CN115608803A - A kind of preparation method of tantalum or tantalum alloy fiber - Google Patents

Abstract

The invention discloses a method for preparing tantalum or tantalum alloy fibers. The method comprises: 1. cleaning tantalum wire or tantalum alloy wire and copper foil with acid and alkali, drying and preheating respectively; The heated copper foil extrudes and wraps the preheated tantalum wire or tantalum alloy wire to obtain copper-coated tantalum wire or copper-coated tantalum alloy wire; Pulled diameter reduction processing, after annealing to obtain composite wire; 4. After pickling, wash with water and dry to obtain tantalum fiber or tantalum alloy fiber. The invention realizes metallurgical bonding between the copper isolation layer and the core wire of the tantalum wire or tantalum alloy wire through preheating and extrusion coating, and improves the bonding strength and bonding uniformity between the copper isolation layer and the core wire , to avoid the adhesion and broken wires between the core wires, improve the quality of tantalum fiber or tantalum alloy fiber, and can be used as a blendable metal fiber yarn for the field of radiation protection fabrics.

Description

A kind of preparation method of tantalum or tantalum alloy fiber

technical field

The invention belongs to the technical field of metal processing, and in particular relates to a preparation method of tantalum or tantalum alloy fibers.

Background technique

Tantalum has physical properties such as high density, radiation resistance, high ductility, strong corrosion resistance and excellent biocompatibility, and has broad application prospects. In chemical, electronic, electrical and other industries, tantalum can be used to replace stainless steel, and its service life can be increased by dozens of times compared with stainless steel. The capacitor equipment manufactured replaces the precious metal platinum, which greatly reduces the required cost. As a biological material, tantalum has good biocompatibility with human body fluids. The relevant literature shows that tantalum staples are used in thoracic surgery to close blood vessels and arteries without allergic reactions, and in craniotomy to seal the skull Medical fields such as porosity account for about 1% of tantalum usage. The hybridization of tantalum or tantalum alloy wire (especially with a wire diameter of less than 0.05mm) and implant material can also improve the high affinity of cells, thereby improving the combination of bone and implant. In addition, tantalum or tantalum alloys have excellent shielding properties against X, γ and other rays, and tantalum or tantalum alloy fibers can be blended with chemical fibers to fabrics, used as protective clothing, and have the characteristics of breathability and moisture permeability. Therefore, tantalum metal has been widely used in biomedicine, aviation, aerospace, marine, military and other fields.

Micron-level metal fibers can be prepared by cluster drawing technology, which has been widely used in stainless steel, nickel-based alloy fibers and other metals. The process first requires electroplating copper on the surface of the wire, which plays an isolation role during the drawing process. Due to the excellent corrosion resistance of tantalum wire and tantalum alloy wire, it is easy to form an oxide film during electroplating, resulting in poor adhesion of the copper coating and uneven coating. Cohesion and broken wires between tantalum alloy wires will lead to poor dispersion of subsequent fibers, which will affect the use. Therefore, solving the binding force and uniformity of the isolation layer is the key to preparing tantalum or tantalum alloy fibers by the cluster drawing method.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for preparing tantalum or tantalum alloy fibers for the above-mentioned deficiencies in the prior art. This method realizes metallurgical bonding between the copper isolation layer and the core wire of the tantalum wire or tantalum alloy wire through preheating and extrusion coating, and improves the bonding strength and bonding uniformity between the copper isolation layer and the core wire , which greatly improves the quality of tantalum fiber or tantalum alloy fiber, and solves the problems of uneven copper plating, poor bonding strength between copper plating and core wire, and easy delamination and shedding in the subsequent drawing process.

In order to solve the above technical problems, the technical solution adopted in the present invention is: a method for preparing tantalum or tantalum alloy fibers, characterized in that the method comprises the following steps:

Step 1. Cleaning and drying the tantalum wire or tantalum alloy wire and the copper foil with acid and alkali respectively, and then preheating respectively; the diameter of the tantalum wire or tantalum alloy wire is 0.2mm~0.4mm, and the The thickness of the copper foil is 0.02mm~0.04mm;

Step 2, extruding and winding the preheated tantalum wire or tantalum alloy wire with the preheated copper foil in step 1 to obtain copper-coated tantalum wire or copper-coated tantalum alloy wire;

Step 3, combining the copper-coated tantalum wire or copper-coated tantalum alloy wire obtained in step 2 to obtain a composite body, and then performing forging and drawing on the composite body for diameter reduction, and then annealing to obtain a composite wire;

Step 4: Pickling the composite wire obtained in Step 3, washing with water and drying to obtain tantalum fibers or tantalum alloy fibers.

Different from the existing cladding preparation technology and equipment, it mainly uses thicker metal strips (thickness above 0.2mm) to coat thicker rods (diameter 2mm~10mm), and does not continue the second time after cladding is completed. For deformation processing, the present invention uses copper foil with a thickness of 0.02mm~0.04mm to cover tantalum wire or tantalum alloy wire with a wire diameter of 0.2mm~0.4mm. Since the specifications of copper foil and wire are smaller, the wrapping It is more difficult to cover. In this regard, in the present invention, the tantalum wire or tantalum alloy wire and the copper foil material are respectively acid- and alkali-cleaned, dried, and preheated, and then the copper foil material is used as a coating isolation layer, and the tantalum wire or tantalum alloy wire is used as a core wire. , the extrusion coating method is used to make the preheated copper foil material coated on the surface of the preheated tantalum wire or tantalum alloy wire and form a firm interatomic metallurgical solid-phase combination, forming a firm and indivisible overall structure, and obtaining Copper-coated tantalum wire or copper-coated tantalum alloy wire, and then through cluster drawing, diameter reduction processing, and annealing to obtain multi-core composite wire, use pickling to remove the coated surface copper layer and cluster composite sheathing material to obtain Tantalum fiber or tantalum alloy fiber realizes the synergistic deformation ability of the three materials of copper cladding layer, core wire and cladding layer, improves the bonding force and coating uniformity of copper cladding layer and wire material, and avoids pulling, The delamination of the copper cladding layer during the diameter reduction process prevents adhesion and wire breakage between the tantalum wire and the tantalum alloy wire.

The above-mentioned preparation method of tantalum or tantalum alloy fibers is characterized in that the pickling liquid used in the acid and alkali cleaning in step 1 consists of oxalic acid with a mass content of 5% to 15%, oxalic acid with a mass content of 3% to 5%. Composed of nitric acid and water, the alkali washing solution used is composed of sodium hydroxide and water with a mass content of 5% to 10%, and the acid and alkali cleaning time is 20s to 30s. The above pickling solution, alkaline cleaning solution and acid and alkali cleaning time effectively remove the oxide layer and oil stain on the surface of the tantalum wire or tantalum alloy wire substrate and the copper foil cladding layer, and form etching pits on the substrate and cladding layer , which is conducive to enhancing the coating binding force of the two.

The above-mentioned method for preparing tantalum or tantalum alloy fibers is characterized in that the preheating of the tantalum wire or tantalum alloy wire in step 1 adopts induction preheating under a protective atmosphere, and the preheating temperature is 800°C~1000°C , the preheating of the copper foil material adopts electric preheating, and the preheating temperature is 500°C~800°C. Due to the high resistivity and poor electrical conductivity of tantalum or tantalum alloy wire, the heating speed of induction preheating is fast, and it will not cause changes in the structure and properties of tantalum or tantalum alloy; due to the low melting point of copper, poor high-temperature mechanical properties, too high The preheating temperature will lead to deformation, distortion, and fracture of the copper foil. At the same time, the preheating temperature is too low to realize the metallurgical bonding of copper and tantalum during the extrusion process. Therefore, the two materials use the above two different preheating temperatures. and preheating methods.

The above-mentioned method for preparing tantalum or tantalum alloy fibers is characterized in that the process of extrusion coating in step 2 is as follows: the preheated copper foil is respectively placed on the preheated tantalum wire or tantalum The upper and lower parts of the alloy wire are then fed into the bonding roller at the same time for extrusion under a protective atmosphere, so that the upper and lower copper foil materials are coated on the surface of the tantalum wire or tantalum alloy wire to form a solid phase metallurgical bond; the protection The atmosphere is nitrogen, argon or helium.

The above-mentioned method for preparing tantalum or tantalum alloy fibers is characterized in that the upper and lower copper foils are center-symmetrically coated on the surface of the tantalum wire or tantalum alloy wire. By adopting symmetrical coating, it is ensured that there is no gap between the copper foil material and the tantalum wire or tantalum alloy wire, and the thickness of the coating layer is uniform.

The above-mentioned method for preparing tantalum or tantalum alloy fibers is characterized in that the number of cores of the complex described in step 3 is 1000-3000 cores, and the cladding material of the complex is copper pipe, steel pipe or high-temperature alloy pipe. The invention controls the number of cores of the composite body to reduce subsequent drawing passes, shorten the processing cycle, reduce production costs, obtain the required tantalum or tantalum alloy fiber diameter, and avoid copper cladding in the composite body caused by too many cores Tantalum-coated wire or copper-coated tantalum alloy wire is entangled, resulting in inconsistent deformation. Usually, the cladding material of the complex in the present invention is selected to be a metal material with high temperature resistance and good elongation, which is similar to tantalum and copper materials in elongation and consistent deformation, so as to facilitate the smooth progress of the subsequent composite diameter reduction process.

The above method for preparing tantalum or tantalum alloy fibers is characterized in that the drawing in step 3 is hot drawing, the temperature of hot drawing is 500°C~700°C, and the pass processing rate is 30%~40 %, the total processing rate is 80%~90%, the temperature of the annealing treatment is 500°C~1000°C, and the holding time is 10min~30min. The present invention adopts a hot drawing process, and the temperature of hot drawing is adjusted according to the material of the sheath material and the wire diameter of the composite body. At the same time, because the copper isolation layer and the core wire in the composite body of the present invention realize a firm metallurgical bond, It overcomes the delamination and shedding phenomenon in the drawing process, thereby increasing the processing rate of hot drawing passes, reducing the number of annealing, reducing the diffusion of copper and tantalum, and further improving the surface quality of tantalum or tantalum alloy fibers.

The above-mentioned preparation method of tantalum or tantalum alloy fibers is characterized in that the pickling solution used in the pickling in step 4 consists of nitric acid solution with a mass concentration of 25% to 30%, hydrochloric acid with a mass concentration of 30% to 35%, The solution and water are mixed according to the volume ratio of 1:4~5:5~8. The above-mentioned pickling solution effectively removes the bundled composite sheath material and the copper cladding layer on the surface of the composite wire, and also corrodes and removes the tantalum-copper diffusion layer formed during the annealing process, thereby improving the quality of the tantalum or tantalum alloy fiber.

Compared with the prior art, the present invention has the following advantages:

1. Different from the traditional electroplating copper process, the present invention achieves metallurgical bonding between the copper isolation layer and the core wire of the tantalum wire or tantalum alloy wire through preheating and extrusion coating, and improves the copper isolation layer and the core wire. The bonding strength and bonding uniformity between the wires overcome the problems of uneven copper plating, poor bonding strength between the copper plating and the core wire, and easy delamination and shedding in the subsequent drawing process, and avoid the gap between the core wires. The adhesion and broken wires of the tantalum fiber or tantalum alloy fiber are realized smoothly, and the quality of the tantalum fiber or tantalum alloy fiber is greatly improved.

2. The present invention overcomes the phenomenon of delamination and shedding during the drawing process by preheating and extrusion coating, thereby increasing the pass processing rate of hot drawing, reducing the number of annealing times, and reducing the copper tantalum Diffusion phenomenon further improves the surface quality of tantalum or tantalum alloy fibers.

3. The surface of the tantalum fiber or tantalum alloy fiber prepared by the present invention is smooth and good in dispersibility, which ensures the performance stability of the mass-produced tantalum or tantalum alloy fiber, improves product quality, and expands its application range.

4. The tantalum or tantalum alloy fiber prepared by the present invention is used as a blendable metal fiber yarn to weave a radiation protection fabric with air permeability and moisture permeability, and the protection efficiency to X or gamma rays with energy less than 200keV is greater than 50%. At the same time, Compared with the traditional electroplating wire bundle drawing method, the preparation method of the invention has stable process and low cost, and has good application value and social benefits.

The technical solutions of the present invention will be described in further detail below with reference to the drawings and embodiments.

Description of drawings

Figure 1 is a schematic diagram of the operation of the extrusion coating and winding process of the present invention.

Explanation of reference signs:

1—tantalum wire or tantalum alloy wire; 2—copper foil material; 3—acid-base cleaning tank; 4—insulation tube; 5—bonding roller; 6—copper-coated tantalum wire or copper-coated tantalum alloy wire; 7—cooling Box; 8—take-up mechanism.

detailed description

Example 1

As shown in Figure 1, this embodiment includes the following steps:

Step 1. Use an automatic feeding device to make the tantalum wire 1 with a wire diameter of 0.4mm and the copper foil material 2 with a thickness of 0.04mm on and below the tantalum wire 1 enter the acid-base cleaning tank 3 for acid and alkali cleaning and drying Dry, wherein, the pickling solution used for acid and alkali cleaning is composed of 15% oxalic acid by mass content, 5% nitric acid by mass content and water, and the alkaline cleaning solution used is composed of 10% sodium hydroxide and water by mass content, and The acid and alkali cleaning time is 30s, and then the dried tantalum wire 1 is sent to the insulating tube 4 wound by the heating coil for induction preheating under the protective atmosphere of nitrogen, and the induction preheating temperature is 800°C, and the dried Finally, the copper foil material 2 located above and below the tantalum wire 1 is energized and preheated by the energized contact roller, and the energized preheating temperature is 500°C;

Step 2. Keep the preheated copper foil material 2 in step 1 above and below the preheated tantalum wire 1, and then simultaneously send it to the bonding roller 5 placed up and down in a protective atmosphere under nitrogen. Squeeze, so that the center of the upper and lower copper foil 2 is symmetrically coated on the surface of the tantalum wire 1 to form a solid-phase metallurgical bond, and is drawn out by the wire take-up mechanism 8 and sent to the cooling box 7 for cooling, and then passed through the winding machine Winding and winding to obtain copper-coated tantalum wire 6;

Step 3: Combine 3,000 copper-coated tantalum wires 6 obtained in Step 2 in an iron pipe to obtain a complex, and then heat the complex to 500°C for forging. The pass processing rate of forging is 30%. When the total processing rate is 80%, the vacuum annealing treatment is carried out at 1000 ° C for 30 minutes to obtain a forged billet with a diameter of 8 mm. When the forged billet is heated to 400 ° C, hot drawing is carried out. The processing rate of the hot drawing pass is 40%. When the total processing rate of hot drawing is 90%, carry out vacuum annealing treatment at 1000 ° C for 30 minutes to obtain a composite wire with a wire diameter of 0.6 mm;

Step 4: pickling the composite wire obtained in step 3 to remove iron by using the pickling solution obtained by mixing nitric acid solution with a mass concentration of 25%, hydrochloric acid solution with a mass concentration of 30%, and water in a volume ratio of 1:5:8 The tube and the clad copper layer were then washed with deionized water and dried at 40°C to 60°C to obtain tantalum fibers with 3000 cores and a wire diameter of 10 μm.

The sheathing material in this embodiment can also be replaced by copper pipes, steel pipes or superalloy pipes other than iron pipes.

Example 2

As shown in Figure 1, this embodiment includes the following steps:

Step 1. Use an automatic feeding device to make the tantalum alloy wire 1 with a wire diameter of 0.3mm and the copper foil material 2 with a thickness of 0.03mm on and below the tantalum alloy wire 1 enter the acid-base cleaning tank 3 for acid and alkali cleaning respectively. And dry, wherein, the pickling liquid that acid, alkali cleaning adopts is made up of the oxalic acid of mass content 10%, the nitric acid of mass content 4% and water, and the alkali washing liquid that adopts is made up of sodium hydroxide and water of mass content 8% , and the acid and alkali cleaning time is 15s, and then the dried tantalum alloy wire 1 is sent into the insulating tube 4 wound by the heating coil, and the induction preheating is carried out under the protective atmosphere of nitrogen, and the induction preheating temperature is 900°C, After drying, the copper foil material 2 positioned above and below the tantalum alloy wire 1 is preheated by passing through the electrified contact roller, and the electrified preheating temperature is 900°C;

Step 2. Keep the preheated copper foil material 2 in step 1 above and below the preheated tantalum alloy wire 1, and then simultaneously feed it into the bonding roller 5 placed up and down in a protective atmosphere under nitrogen. Squeeze, so that the upper and lower copper foil materials 2 are symmetrically coated on the surface of the tantalum alloy wire 1 to form a solid-phase metallurgical bond, and are drawn out by the wire take-up mechanism 8 and sent to the cooling box 7 for cooling, and then rolled Winding machine winding take-up to obtain copper-coated tantalum alloy wire 6;

Step 3: Combine 2,000 copper-coated tantalum alloy wires 6 obtained in Step 2 in an iron pipe to obtain a complex, and then heat the complex to 600°C for forging. The pass processing rate of forging is 35%. When forging When the total processing rate is 80%, carry out vacuum annealing treatment at 600°C for 50 minutes to obtain a forged billet with a diameter of 10mm. When the forged billet is heated to 500°C, hot drawing is carried out, and the pass processing rate of hot drawing is 35%. , when the total processing rate of hot drawing is 90%, vacuum annealing treatment is carried out at 900 °C for 30 minutes to obtain a composite wire with a wire diameter of 0.8 mm;

Step 4: Use the pickling solution obtained by mixing nitric acid solution with a mass concentration of 28%, hydrochloric acid solution with a mass concentration of 32%, and water in a volume ratio of 1:4:6 to pickle the composite wire obtained in step 3 to remove iron The tube and the clad copper layer were then washed with deionized water and dried at 40°C to 60°C to obtain tantalum alloy fibers with 2000 cores and a wire diameter of 10 μm.

Example 3

As shown in Figure 1, this embodiment includes the following steps:

Step 1. Using an automatic feeding device, the tantalum alloy wire 1 with a wire diameter of 0.2mm and the copper foil material 2 with a thickness of 0.02mm on and below the tantalum alloy wire 1 enter the acid-base cleaning tank 3 for acid and alkali cleaning respectively. And dry, wherein, the pickling liquid that acid, alkali cleaning adopts is made up of the oxalic acid of mass content 5%, the nitric acid of mass content 3% and water, and the alkali washing liquid that adopts is made up of sodium hydroxide and water of mass content 5% , and the acid and alkali cleaning time is 20s, and then the dried tantalum alloy wire 1 is sent into the insulating tube 4 wound by the heating coil, and the induction preheating is carried out under the protective atmosphere of nitrogen, and the induction preheating temperature is 1000°C, After drying, the copper foil material 2 positioned above and below the tantalum alloy wire 1 is preheated by passing through the electrified contact roller, and the electrified preheating temperature is 800°C;

Step 2. Keep the preheated copper foil material 2 in step 1 above and below the preheated tantalum alloy wire 1, and then simultaneously feed it into the bonding roller 5 placed up and down in a protective atmosphere under nitrogen. Squeeze, so that the upper and lower copper foil materials 2 are symmetrically coated on the surface of the tantalum alloy wire 1 to form a solid-phase metallurgical bond, and are drawn out by the wire take-up mechanism 8 and sent to the cooling box 7 for cooling, and then rolled Winding machine winding take-up to obtain copper-coated tantalum alloy wire 6;

Step 3: Combine 1,000 copper-clad tantalum alloy wires 6 obtained in Step 2 in an iron pipe to obtain a complex, and then heat the complex to 700°C for forging. The pass processing rate of forging is 35%. When forging When the total processing rate is 80%, carry out vacuum annealing treatment at 1000 °C for 60 minutes to obtain a forged billet with a diameter of 10 mm. When the forged billet is heated to 700 °C, hot drawing is carried out, and the processing rate of hot drawing pass is 35%. , when the total processing rate of hot drawing is 90%, vacuum annealing treatment is carried out at 950°C for 30 minutes to obtain a composite wire with a wire diameter of 0.7mm;

Step 4: pickling the composite wire obtained in step 3 to remove iron by using the pickling solution obtained by mixing nitric acid solution with a mass concentration of 30%, hydrochloric acid solution with a mass concentration of 35%, and water in a volume ratio of 1:4:5 The tube and the clad copper layer were then washed with deionized water and dried at 40°C to 60°C to obtain tantalum alloy fibers with 1000 cores and a wire diameter of 25 μm.

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any way. All simple modifications, changes and equivalent changes made to the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.

Claims (8)

1. a preparation method of tantalum or tantalum alloy fiber, is characterized in that, the method comprises the following steps: Step 1. Cleaning and drying the tantalum wire or tantalum alloy wire and the copper foil with acid and alkali respectively, and then preheating respectively; the diameter of the tantalum wire or tantalum alloy wire is 0.2mm~0.4mm, and the The thickness of the copper foil is 0.02mm~0.04mm; Step 2, extruding and winding the preheated tantalum wire or tantalum alloy wire with the preheated copper foil in step 1 to obtain copper-coated tantalum wire or copper-coated tantalum alloy wire; Step 3, combining the copper-coated tantalum wire or copper-coated tantalum alloy wire obtained in step 2 to obtain a composite body, and then performing forging and drawing on the composite body for diameter reduction, and then annealing to obtain a composite wire; Step 4: Pickling the composite wire obtained in Step 3, washing with water and drying to obtain tantalum fibers or tantalum alloy fibers. 2. the preparation method of a kind of tantalum or tantalum alloy fiber according to claim 1, it is characterized in that, the pickling liquid that the acid in the step 1, alkali cleaning adopts is by the oxalic acid of mass content 5%～15%, mass content Nitric acid with a content of 3% to 5% and water, the alkali washing solution used is composed of sodium hydroxide and water with a mass content of 5% to 10%, and the acid and alkali cleaning time is 20s to 30s. 3. the preparation method of a kind of tantalum or tantalum alloy fiber according to claim 1, is characterized in that, the preheating of tantalum wire or tantalum alloy wire described in step 1 adopts induction preheating under protective atmosphere, and preheating The temperature is 800°C-1000°C, and the preheating of the copper foil material is conducted by electrification, and the preheating temperature is 500°C-800°C. 4. A method for preparing tantalum or tantalum alloy fibers according to claim 1, characterized in that, the process of extrusion coating in step 2 is as follows: the preheated copper foils are respectively placed on the preheated The upper and lower sides of the heated tantalum wire or tantalum alloy wire are then sent to the bonding roller at the same time for extrusion under a protective atmosphere, so that the upper and lower copper foils are covered on the surface of the tantalum wire or tantalum alloy wire to form a solid phase metallurgical combination; the protective atmosphere is nitrogen, argon or helium. 5 . The method for preparing tantalum or tantalum alloy fibers according to claim 4 , wherein the upper and lower copper foils are center-symmetrically coated on the surface of the tantalum wire or tantalum alloy wire. 6. the preparation method of a kind of tantalum or tantalum alloy fiber according to claim 1 is characterized in that, the number of cores of the composite body described in step 3 is 1000～3000 cores, and the cladding material of the composite body is copper tube, Steel pipe or superalloy pipe. 7. The preparation method of a tantalum or tantalum alloy fiber according to claim 1, characterized in that the drawing in step 3 is hot drawing, the temperature of hot drawing is 500°C~700°C, and the pass The processing rate is 30%~40%, the total processing rate is 80%~90%, the temperature of the annealing treatment is 500°C~1000°C, and the holding time is 10min~30min. 8. the preparation method of a kind of tantalum or tantalum alloy fiber according to claim 1, is characterized in that, the pickling solution that pickling adopts in step 4 is by the nitric acid solution of mass concentration 25%～30%, mass concentration 30%~35% hydrochloric acid solution and water are mixed according to the volume ratio of 1:4~5:5~8.

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