unit 311
It is offered towards mounting assembly 5 and several brushes hole 313.
It is provided with several snap rings 21 on 2 inner wall of autoclave body, brushes pipe 31 and is arranged in snap ring 21, brush pipe to realize
31 installation is fixed.
Mounting assembly 5 includes the mounting bracket 51 for being installed on 2 middle part of autoclave body, is installed on the driving motor 52 at 2 top of autoclave body
With several mounting heads 53 being installed in mounting bracket 51.Include turn synchronous with the shaft of driving motor 52 in mounting bracket 51
Dynamic support shaft 511 and the support plate 512 mounted on 511 top of the support shaft, mounting head 53 are uniformly distributed in support plate
512 lower surface.
Refer to the attached drawing 3 and attached drawing 4, the middle part of mounting head 53 offers the mounting hole 531 being inserted into for wire rod, mounting head 53
Side wall lower end offer several deformation slot 532, deformation slot 532 side wall of mounting head 53 is separated into several deformation sheets
533, the top of mounting head 53 is equipped with the binding nut 54 for compressing deformation sheet 533.Mounting head 53 is from far from mounting hole 531
One end of oral area gradually increases to one end diameter close to 531 oral area of mounting hole.
When installing wire rod, wire rod is packed into mounting hole 531, by rotating binding nut 54, deformation sheet 533 is pressed
Tightly, deformation sheet 533 clamps wire rod, and the installation to realize wire rod is fixed.
The inside of deformation sheet 533 is provided with non-slip texture 534, to increase the frictional force between wire rod, improves line
The stability of material installation.
At work, carbon dioxide blows to mounting bracket 51 by air pump 33 by brushing pipe 31, and driving motor 52 drives
Mounting assembly 5 rotates, and then the wire rod being mounted in mounting assembly 5 is driven to be rotated so that so that carbon dioxide is to line
Material brushes more uniformly.On the one hand, high temperature gas flow blows out the hydrogen of wire surface, quickly reduces and is attached to wire surface
The amount of hydrogen；On the other hand, under high temperature environment, carbon dioxide reacts with hydrogen, to remove hydrogen.
B alloy wire in use, is in the condition of high temperature, thus the fusing-off temperature of B alloy wire will directly determine B alloy wire
Use temperature range.Fusing-off temperature detection is carried out made of the B alloy wire for thermoelectric generator to different ratios of raw materials.
Resistance value detection before the fusing-off temperature of the B alloy wire of 1 different component content of table and fusing
Can be obtained from upper table, according in this patent component proportion and preparation process prepare B alloy wire, fusing-off temperature is equal
Reached 1500 DEG C or more, and before fusing resistance value do not increase thus B alloy wire use temperature range it is big, be not easy to fuse.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, people in the art
Member can as needed make the present embodiment the modification of not creative contribution after reading this specification, but as long as at this
It is all protected by Patent Law in the right of invention.
Claims (10)
1. a kind of B alloy wire for thermoelectric generator, which is characterized in that be made of nisiloy magnesium alloy, including mass fraction is
The silicon of 3.5%-4%, the cobalt of 0.1%-0.5%, the iron of 0.1%-0.3%, the magnesium of 0.1%-0.3%, 0.05%-0.2%'s
Yttrium, the niobium of 0.1%-0.5%, the vanadium of 0.1%-0.5%, the carbon of 0.1%-0.25%, remaining is nickel.
2. a kind of B alloy wire for thermoelectric generator according to claim 1, which is characterized in that be used for thermoelectric generator
B alloy wire in further include have mass fraction be 0.05%-0.2% lanthanum rich rare earth.
3. a kind of B alloy wire for thermoelectric generator according to claim 2, which is characterized in that be used for thermoelectric generator
B alloy wire in further include have mass fraction be 0.2%-0.3% antimony.
4. a kind of B alloy wire for thermoelectric generator according to claim 1, which is characterized in that be used for thermoelectric generator
B alloy wire in further include have mass fraction be 0.4%-0.8% copper.
5. a kind of preparation process of B alloy wire for thermoelectric generator, which is characterized in that include the following steps：
S1, shearing：Raw material are cut into strip and block or spherical；
S2, dispensing：Raw material after shearing are subjected to dispensing in proportion；
S3, melting：Raw material after dispensing are put into vacuum melting furnace and carries out vacuum melting and is cooled and shaped；
S4, it forges：Wire rod after melting is carried out to forge amendment；
S5, working process：Wire rod after forging carries out drawing process and forms finished product；
S6, storage is examined：It tests to the finished product after working process, certified products are stored in storehouse.
6. a kind of preparation process of B alloy wire for thermoelectric generator according to any one of claim 1 to 5,
It is characterized in that, the S5 is specifically included：
A1, it makes annealing treatment for the first time：Wire rod after forging is done and is made annealing treatment for the first time, annealing is moved back for bell-type for the first time
Fire；
A2, first round drawing process：Multiple drawing is gradually drawn to 2.6mm by a diameter of 8.5mm；
A3, first time pickling：Wire rod after first round drawing process is subjected to pickling, removes surface scale and rust；
A4, it makes annealing treatment for second：Second of annealing is done to the wire rod after forging, second of annealing is continuously to move back
Fire；
A5, the second wheel drawing process：Multiple drawing is gradually drawn to 1.37mm by a diameter of 2.6mm and semi-finished product is made；
A6, screening：Product of accomplishing after second wheel drawing process are sieved, other productions are according to circumstances made in underproof product
Product, qualified semi-finished product continue A7；
A7, third round drawing process：Multiple drawing is gradually drawn to 0.53mm by a diameter of 1.37mm and finished product is made；
A8, second of pickling：Semi-finished product qualified after screening are subjected to pickling, remove qualified surface of semi-finished oxide skin and corrosion
Object.
7. a kind of preparation process of B alloy wire for thermoelectric generator according to claim 1, which is characterized in that described
S3 specifically comprises the following steps：
B1, first by magnesium and Ni-B alloy at intermediate alloy, intermediate alloy includes the nickel that mass fraction is 60% and mass fraction is
Proportioned magnesium and nickel are added in vacuum melting furnace and carry out melting by 40% magnesium；
B2, after magnesium and nickel fully melt, lanthanum rich rare earth is added, continues melting, at 1500 DEG C after melting 1 minute,
Enter cooling in punching block；
B3, it carries out, to nisiloy magnesium alloy sample detection, the amount that intermediate alloy is added being calculated by the requirement of content of magnesium in formula, and add
Enter remaining nickel；
B4, proportioned intermediate alloy and nickel are put into vacuum melting furnace, heat melting, waits for that intermediate alloy is fully melted with nickel
Afterwards, other small powders are added in vacuum melting furnace.
8. a kind of preparation process of B alloy wire for thermoelectric generator according to claim 5, which is characterized in that wait for A8
After, continue A9, Dehydroepiandrosterone derivative：By melted finished product, finished surface is brushed using high-pressure spray gun.
9. a kind of preparation process of B alloy wire for thermoelectric generator according to claim 8, which is characterized in that dehydrogenation
When processing, finished product is positioned in pyroreaction kettle, the gas used in high-pressure spray gun is carbon dioxide.
10. a kind of preparation process of the B alloy wire for thermoelectric generator of K shapes thermocouple according to claim 9,
It is characterized in that, alkaline drier is placed in pyroreaction kettle.
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