Low-expansion special alloy wire and its preparation process

Abstract

The application relates to the technical field of alloy wires, and discloses a low-expansion special alloy wire and a preparation process thereof. The special alloy wire is prepared from 4J36 alloy as raw material through the processes of hot rolling, cold drawing, low-temperature annealing, cold drawing, high-temperature annealing and surface treatment, and has high precision, high surface quality and excellent comprehensive mechanical properties; cobalt carbide nanoparticles are deposited on the surface of the hot-rolled wire rod to reduce the friction in the cold drawing process; cobalt elements diffuse into the alloy during high-temperature annealing to improve the strength, and a protective layer is formed to relieve the hydrogen embrittlement phenomenon in the pickling and phosphorizing process, which is beneficial to the generation of the phosphorizing film; a phosphorizing liquid is prepared, part of dilute phosphoric acid is polymerized into polyphosphoric acid through short-time high-temperature heating, and a composite additive obtained by compounding sodium dodecyl benzene sulfonate and polyethylene glycol is added to prepare a phosphorizing liquid which can form a complete and smooth phosphorizing layer on the surface of the alloy wire.

Description

Technical Field

[0001] This invention relates to the field of alloy wire technology, and discloses a low-expansion special alloy wire and its preparation process. Background Technology

[0002] With technological advancements, the 3C and 5G industries are developing rapidly, with an increasing variety of products and functions, leading to higher requirements for raw material performance. Commonly used materials in the 3C and 5G industries include special alloys such as cobalt-chromium alloys and titanium alloys. Due to the extremely high transmission efficiency required, electronic components generate a great deal of heat during operation. The thermal expansion and contraction of raw materials can cause dimensional accuracy deviations in electronic components, resulting in negative impacts.

[0003] Currently, low-expansion special alloy wires are still in the development stage and there is relatively little research. 4J36 alloy has good machinability and a very low coefficient of expansion, and is widely used in industries such as radio and precision instruments. It is an indispensable material in the 3C and 5G industries. However, products made with current technology often have unstable quality issues such as cracking and peeling, and the existing quality problems make it difficult to meet market demands.

[0004] Therefore, it is of great significance to study a special alloy wire product with high precision, high surface quality, and excellent comprehensive mechanical properties and its preparation process. Summary of the Invention

[0005] The purpose of this invention is to provide a preparation process for low-expansion special alloy wires to solve the problems mentioned in the background art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] A process for preparing a low-expansion special alloy wire includes the following steps: taking alloy material and hot rolling it to obtain hot-rolled wire rod; taking the hot-rolled wire rod and cold drawing, low-temperature annealing, cold drawing, and high-temperature annealing to obtain annealed wire rod; taking the annealed wire rod and surface treating it to obtain special alloy wire.

[0008] A more optimized hot rolling process involves: taking alloy material, heating it to 900–1100℃ for hot rolling to obtain a hot-rolled wire rod with a specification of Φ5mm; cold drawing speed of 50–60m / min, with a diameter reduction of 1mm–2mm controlled for each drawing; low-temperature annealing temperature of 500–600℃, holding time of 2–3h; and high-temperature annealing temperature of 800–1000℃, holding time of 3–4h.

[0009] In a more optimized manner, the hot-rolled wire rod undergoes modification treatment, specifically by spraying a cobalt carbide nanoparticle dispersion onto the surface of the hot-rolled wire rod at a spraying amount of 8–15 mL / m. 2The modified hot-rolled wire rod is obtained by heat treatment at 80-100℃ for 0.5-1h.

[0010] In a more optimized manner, the cobalt carbide nanoparticle dispersion comprises the following raw materials, by weight: 10-12 parts of nano-cobalt carbide powder, 50-60 parts of ethanol, 50-60 parts of water, and 0.2-0.5 parts of sodium dodecylbenzenesulfonate.

[0011] In a more optimized manner, the preparation of the nano-cobalt carbide powder includes the following steps: adding cobalt chloride, potassium ferrous sulfate, sodium dodecylbenzenesulfonate, and carbon nanotubes to a certain amount of water, stirring evenly, rapidly spray drying at low temperature, and then reducing at 900-1000℃ for 1-2 hours to obtain nano-cobalt carbide powder.

[0012] More preferably, the nano-cobalt carbide powder comprises the following raw materials in parts by weight: 40-50 parts cobalt chloride, 3-6 parts potassium ferrocyanide, 0.1-2 parts sodium dodecylbenzenesulfonate, 10-20 parts carbon nanotubes, and 350-400 parts water.

[0013] In a more optimized manner, the surface treatment includes the following steps: taking annealed wire rod, removing the surface layer by peeling and grinding, controlling the diameter reduction to be 0.2mm to 0.4mm, adding pickling solution, soaking at room temperature for 20 to 40 minutes, washing and drying with water, adding phosphating solution, heating to 50 to 60℃ and soaking for 10 to 20 minutes, washing and drying with water to obtain special alloy wire.

[0014] In a more optimized manner, the preparation of the phosphating solution includes the following steps: adding phosphoric acid to water, heating to 200-220°C, reacting for 2-4 hours, then adding water, zinc oxide, copper nitrate, and composite additives, stirring evenly to obtain the phosphating solution.

[0015] In a more optimized manner, the raw materials of the phosphating solution include, by weight: 40-60 parts phosphoric acid, 400-550 parts water, 8-10 parts zinc oxide, 0.5-1 parts copper nitrate, and 0.5-3 parts composite additives; the composite additives include sodium dodecylbenzenesulfonate and polyethylene glycol in a mass ratio of 2:1.

[0016] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0017] (1) The hot-rolled wire rod is surface modified by depositing cobalt carbide nanoparticles on its surface to reduce friction during the drawing process, effectively reduce surface damage, and achieve the requirements of high surface quality. During high-temperature annealing, the cobalt element in the cobalt carbide nanoparticles diffuses into the alloy, thereby generating reinforcement and improving the strength of the alloy.

[0018] (2) The cobalt carbide nanoparticles on the surface layer can also serve as a protective layer to suppress hydrogen embrittlement during pickling and phosphating, and reduce the adverse effects caused by excessive surface pickling, such as increased roughness and residue. This protective layer ensures the smoothness of the alloy wire surface, which is conducive to the adhesion of the phosphating film. The complete phosphating film helps to improve corrosion resistance and mechanical properties.

[0019] (3) Prepare a phosphating solution by raising the phosphoric acid solution to a high temperature and reacting for a short time to polymerize a portion of the phosphoric acid in the solution to generate polyphosphoric acid, thereby obtaining a phosphoric acid-polyphosphoric acid composite phosphating solution, which makes the structure of the phosphating film more compact and regular.

[0020] (4) Add a composite additive made of sodium dodecylbenzenesulfonate and polyethylene glycol, with a mass ratio of 2:1. Sodium dodecylbenzenesulfonate is an anionic surfactant that can enhance the wettability of the alloy surface and make the phosphate group more evenly distributed on the alloy surface. Polyethylene glycol macromolecules can adjust the viscosity of the phosphating solution. When the two are used in a certain proportion, a phosphating solution that can form a complete and smooth phosphating layer on the surface of the alloy wire can be obtained. Detailed Implementation

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] The following examples include the following raw materials: phosphoric acid (CAS: 7664-38-2), zinc oxide (~50nm, Sigma-Aldrich Trading Co., Ltd.), copper nitrate (CAS: 3251-23-8), sodium dodecylbenzenesulfonate (CAS: 25155-30-0), polyethylene glycol (Mn~3350, Sigma-Aldrich Trading Co., Ltd.), pickling solution (model: KT-008, Zaozhuang Tengzhou Sende Building Materials Business Department), 4J36 alloy (model: INVAR, Dongguan Yuegang Mold Steel Co., Ltd.); cobalt chloride (CAS: 7791-13-1); potassium ferrous sulfate (CAS: 14459-95-1, Nanjing Bermuda Biotechnology Co., Ltd.); carbon nanotubes (CAS: 16291-96-6, Shanghai Yuanye Biotechnology Co., Ltd.); ethanol (CAS: 64-17-5);

[0023] The following quantities are by weight;

[0024] Example 1: S1: Take 50 parts of phosphoric acid and 100 parts of water, stir evenly, heat to 210°C, react for 3 hours, then add 400 parts of water, 9 parts of zinc oxide, 0.5 parts of copper nitrate, 2 parts of sodium dodecyl sulfate, and 1 part of polyethylene glycol, stir evenly to obtain phosphating solution;

[0025] S2: Take alloy material, heat it to 1000℃ and hot roll it to obtain hot rolled wire rod with a specification of Φ5mm;

[0026] S3: Add 40 parts cobalt chloride, 4 parts potassium ferrocyanide, 0.5 parts sodium dodecylbenzenesulfonate, and 15 parts carbon nanotubes to 360 parts water, stir for 30 minutes, with an inlet temperature of 150℃ and an outlet temperature of only 70℃, perform rapid low-temperature spray drying, and then reduce at 900℃ for 1 hour to obtain nano cobalt carbide powder.

[0027] S4: Take 10 parts of nano-cobalt carbide powder, 50 parts of ethanol, 50 parts of water, and 0.3 parts of sodium dodecylbenzenesulfonate, and stir at 800 r / min for 0.5 h to obtain a cobalt carbide nanoparticle dispersion. Spray the cobalt carbide nanoparticle dispersion onto the surface of hot-rolled wire rod at a coating amount of 10 mL / m. 2 The modified hot-rolled wire rod was obtained by heat treatment at 90℃ for 0.5h.

[0028] S5: Take the modified hot-rolled wire rod and cold-draw it at a speed of 55 m / min to reduce the diameter of the hot-rolled wire rod from 5 mm to 3 mm; heat it to 550℃ and hold it for 2 hours. After the holding time is completed, nitrogen gas is introduced and the wire rod is cooled to room temperature at a speed of 150 m / min. Then, cold-draw it again at a speed of 55 m / min to reduce the diameter of the hot-rolled wire rod from 3 mm to 1.8 mm. Heat it to 950℃ and hold it for 4 hours. After the holding time is completed, allow it to cool naturally to room temperature to obtain the annealed wire rod.

[0029] S6: Take annealed wire rod, peel and grind it to obtain a Φ1.5mm peeled wire rod, immerse the peeled wire rod in pickling solution, soak at room temperature for 30 minutes, wash and dry it with water, then immerse it in phosphating solution, heat it to 55℃, soak it for 15 minutes, wash and dry it with water to obtain special alloy wire.

[0030] Example 2: S1: Take 60 parts of phosphoric acid and 100 parts of water, stir evenly, heat to 210°C, react for 3 hours, then add 400 parts of water, 10 parts of zinc oxide, 1 part of copper nitrate, 0.6 parts of sodium dodecyl sulfate, and 0.3 parts of polyethylene glycol, stir evenly to obtain phosphating solution;

[0031] S2: Take alloy material, heat it to 1000℃ and hot roll it to obtain hot rolled wire rod with a specification of Φ5mm;

[0032] S3: Add 50 parts cobalt chloride, 6 parts potassium ferrocyanide, 2 parts sodium dodecylbenzenesulfonate, and 20 parts carbon nanotubes to 360 parts water, stir for 30 minutes, with an inlet temperature of 150℃ and an outlet temperature of only 70℃, perform rapid low-temperature spray drying, and then reduce at 900℃ for 1 hour to obtain nano cobalt carbide powder.

[0033] S4: Take 12 parts of nano-cobalt carbide powder, 50 parts of ethanol, 50 parts of water, and 0.5 parts of sodium dodecylbenzenesulfonate, and stir at 800 r / min for 0.5 h to obtain a cobalt carbide nanoparticle dispersion. Spray the cobalt carbide nanoparticle dispersion onto the surface of hot-rolled wire rod at a coating amount of 10 mL / m. 2 The modified hot-rolled wire rod was obtained by heat treatment at 90℃ for 0.5h.

[0034] S5: Take the modified hot-rolled wire rod and cold-draw it at a speed of 60 m / min to reduce the diameter of the hot-rolled wire rod from 5 mm to 3 mm; heat it to 550℃ and hold it for 2 hours. After the holding time is completed, nitrogen gas is introduced and the wire rod is cooled to room temperature at a speed of 150 m / min. Then, cold-draw it again at a speed of 50 m / min to reduce the diameter of the hot-rolled wire rod from 3 mm to 1.8 mm. Heat it to 950℃ and hold it for 4 hours. After the holding time is completed, allow it to cool naturally to room temperature to obtain the annealed wire rod.

[0035] S6: Take annealed wire rod, peel and grind it to obtain a Φ1.5mm peeled wire rod, immerse the peeled wire rod in pickling solution, soak at room temperature for 30 minutes, wash and dry it with water, then immerse it in phosphating solution, heat it to 55℃, soak it for 15 minutes, wash and dry it with water to obtain special alloy wire.

[0036] Example 3: S1: Take 40 parts of phosphoric acid and 100 parts of water, stir evenly, heat to 210°C, react for 3 hours, then add 400 parts of water, 8 parts of zinc oxide, 1 part of copper nitrate, 0.6 parts of sodium dodecyl sulfate, and 0.3 parts of polyethylene glycol, stir evenly to obtain phosphating solution;

[0037] S2: Take alloy material, heat it to 1100℃ and hot roll it to obtain hot rolled wire rod with a specification of Φ5mm;

[0038] S3: Add 45 parts cobalt chloride, 3 parts potassium ferrocyanide, 1 part sodium dodecylbenzenesulfonate, and 10 parts carbon nanotubes to 360 parts water, stir for 30 minutes, with an inlet temperature of 150°C and an outlet temperature of only 70°C, perform rapid low-temperature spray drying, and then reduce at 900°C for 1 hour to obtain nano cobalt carbide powder.

[0039] S4: Take 11 parts of nano-cobalt carbide powder, 50 parts of ethanol, 50 parts of water, and 0.3 parts of sodium dodecylbenzenesulfonate, and stir at 600 r / min for 1 h to obtain a cobalt carbide nanoparticle dispersion. Spray the cobalt carbide nanoparticle dispersion onto the surface of hot-rolled wire rod at a coating amount of 10 mL / m.2 The modified hot-rolled wire rod was obtained by heat treatment at 90℃ for 0.5h.

[0040] S5: Take the modified hot-rolled wire rod and cold-draw it at a speed of 50 m / min to reduce the diameter of the hot-rolled wire rod from 5 mm to 3 mm; heat it to 550℃ and hold it for 2 hours. After the holding time is completed, nitrogen gas is introduced and the wire rod is cooled to room temperature at a speed of 150 m / min. Then, cold-draw it again at a speed of 60 m / min to reduce the diameter of the hot-rolled wire rod from 3 mm to 1.8 mm. Heat it to 950℃ and hold it for 4 hours. After the holding time is completed, allow it to cool naturally to room temperature to obtain the annealed wire rod.

[0041] S6: Take annealed wire rod, peel and grind it to obtain a Φ1.5mm peeled wire rod, immerse the peeled wire rod in pickling solution, soak at room temperature for 30 minutes, wash and dry it with water, then immerse it in phosphating solution, heat it to 55℃, soak it for 15 minutes, wash and dry it with water to obtain special alloy wire.

[0042] Comparative Example 1 (no modification of hot-rolled wire rod, the rest of the methods and steps are the same as in Example 1): S1: Take 50 parts of phosphoric acid and 100 parts of water, stir evenly, heat to 210°C, react for 3 hours, then add 400 parts of water, 9 parts of zinc oxide, 0.5 parts of copper nitrate, 2 parts of sodium dodecyl sulfate, and 1 part of polyethylene glycol, stir evenly to obtain phosphating solution.

[0043] S2: Take alloy material, heat it to 1000℃ and hot roll it to obtain hot rolled wire rod with a specification of Φ5mm;

[0044] S3: Take hot-rolled wire rod and cold-draw it at a speed of 55 m / min to reduce the diameter of the hot-rolled wire rod from 5 mm to 3 mm; heat it to 550℃ and hold it for 2 hours. After the holding time is completed, nitrogen gas is introduced and the wire rod is cooled to room temperature at a speed of 150 m / min. Then cold-draw it again at a speed of 55 m / min to reduce the diameter of the hot-rolled wire rod from 3 mm to 1.8 mm. Heat it to 950℃ and hold it for 4 hours. After the holding time is completed, allow it to cool naturally to room temperature to obtain annealed wire rod.

[0045] S4: Take annealed wire rod, peel and grind it to obtain a Φ1.5mm peeled wire rod, immerse the peeled wire rod in pickling solution, soak at room temperature for 30 minutes, wash and dry it with water, then immerse it in phosphating solution, heat it to 55℃, soak it for 15 minutes, wash and dry it with water to obtain special alloy wire.

[0046] Comparative Example 2 (the nanoparticle modification step is placed before the hot rolling process, and the remaining steps are the same as in Example 1): S1: Take 50 parts of phosphoric acid and 100 parts of water, stir evenly, heat to 210°C, react for 3 hours, then add 400 parts of water, 9 parts of zinc oxide, 0.5 parts of copper nitrate, 2 parts of sodium dodecyl sulfate, and 1 part of polyethylene glycol, stir evenly to obtain phosphating solution;

[0047] S2: Add 40 parts cobalt chloride, 4 parts potassium ferrocyanide, 0.5 parts sodium dodecylbenzenesulfonate, and 15 parts carbon nanotubes to 360 parts water, stir for 30 minutes, with an inlet temperature of 150℃ and an outlet temperature of only 70℃, perform rapid low-temperature spray drying, and then reduce at 900℃ for 1 hour to obtain nano cobalt carbide powder.

[0048] S3: Take 10 parts of nano-cobalt carbide powder, 50 parts of ethanol, 50 parts of water, and 0.3 parts of sodium dodecylbenzenesulfonate, and stir at 800 r / min for 0.5 h to obtain a cobalt carbide nanoparticle dispersion. Spray the cobalt carbide nanoparticle dispersion onto the surface of the alloy material at a spraying amount of 10 mL / m. 2 The modified alloy material was obtained by heat treatment at 90℃ for 0.5h.

[0049] S4: Take the modified alloy material, heat it to 1000℃ and hot roll it to obtain a hot-rolled wire rod with a specification of Φ5mm;

[0050] S5: Take hot-rolled wire rod and cold-draw it at a speed of 55 m / min to reduce the diameter of the hot-rolled wire rod from 5 mm to 3 mm; heat it to 550℃ and hold it for 2 hours. After the holding time is completed, nitrogen gas is introduced and the wire rod is cooled to room temperature at a speed of 150 m / min. Then cold-draw it again at a speed of 55 m / min to reduce the diameter of the hot-rolled wire rod from 3 mm to 1.8 mm. Heat it to 950℃ and hold it for 4 hours. After the holding time is completed, allow it to cool naturally to room temperature to obtain annealed wire rod.

[0051] S6: Take annealed wire rod, peel and grind it to obtain a Φ1.5mm peeled wire rod, immerse the peeled wire rod in pickling solution, soak at room temperature for 30 minutes, wash and dry it with water, then immerse it in phosphating solution, heat it to 55℃, soak it for 15 minutes, wash and dry it with water to obtain special alloy wire.

[0052] Comparative Example 3 (the high-temperature annealing process was changed, and the other steps were the same as in Example 1): S1: Take 50 parts of phosphoric acid and 100 parts of water, stir evenly, heat to 210°C, react for 3 hours, then add 400 parts of water, 9 parts of zinc oxide, 0.5 parts of copper nitrate, 2 parts of sodium dodecyl sulfate, and 1 part of polyethylene glycol, stir evenly to obtain phosphating solution.

[0053] S2: Take alloy material, heat it to 1000℃ and hot roll it to obtain hot rolled wire rod with a specification of Φ5mm;

[0054] S3: Add 40 parts cobalt chloride, 4 parts potassium ferrocyanide, 0.5 parts sodium dodecylbenzenesulfonate, and 15 parts carbon nanotubes to 360 parts water, stir for 30 minutes, with an inlet temperature of 150℃ and an outlet temperature of only 70℃, perform rapid low-temperature spray drying, and then reduce at 900℃ for 1 hour to obtain nano cobalt carbide powder.

[0055] S4: Take 10 parts of nano-cobalt carbide powder, 50 parts of ethanol, 50 parts of water, and 0.3 parts of sodium dodecylbenzenesulfonate, and stir at 800 r / min for 0.5 h to obtain a cobalt carbide nanoparticle dispersion. Spray the cobalt carbide nanoparticle dispersion onto the surface of hot-rolled wire rod at a coating amount of 10 mL / m. 2 The modified hot-rolled wire rod was obtained by heat treatment at 90℃ for 0.5h.

[0056] S5: Take the modified hot-rolled wire rod and cold-draw it at a speed of 55 m / min to reduce the diameter of the hot-rolled wire rod from 5 mm to 3 mm; heat it to 550℃ and hold it for 2 hours. After the holding time is completed, nitrogen gas is introduced and the wire rod is cooled to room temperature at a speed of 150 m / min. Then cold-draw it again at a speed of 55 m / min to reduce the diameter of the hot-rolled wire rod from 3 mm to 1.8 mm. Heat it to 1100℃ and hold it for 6 hours. After the holding time is completed, allow it to cool naturally to room temperature to obtain the annealed wire rod.

[0057] S6: Take annealed wire rod, peel and grind it to obtain a Φ1.5mm peeled wire rod, immerse the peeled wire rod in pickling solution, soak at room temperature for 30 minutes, wash and dry it with water, then immerse it in phosphating solution, heat it to 55℃, soak it for 15 minutes, wash and dry it with water to obtain special alloy wire.

[0058] Comparative Example 4 (the prepared phosphating solution was replaced with the commercially available 2722 phosphating solution, and the remaining methods and steps were the same as in Example 1): S1: Take the alloy material, heat it to 1000℃ and hot roll it to obtain a hot-rolled wire rod with a specification of Φ5mm.

[0059] S2: Add 40 parts cobalt chloride, 4 parts potassium ferrocyanide, 0.5 parts sodium dodecylbenzenesulfonate, and 15 parts carbon nanotubes to 360 parts water, stir for 30 minutes, with an inlet temperature of 150℃ and an outlet temperature of only 70℃, perform rapid low-temperature spray drying, and then reduce at 900℃ for 1 hour to obtain nano cobalt carbide powder.

[0060] S3: Take 10 parts of nano-cobalt carbide powder, 50 parts of ethanol, 50 parts of water, and 0.3 parts of sodium dodecylbenzenesulfonate, and stir at 800 r / min for 0.5 h to obtain a cobalt carbide nanoparticle dispersion. Spray the cobalt carbide nanoparticle dispersion onto the surface of hot-rolled wire rod at a coating amount of 10 mL / m. 2 The modified hot-rolled wire rod was obtained by heat treatment at 90℃ for 0.5h.

[0061] S4: Take hot-rolled wire rod and cold-draw it at a speed of 55 m / min to reduce the diameter of the hot-rolled wire rod from 5 mm to 3 mm; heat it to 550℃ and hold it for 2 hours. After the holding time is completed, nitrogen gas is introduced and the wire rod is cooled to room temperature at a speed of 150 m / min. Then cold-draw it again at a speed of 55 m / min to reduce the diameter of the hot-rolled wire rod from 3 mm to 1.8 mm. Heat it to 950℃ and hold it for 4 hours. After the holding time is completed, allow it to cool naturally to room temperature to obtain annealed wire rod.

[0062] S5: Take annealed wire rod, peel and grind it to obtain a Φ1.5mm peeled wire rod, immerse the peeled wire rod in pickling solution, soak at room temperature for 30 minutes, wash and dry it with water, then immerse it in phosphating solution 2722, heat it to 55℃, soak it for 15 minutes, wash and dry it with water to obtain special alloy wire.

[0063] Experiment: Special alloy wires obtained from Examples 1-3 and Comparative Examples 1-4 were used. The tensile strength, yield strength, elongation, reduction of area, and Vickers hardness of the special alloy wires at 20℃ were tested according to the test standards GB / T 228, GB / T6569-86, and GB / T 4340.1-2009. The surface morphology of the special alloy wires was also observed. The data are shown in the table below:

[0064]

[0065] Conclusion: As shown in the table above, the method provided in Example 1 is the optimal solution. The comparative examples show that without modification of the hot-rolled wire rod with cobalt carbide nanoparticles, the resulting alloy wire exhibits decreased performance and poor surface quality, failing to meet the requirements for high precision and high surface quality. Changing the position of the cobalt carbide nanoparticle modification process also affects the alloy wire's performance. Comparative Example 3 shows that excessively long high-temperature annealing time leads to a decrease in the alloy's tensile strength, yield strength, and reduction of area. Although the elongation increases, surface scars remain, failing to meet requirements. Comparative Example 4 shows that the phosphating solution prepared by this invention can make the phosphating film structure more compact and regular, forming a complete and smooth phosphating layer on the alloy wire surface.

[0066] In summary, the method provided by this invention can prepare a low-expansion special alloy wire with high precision, high surface quality, and excellent comprehensive mechanical properties.

[0067] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0068] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A process for the production of low expansion special alloy wire, characterized in that: It comprises the following steps: Take the alloy material, heat to 900-1100℃ for hot rolling to obtain hot-rolled wire rod with a specification of Φ5mm; take the hot-rolled wire rod for cold drawing, low-temperature annealing, cold drawing, high-temperature annealing to obtain annealed wire rod; take the annealed wire rod to remove the surface layer by peeling and grinding, control the diameter reduction amount to be 0.2-0.4mm, add pickling solution, soak at room temperature for 20-40min, wash with water and dry, add phosphating solution, heat to 50-60℃ for 10-20min, wash with water and dry to obtain the special alloy wire; The alloy material is 4J36 alloy; The cold drawing speed is 50-60m / min, and the diameter reduction amount is controlled to be 1-2mm each time; The low-temperature annealing temperature is 500-600℃, and the time is 2-3h; The high-temperature annealing temperature is 800-1000℃, and the time is 3-4h; The hot-rolled wire rod is subjected to modification treatment, and the specific steps are as follows: spraying cobalt carbide nanoparticle dispersion liquid on the surface of the hot-rolled wire rod, and the spraying amount is 8-15 mL / m 2 , 80-100 ℃ heat treatment for 0.5-1 h, and the modified hot-rolled wire rod is obtained. The raw materials of the phosphating solution include: 40-60 parts of phosphoric acid, 400-550 parts of water, 8-10 parts of zinc oxide, 0.5-1 part of copper nitrate, and 0.5-3 parts of composite additives; the composite additives include sodium dodecyl benzene sulfonate and polyethylene glycol, and the mass ratio is 2:

1.

2. A process for the production of low expansion special alloy wire as claimed in claim 1, wherein: The preparation of the cobalt carbide nanoparticle dispersion liquid comprises the following raw materials, by weight fraction: 10-12 parts of nanometer cobalt carbide powder, 50-60 parts of ethanol, 50-60 parts of water, and 0.2-0.5 parts of sodium dodecyl benzene sulfonate.

3. A process for the production of low expansion special alloy wire as claimed in claim 2, wherein: The preparation of the nanometer cobalt carbide powder comprises the following steps: Take cobalt chloride, potassium ferrite, sodium dodecyl benzene sulfonate, and carbon nanotubes, add water, stir uniformly, fast low-temperature spray drying, then reduce at 900-1000℃ for 1-2h to obtain nanometer cobalt carbide powder.

4. The process for producing a low expansion special alloy wire according to claim 3, wherein: The preparation of the nanometer cobalt carbide powder comprises the following raw materials, by weight fraction: 40-50 parts of cobalt chloride, 3-6 parts of potassium ferrite, 0.1-2 parts of sodium dodecyl benzene sulfonate, 10-20 parts of carbon nanotubes, and 350-400 parts of water.

5. The process for producing a low expansion special alloy wire as claimed in claim 1, wherein: The preparation of the phosphating solution comprises the following steps: Take phosphoric acid, add water, heat to 200-220℃, react for 2-4h, then add water, zinc oxide, copper nitrate, and composite additives, stir uniformly to obtain the phosphating solution.

6. The low-expansion special alloy wire prepared by the preparation process of the low-expansion special alloy wire according to any one of claims 1-5.

Images