CN108486418B - Alloy wire for thermoelectric generator and preparation process thereof - Google Patents
Alloy wire for thermoelectric generator and preparation process thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C19/00—Alloys based on nickel or cobalt
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- 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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Abstract
The invention relates to the field of power generation equipment, in particular to an alloy wire for a thermoelectric generator and a preparation process thereof, which solve the problem of low power generation efficiency by using fuel gas in the prior art, and the technical scheme is characterized in that the alloy wire for the thermoelectric generator is made of nickel-silicon-magnesium alloy and comprises 3.5-4% of silicon, 0.1-0.5% of cobalt, 0.1-0.3% of iron, 0.1-0.3% of magnesium, 0.05-0.2% of yttrium, 0.1-0.5% of niobium, 0.1-0.5% of vanadium, 0.1-0.25% of carbon and the balance of nickel by mass, and the fusing temperature of the alloy wire is improved by improving the heat resistance and the high-temperature stability of the alloy wire; meanwhile, the oxidation resistance of the alloy wire is improved, so that the resistance value of the alloy wire is prevented from being increased due to oxidation, and the good conductivity of the alloy wire is ensured.
Description
Technical Field
The invention relates to the field of power generation equipment, in particular to an alloy wire for a thermoelectric generator and a preparation process thereof.
Background
The power generation is to convert water energy, heat energy of fossil fuel, nuclear energy, solar energy, wind energy, geothermal energy, ocean energy and the like into electric energy by utilizing a power generation power device. The most common way is to generate electricity by using the heat energy of fossil fuel, and the existing fossil fuel generation has low power generation efficiency and generates certain pollution.
The gas power generation is one of the most stable power generation modes in the power generation by using fossil fuel, and the gas generator set in the prior art is mainly divided into two types, namely a combined cycle gas turbine and a gas internal combustion engine, and the common point of the two types is a power generation mode for converting internal energy into kinetic energy and then converting the kinetic energy into electric energy. Each time of energy conversion generates certain energy loss, and two times of energy conversion is performed through the power generation mode of internal energy → kinetic energy → electric energy, so that two times of energy loss are generated, and therefore, the common power generation efficiency is less than 50 percent, and the cooling, heating and power triple power generation system is difficult to popularize and use in some small-sized power stations due to the complex structure and high cost of the cooling, heating and power triple power generation system.
Therefore, in the prior art, the thermoelectric generator is invented, has no rotating part, small volume and long service life, and utilizes the Seebeck effect to directly convert heat energy into electric energy, thereby improving the generating efficiency. When the thermoelectric element is used, a p-type thermoelectric element and an n-type thermoelectric element are connected by metal conductor electrodes at the hot end, and the cold ends of the p-type thermoelectric element and the n-type thermoelectric element are respectively connected with cold end electrodes, so that a single thermoelectric element or a single thermocouple is formed. The metal conductor electrode connecting the p-type thermoelectric element and the n-type thermoelectric element is often fused due to the operation under high temperature, so that the use is inconvenient.
Disclosure of Invention
The invention aims to provide an alloy wire for a thermoelectric generator and a preparation process thereof, and the alloy wire has the advantages of strong high-temperature stability and difficulty in fusing.
The technical purpose of the invention is realized by the following technical scheme:
an alloy wire for a thermoelectric generator is made of nickel-silicon-magnesium alloy and comprises, by mass, 3.5% -4% of silicon, 0.1% -0.5% of cobalt, 0.1% -0.3% of iron, 0.1% -0.3% of magnesium, 0.05% -0.2% of yttrium, 0.1% -0.5% of niobium, 0.1% -0.5% of vanadium, 0.1% -0.25% of carbon and the balance of nickel.
By adopting the technical scheme, the fusing temperature of the alloy wire is improved by improving the heat resistance and the stability at high temperature of the alloy wire; meanwhile, the oxidation resistance of the alloy wire is improved, so that the resistance value of the alloy wire is prevented from being increased due to the oxidation inside the alloy wire, and the good conductivity of the alloy wire is ensured.
By adding silicon and magnesium, a silicon-magnesium composite oxide film is easily formed on the surface of the alloy, and compared with a common magnesium oxide film, the silicon-magnesium composite oxide film has higher density and extremely strong oxidation resistance; meanwhile, magnesium and silicon form a magnesium-silicon binary alloy, the magnesium-silicon binary alloy has soft alpha-magnesium and hard phase silicon, has good wear resistance, does not generate the phenomenon of enhanced dissolution or aggregation after the temperature is raised, and has good heat resistance.
By adding iron, the toughness of the alloy wire is improved.
After magnesium is added, the oxidation resistance of the alloy wire for the thermoelectric generator is greatly improved, a compact magnesium oxide film is formed on the surface, and particularly, the magnesium oxide film has good thermal stability at a high temperature and can prevent the continuous oxidation; meanwhile, the magnesium has the effect of refining grains and improves the high-temperature corrosion resistance of the alloy wire.
By adding yttrium, the diffusion of magnesium in the alloy is accelerated, and the forming speed of a magnesium oxide film is improved; meanwhile, at the junction of the magnesium yttrium oxide film and the alloy matrix, yttrium oxide is distributed to the matrix in a dendritic form to play a role of pinning, and the scattered yttrium oxide causes a vacancy trap effect, so that the bonding strength of the oxide film and the matrix is improved, and the oxidation resistance of the alloy is improved; meanwhile, compared with the common magnesium oxide film, the yttrium-magnesium composite oxide film has stronger oxidation resistance and stability, and improves the stability of the alloy wire at high temperature.
By adding vanadium and carbon, vanadium can play a role in refining grains, so that the strength and the toughness are improved, and simultaneously, vanadium and carbon form carbides in the alloy, so that the hydrogen corrosion resistance is improved.
Preferably, the alloy wire for the thermoelectric generator also comprises lanthanum-rich rare earth with the mass fraction of 0.05-0.2%.
By adopting the technical scheme, the lanthanum-rich rare earth is added to play a role in refining crystal grains in the alloy, and meanwhile, the lanthanum-rich rare earth plays a role in a long-acting weaving agent in the alloy, so that the remelting and recession resistance of the alloy is improved. Therefore, the alloy wire can still keep a stable state in the process of using at high temperature, and the thermal stability of the alloy wire for the thermoelectric generator is improved.
Preferably, the alloy wire for the thermoelectric generator also comprises 0.1-0.3 mass percent of antimony.
By adopting the technical scheme, the heat resistance of the alloy wire is improved by adding antimony, and after the antimony is added, on one hand, the antimony is dissolved into β phase in a solid mode, and on the other hand, the antimony is dispersed and precipitated to form hexagonal D5 phase2Crystalline form of Mg3Sb2Phase, having the advantage of high thermal stability, Mg3Sb2The phase is dispersed in the alloy matrix to play a role in dispersion strengthening, simultaneously, the deficiency of β phase is made up, the phase is used as a non-spontaneous nucleation substrate of α -Mg matrix, and the Mg with an intercrystalline structure and an alloy matrix coherent structure is promoted17Sb12And separating out the phases. Mg (magnesium)17Sb12The phase has the advantages of fine, continuous and uniform distribution, thereby improving the high-temperature performance of the alloy.
On the one hand, the alloy contains silicon and antimony, and on the other hand, heterogeneous crystal nucleus core Mg is synthesized3Sb2Promoting fine dispersion of Mg2Si particles are formed to make the original coarse Mg in the alloy2Si is changed into granular Mg with fine dispersion distribution2Si; on the other hand, the alloy matrix structure is further refined, and the creep resistance of the alloy at the temperature of 150-200 ℃ is obviously improved.
Preferably, the alloy wire for the thermoelectric generator also comprises 0.4-0.8 mass percent of copper.
By adopting the technical scheme, the nickel and the copper form high-strength single-phase austenite, and the single-phase austenite is more corrosion-resistant than other nickel-based alloys in a reducing medium and more corrosion-resistant than nickel and copper in an oxidizing medium facing phosphoric acid, sulfuric acid, hydrochloric acid and organic acid.
A preparation process of an alloy wire for a thermoelectric generator is characterized by comprising the following steps:
s1, shearing: shearing the raw materials into strip blocks or balls;
s2, batching: proportioning the raw materials after shearing according to a proportion;
s3, smelting: putting the raw materials after the burdening into a vacuum smelting furnace for vacuum smelting and cooling and forming;
s4, forging: forging and correcting the smelted wire;
s5, processing: drawing the forged wire to form a finished product;
s6, checking and warehousing: and (5) inspecting the processed finished product, and storing the qualified product in a warehouse.
By adopting the technical scheme, the raw materials are cut into small pieces by shearing, so that the raw materials are convenient to mix and smelt; and the cooled and formed wire is forged through forging, so that the defects of air holes and shrinkage cavities on the wire are reduced, and the microtube structure of the wire is optimized.
Preferably, S5 specifically includes:
a1, first annealing treatment: performing primary annealing treatment on the forged wire rod, wherein the primary annealing treatment is cover annealing;
a2, first drawing treatment: drawing for multiple times, and gradually drawing from 8.5mm to 2.6mm in diameter;
a3, first acid washing: pickling the wire subjected to the first round of drawing treatment to remove surface oxide skin and rusty materials;
a4, second annealing treatment: carrying out secondary annealing treatment on the forged wire rod, wherein the secondary annealing treatment is continuous annealing;
a5, second round drawing treatment: drawing for multiple times, and gradually drawing from the diameter of 2.6mm to 1.37mm to prepare a semi-finished product;
a6, screening: screening finished products after the second round of drawing treatment, manufacturing unqualified products into other products according to conditions, and continuously performing A7 on qualified semi-finished products;
a7, third drawing treatment: drawing for multiple times, and gradually drawing to 0.53mm from 1.37mm in diameter to obtain a finished product;
a8, secondary acid washing: and (4) pickling the screened qualified semi-finished product, and removing oxide skin and rusty materials on the surface of the qualified semi-finished product.
By adopting the technical scheme, the coiled wire is subjected to heat treatment by first annealing treatment and cover annealing, and the single heat treatment amount is large and the use is convenient; through the second annealing treatment and continuous annealing, the wire rod passes through the heat treatment furnace at a high speed, so that deformed crystal grains in the wire rod are converted into uniform equiaxial crystal grains again, and simultaneously, the work hardening and residual internal stress are eliminated.
The defects of inconsistent size or deformation and the like can occur in the drawing process of part of the wire rods, so that the defects can be found in time after screening after the first round of drawing, the semi-finished products which do not meet the requirements can be screened out in advance, and the unqualified products can be made into other products with lower requirements according to the actual conditions; and the qualified product is continuously drawn by the second round to be made into a finished product, so that the yield is greatly improved, and the waste of materials is reduced.
After the wire is drawn, oxide scale and rusty materials remain on the surface of the wire, and the oxide scale and the rusty materials are removed by reacting with acid after twice pickling.
Preferably, the S3 specifically includes the following steps:
b1, firstly, smelting magnesium and nickel into an intermediate alloy, wherein the intermediate alloy comprises 60 mass percent of nickel and 40 mass percent of magnesium, and adding the proportioned magnesium and nickel into a vacuum smelting furnace for smelting;
b2, after the magnesium and the nickel are fully melted, adding lanthanum-rich rare earth, continuing to melt, melting at 1500 ℃ for 1 minute, and pouring into a steel mould for cooling;
b3, sampling and detecting the nickel-silicon-magnesium alloy, calculating the amount of the added intermediate alloy according to the requirement of the magnesium content in the formula, and adding the rest nickel;
and B4, putting the proportioned intermediate alloy and nickel into a vacuum smelting furnace, heating and smelting, and adding other small materials into the vacuum smelting furnace after the intermediate alloy and the nickel are fully molten.
By adopting the technical scheme, the fusing temperature of magnesium is 648 ℃, the fusing temperature of nickel is 1453 ℃, and the density of magnesium is 1.74g/cm3And the density of nickel is 8.9g/cm3In the conventional smelting mode, because the fusing temperature and density of magnesium and nickel are greatly different, the heating temperature needs to be increased and the smelting time needs to be prolonged in the direct smelting process, and meanwhile, the phenomena of burning loss and segregation are easy to generate, and the actual yield is low, so that the phase melting of magnesium and nickel is difficult to realize. Especially as thermoelectricityIn the alloy wire, because the proportion of nickel in the alloy is far greater than that of magnesium, and magnesium is added into nickel, the fusing temperature difference is large, and magnesium and nickel are difficult to form uniform crystal grains, the produced alloy wire has uneven texture and uneven properties, and the accuracy of thermocouple temperature measurement is influenced.
The intermediate alloy of magnesium and nickel is firstly prepared, the content of nickel is more than that of magnesium, and the burning loss rate is lower after vacuum melting; after the lanthanum-rich rare earth is added, the wetting visual angle between the nickel solution and the magnesium is increased, the uniform degree of the magnesium distribution in the nickel is improved, and the segregation of the magnesium is prevented. The produced magnesium-nickel intermediate alloy has uniform and dispersed distribution and fine crystal grains, so that when the intermediate alloy is added into other raw materials to be mixed, the phase melting speed is accelerated, and the burning loss and the uneven distribution of magnesium are reduced.
Preferably, after A8 is finished, the method continues
A9, dehydrogenation treatment: and blowing the surface of the smelted finished product by using a high-pressure spray gun.
By adopting the technical scheme, the high-pressure spray gun is used for blowing the surface of the finished product, so that on one hand, the possibly residual oxide skin or rust on the surface of the wire rod is blown off, and the influence of the oxide skin and the rust on the performance of the wire rod is reduced.
On the other hand, after the acid pickling, the scale or rust reacts with the acid to generate hydrogen, and part of the hydrogen adheres to the surface of the wire rod. Although the wire has good hydrogen corrosion resistance, the wire has extremely strict dimensional requirements due to the special use of the thermocouple, and therefore, small amount of hydrogen corrosion on the surface of the wire still causes small change on the dimension of the wire, thereby causing reduction of the temperature measurement precision of the thermocouple. The hydrogen attached to the surface of the wire is blown out by the high-pressure spray gun, so that the source of the diffused hydrogen is cut off, the hydrogen corrosion is further reduced, and the temperature measurement precision of the thermocouple made of the alloy wire is improved.
Preferably, during dehydrogenation treatment, the finished product is placed in a high-temperature reaction kettle, and the gas used by the high-pressure spray gun is carbon dioxide.
By adopting the technical schemeCarbon dioxide reacts with hydrogen at high temperature, CO2+H2→CO+H2O, thereby facilitating the removal of hydrogen from the high pressure lance.
Preferably, an alkaline drying agent is placed in the high-temperature reaction kettle.
By adopting the technical scheme, on one hand, the alkaline drying agent in the high-temperature reaction kettle can absorb water generated by the reaction of carbon dioxide and hydrogen in time, so that the forward proceeding of the reaction of carbon dioxide and hydrogen is facilitated, and simultaneously, the reaction of carbonic acid molecules generated by mixing carbon dioxide and water and the alkaline drying agent is reduced, so that the waste of carbon dioxide is reduced;
on the other hand, because the alloy has good acid corrosion resistance, part of acid can be attached to the surface of the wire after acid washing, volatilization can be generated under a high-temperature environment, and more acid can be absorbed through the alkaline drying agent, so that the corrosion of the more acid to the high-temperature reaction kettle is reduced.
In conclusion, the invention has the following beneficial effects:
1. through multi-wheel drawing and screening, the yield is improved, and the waste of materials is reduced;
2. by adding the intermediate alloy, the problem that nickel and magnesium are difficult to melt is solved, and the reliability of the alloy wire is improved;
3. the wire rod after acid cleaning is blown with carbon dioxide by a high-pressure spray gun, so that the surface hydrogen corrosion of the wire rod is reduced;
4. the fusing temperature of the alloy wire is improved by improving the heat resistance and the stability at high temperature of the alloy wire; meanwhile, the oxidation resistance of the alloy wire is improved, so that the resistance value of the alloy wire is prevented from being increased due to oxidation, and the good conductivity of the alloy wire is ensured. .
Drawings
FIG. 1 is a schematic structural view of a high-temperature reaction kettle;
FIG. 2 is a schematic view of the internal structure of a high-temperature reaction vessel;
FIG. 3 is a schematic view of the blowing apparatus and mounting assembly;
fig. 4 is an enlarged view of a portion a in fig. 3.
In the figure: 1. a base; 11. a control panel; 2. a kettle body; 21. a snap ring; 3. a blowing device; 31. blowing a pipe; 311. a blowing unit; 312. a breather pipe; 313. blowing holes; 32. a gas cylinder; 33. an air pump; 4. a heating assembly; 5. mounting the component; 51. mounting a bracket; 511. a support shaft; 512. a support disc; 52. a drive motor; 53. a mounting head; 531. mounting holes; 532. a deformation groove; 533. a deformable sheet; 534. anti-skid lines; 54. and (4) clamping the nut.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The various raw materials and sources used in this patent are as follows:
the lanthanum-rich rare earth (the mass fractions of the components are 45% of lanthanum, 15% of cerium, 18% of praseodymium, 16% of neodymium and 6% of other rare earth elements) is tin-free.
An alloy wire for a thermoelectric generator is made of nickel-silicon-magnesium alloy and comprises, by mass, 3.5% -4% of silicon, 0.1% -0.5% of cobalt, 0.1% -0.3% of iron, 0.1% -0.3% of magnesium, 0.05% -0.2% of yttrium, 0.1% -0.5% of niobium, 0.1% -0.5% of vanadium, 0.1% -0.25% of carbon, 0.2% -0.3% of antimony, 0.4% -0.8% of copper, 0.05% -0.2% of lanthanum-rich rare earth and the balance of nickel.
A preparation process of an alloy wire for a thermoelectric generator comprises the following steps:
s1, shearing: shearing the raw materials into strip blocks or balls;
cutting nickel into strips with the length of 5-8cm, the width of 5-8cm and the height of 20-30 cm; cutting the cobalt, yttrium and lanthanum-rich rare earth into 1 × 3cm strips.
S2, batching: proportioning the raw materials after shearing according to a proportion;
s3, smelting: putting the raw materials after the burdening into a vacuum smelting furnace for vacuum smelting;
wherein S3 specifically includes:
b1, firstly, smelting magnesium and nickel into an intermediate alloy, wherein the intermediate alloy comprises 60 mass percent of nickel and 40 mass percent of magnesium, and adding the proportioned magnesium and nickel into a vacuum smelting furnace for smelting;
b2, after the magnesium and the nickel are fully melted, adding lanthanum-rich rare earth, continuing to melt, melting at 1500 ℃ for 1 minute, and pouring into a steel mould for cooling;
b3, sampling and detecting the nickel-silicon-magnesium alloy, calculating the amount of the added intermediate alloy according to the requirement of the magnesium content in the formula, and adding the rest nickel;
and B4, putting the proportioned intermediate alloy and nickel into a vacuum smelting furnace, heating and smelting, and adding other small materials into the vacuum smelting furnace after the intermediate alloy and the nickel are fully molten.
S4, forging: forging and correcting the smelted wire, wherein the surface is required to be smooth, burr-free and pit-free;
s5, processing: processing the forged wire rod into a finished product;
wherein, S5 specifically includes:
a1, first annealing treatment: performing primary annealing treatment on the forged wire rod, wherein the primary annealing treatment is cover annealing;
after the wire rod is charged into a furnace, vacuumizing is firstly carried out, argon is charged until the pressure is-0.4 MPa, the temperature is kept for 0.5h at 400 ℃, then the temperature is raised to 1000 ℃, the temperature is kept for 2.5h, then the temperature is lowered to 400 ℃, the temperature is kept for 0.5h, and then the first annealing treatment is completed;
a2, first drawing treatment: drawing for many times, wherein the diameter is 8.5mm to 8mm, then drawing to 7.5mm, 7mm, 6.5mm, 6mm, 5.5mm, 5mm, 4.5mm, 4mm, 3.5mm and 3mm in sequence, and finally drawing to 2.6 mm;
a3, first acid washing: pickling the wire subjected to the first round of drawing treatment to remove surface oxide skin and rusty materials;
a4, second annealing treatment: carrying out secondary annealing treatment on the forged wire rod, wherein the secondary annealing treatment is continuous annealing;
after the wire rod is charged into a furnace, vacuumizing is firstly carried out, argon is charged until the pressure is-0.1 MPa, the temperature is kept for 0.5h at 1000 ℃, then the temperature is reduced to 900 ℃, the temperature is kept for 1.5h, finally the temperature is reduced to 600 ℃, the temperature is kept for 0.5h, and then secondary annealing is completed;
a5, second round drawing treatment: drawing for multiple times, namely drawing from 2.6mm to 2.3mm in diameter, then drawing to 2mm, 1.8mm, 1.58mm and 1.48mm in sequence, and finally drawing to 1.37mm to prepare a semi-finished product;
a6, screening: screening finished products after the second round of drawing treatment, continuing unqualified products, and continuing A7 on qualified semi-finished products;
a7, third drawing treatment: drawing for multiple times, namely drawing to 1.18mm from the diameter of 1.37mm, then drawing to 1mm, 0.82mm and 0.65mm in sequence, and finally drawing to 0.53mm to obtain a finished product;
a8, secondary acid washing: pickling the screened qualified semi-finished product, and removing oxide skin and rusty materials on the surface of the qualified semi-finished product;
a9, dehydrogenation treatment: and placing the smelted finished product in a high-temperature reaction kettle, and blowing carbon dioxide on the surface of the finished product by using a high-pressure spray gun. And an alkaline drying agent is placed in the high-temperature reaction kettle.
S6, checking and warehousing: and (4) carrying out size inspection on the processed finished product, storing the qualified product in a storehouse, and returning the unqualified product to the furnace for smelting again.
Referring to fig. 1 and 2, the high-temperature reaction kettle used in the preparation process comprises a base 1, a kettle body 2, a blowing device 3, a heating assembly 4 and a mounting assembly 5 for mounting wires. The cauldron body 2 is installed on base 1, and installation component 5 installs in the cauldron body 2, and heating element 4 installs on the inner peripheral surface of the cauldron body 2. One side of the base 1 is provided with a control panel 11.
The blowing device 3 comprises a blowing pipe 31 arranged in the kettle body 2, an air bottle 32 communicated with the blowing pipe 31 and an air pump 33 arranged between the air bottle 32 and the blowing pipe 31. Carbon dioxide in the gas cylinder 32 is sent into the kettle body 2 through the blowing pipe 31 by the air pump 33.
Referring to fig. 3, the blowing pipe 31 is configured in a tower shape with multiple layers, and includes multiple annular blowing units 311, adjacent blowing units 311 are connected by multiple air pipes 312, and the air pipes 312 are uniformly distributed along the blowing units 311. The blowing unit 311 has a plurality of blowing holes 313 opened toward the mounting block 5.
A plurality of clamping rings 21 are arranged on the inner wall of the kettle body 2, and the blowing pipe 31 is clamped in the clamping rings 21, so that the blowing pipe 31 is fixedly installed.
The mounting assembly 5 comprises a mounting bracket 51 mounted in the middle of the kettle body 2, a driving motor 52 mounted on the top of the kettle body 2, and a plurality of mounting heads 53 mounted on the mounting bracket 51. The mounting bracket 51 comprises a supporting shaft 511 which rotates synchronously with the rotating shaft of the driving motor 52 and a supporting plate 512 mounted on the upper part of the supporting shaft 511, and the mounting heads 53 are uniformly distributed on the lower surface of the supporting plate 512.
Referring to fig. 3 and 4, the mounting head 53 is provided at a middle portion thereof with a mounting hole 531 for inserting a wire, the mounting head 53 is provided at a lower end of a sidewall thereof with a plurality of deformation grooves 532, the deformation grooves 532 divide the sidewall of the mounting head 53 into a plurality of deformation pieces 533, and the mounting head 53 is provided at an upper portion thereof with a clamping nut 54 for pressing the deformation pieces 533. The mounting head 53 gradually increases in diameter from an end distant from the mouth of the mounting hole 531 to an end close to the mouth of the mounting hole 531.
When the wire is installed, the wire is installed in the installation hole 531, the deformation piece 533 is pressed by rotating the clamping nut 54, and the deformation piece 533 clamps the wire, thereby realizing the installation and fixation of the wire.
The inner side of the deformation sheet 533 is provided with the anti-slip texture 534, so that the friction force between the deformation sheet and the wire rod is increased, and the stability of the wire rod installation is improved.
During operation, carbon dioxide is blown to the mounting bracket 51 through the blowing pipe 31 by the air pump 33, the driving motor 52 drives the mounting assembly 5 to rotate, and further drives the wires mounted on the mounting assembly 5 to rotate, so that the blowing of the carbon dioxide to the wires is more uniform. On one hand, the high-temperature airflow blows out the hydrogen on the surface of the wire rod, so that the amount of the hydrogen attached to the surface of the wire rod is quickly reduced; on the other hand, in a high-temperature environment, carbon dioxide reacts with hydrogen, thereby removing hydrogen.
The alloy wire is in a high-temperature state in the use process, so the fusing temperature of the alloy wire directly determines the use temperature range of the alloy wire. Fusing temperature detection is carried out on alloy wires which are made of different raw material ratios and used for the thermoelectric generator.
TABLE 1 detection of fusing temperature and resistance before fusing for alloy wires with different component contents
From the above table, it can be seen that the alloy wire prepared according to the component proportion and the preparation process in the patent has the fusing temperature of more than 1500 ℃, and the resistance value before fusing is not increased, so that the alloy wire has a large using temperature range and is not easy to fuse.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (2)
1. An alloy wire for a thermoelectric generator is characterized by being made of nickel-silicon-magnesium alloy and comprising 3.5-4% of silicon, 0.1-0.5% of cobalt, 0.1-0.3% of iron, 0.1-0.3% of magnesium, 0.05-0.2% of yttrium, 0.1-0.5% of niobium, 0.1-0.5% of vanadium, 0.1-0.25% of carbon, 0.05-0.2% of lanthanum-rich rare earth, 0.2-0.3% of antimony and the balance of nickel by mass,
the preparation process of the alloy wire comprises the following steps:
s1, shearing: shearing the raw materials into strip blocks or balls;
s2, batching: proportioning the raw materials after shearing according to a proportion;
s3, smelting: putting the raw materials after the batching into a vacuum smelting furnace for vacuum smelting and cooling and forming, and the method specifically comprises the following steps: b1, firstly, smelting magnesium and nickel into an intermediate alloy, wherein the intermediate alloy comprises 60 mass percent of nickel and 40 mass percent of magnesium, and adding the proportioned magnesium and nickel into a vacuum smelting furnace for smelting;
b2, after the magnesium and the nickel are fully melted, adding lanthanum-rich rare earth, continuing to melt, melting at 1500 ℃ for 1 minute, and pouring into a steel mould for cooling;
b3, sampling and detecting the nickel-silicon-magnesium alloy, calculating the amount of the added intermediate alloy according to the requirement of the magnesium content in the formula, and adding the rest nickel;
b4, putting the proportioned intermediate alloy and nickel into a vacuum smelting furnace, heating and smelting, and adding other small materials into the vacuum smelting furnace after the intermediate alloy and the nickel are fully molten;
s4, forging: forging and correcting the smelted wire;
s5, processing: drawing the forged wire to form a finished product, which specifically comprises the following steps:
a1, first annealing treatment: performing primary annealing treatment on the forged wire rod, wherein the primary annealing treatment is cover annealing;
a2, first drawing treatment: drawing for multiple times, and gradually drawing from 8.5mm to 2.6mm in diameter;
a3, first acid washing: pickling the wire subjected to the first round of drawing treatment to remove surface oxide skin and rusty materials;
a4, second annealing treatment: carrying out secondary annealing treatment on the forged wire rod, wherein the secondary annealing treatment is continuous annealing;
a5, second round drawing treatment: drawing for multiple times, and gradually drawing from the diameter of 2.6mm to 1.37mm to prepare a semi-finished product;
a6, screening: screening finished products after the second round of drawing treatment, manufacturing unqualified products into other products according to conditions, and continuously performing A7 on qualified semi-finished products;
a7, third drawing treatment: drawing for multiple times, and gradually drawing to 0.53mm from 1.37mm in diameter to obtain a finished product;
a8, secondary acid washing: pickling the screened qualified semi-finished product, and removing oxide skin and rusty materials on the surface of the qualified semi-finished product;
a9, dehydrogenation treatment: placing a smelted finished product in a high-temperature reaction kettle, wherein an alkaline drying agent is placed in the high-temperature reaction kettle, and the high-temperature reaction kettle comprises a base (1), a kettle body (2), a blowing device (3), a heating assembly (4) and an installation assembly (5) for installing wires; the kettle body (2) is arranged on the base (1), the mounting component (5) is arranged in the kettle body (2), and the heating component (4) is arranged on the inner circumferential surface of the kettle body (2); a control panel (11) is arranged on one side of the base (1); the blowing device (3) comprises a blowing pipe (31) arranged in the kettle body (2), an air bottle (32) communicated with the blowing pipe (31) and an air pump (33) arranged between the air bottle (32) and the blowing pipe (31); carbon dioxide in the gas cylinder (32) is sent into the kettle body (2) through the blowing pipe (31) by the air pump (33) to blow the surface of the finished product;
s6, checking and warehousing: and (5) inspecting the processed finished product, and storing the qualified product in a warehouse.
2. The alloy wire for a thermoelectric generator according to claim 1, wherein the alloy wire for a thermoelectric generator further comprises copper in an amount of 0.4 to 0.8% by mass.
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| US9870793B2 (en) * | 2013-06-24 | 2018-01-16 | Seagate Technology Llc | Materials for near field transducers and near field transducers containing same |
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| DE3871234D1 (en) * | 1987-05-20 | 1992-06-25 | Nicrobell Pty Ltd | HIGH TEMPERATURE RESISTANT, MINERAL INSULATED AND METAL SHEATHED CABLE. |
| SE528807C2 (en) * | 2004-12-23 | 2007-02-20 | Siemens Ag | Component of a superalloy containing palladium for use in a high temperature environment and use of palladium for resistance to hydrogen embrittlement |
| CN100453669C (en) * | 2007-02-08 | 2009-01-21 | 宜兴市远航合金厂 | High stabilization low resistivity nickel-base material and preparation method thereof |
| DE102010024488B4 (en) * | 2010-06-21 | 2012-04-26 | Thyssenkrupp Vdm Gmbh | Nickel-based alloy |
| DE102013004365B4 (en) * | 2013-03-14 | 2015-09-24 | VDM Metals GmbH | Nickel-based alloy with silicon, aluminum and chrome |
| CN105369067B (en) * | 2015-11-04 | 2017-10-27 | 重庆材料研究院有限公司 | The thermocouple material and preparation method of stable thermometric in oxide isolation |
| CN105220017A (en) * | 2015-11-13 | 2016-01-06 | 无锡清杨机械制造有限公司 | A kind of nickel alloy wire and production method thereof |
| CN105695795A (en) * | 2016-03-09 | 2016-06-22 | 江阴市诚信合金材料有限公司 | High-strength and low-resistance alloy wire and preparation method thereof |
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| US9870793B2 (en) * | 2013-06-24 | 2018-01-16 | Seagate Technology Llc | Materials for near field transducers and near field transducers containing same |
| KR20150017089A (en) * | 2013-08-06 | 2015-02-16 | 창원대학교 산학협력단 | Method of heat treatment of heat-resistant alloy for excellent mechanical properties at very high temperature and heat-resistant alloy the same |
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