CN111778416A - Preparation method of palladium alloy thin-diameter thin-wall capillary tube - Google Patents
Preparation method of palladium alloy thin-diameter thin-wall capillary tube Download PDFInfo
- Publication number
- CN111778416A CN111778416A CN202010668594.9A CN202010668594A CN111778416A CN 111778416 A CN111778416 A CN 111778416A CN 202010668594 A CN202010668594 A CN 202010668594A CN 111778416 A CN111778416 A CN 111778416A
- Authority
- CN
- China
- Prior art keywords
- thin
- palladium alloy
- diameter
- treatment
- ingot
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/06—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
Abstract
The invention discloses a preparation method of a palladium alloy thin-diameter thin-wall capillary tube, which comprises the following steps: firstly, carrying out vacuum induction melting on a palladium alloy raw material, and then pouring to obtain an electrode; secondly, carrying out vacuum arc melting and diffusion annealing on the electrode to obtain an ingot; thirdly, manufacturing a pierced billet from the cast ingot to obtain a pierced billet; fourthly, extruding and straightening the pierced billet to obtain a tube blank; fifthly, rolling the tube blank to obtain a semi-finished tube; and sixthly, drawing the semi-finished pipe to obtain the palladium alloy thin-diameter thin-wall capillary tube. According to the invention, atoms in the ingot are diffused by controlling the technological parameters of duplex smelting and diffusion annealing, so that the uniformity of components and the compactness of the organization structure of the palladium alloy thin-diameter thin-wall capillary tube are ensured, the outer diameter and the wall thickness of the palladium alloy thin-diameter thin-wall capillary tube are reduced by controlling the size of a semi-finished tube and the cooperative optimization among the steps, and the production of the palladium alloy thin-diameter thin-wall capillary tube with high precision, high compactness and high air tightness is realized.
Description
Technical Field
The invention belongs to the technical field of nonferrous metal processing, and particularly relates to a preparation method of a palladium alloy thin-diameter thin-wall capillary tube.
Background
With the application of hydrogen in the fields of petroleum, chemical industry, metallurgy, glass, aerospace, new energy and the like, the requirement on the purity of hydrogen is higher and higher; the main methods for purifying hydrogen include a catalytic method, a metal hydride method, a pressure swing adsorption method, a low-temperature separation method, a palladium alloy membrane diffusion method, a polymer membrane diffusion method and the like, and the membrane diffusion method formed by palladium alloy capillaries is incomparable with other physical methods or chemical methods due to unique purification performance, and is also the current main methods for extracting, separating and purifying hydrogen isotopes.
In order to reduce the comprehensive cost of the device and ensure the reliability and the service life, the hydrogen permeability of the palladium alloy capillary tube is often required to be improved, the alloy components are adjusted, the wall thickness of the capillary tube is reduced, the yield is improved, and the like, so that the efficiency of the device is improved; generally, the wall thickness, the air tightness and the quality of the capillary are controlled to improve the reliability and the service life of the device, and by combining the factors, the wall thickness of the palladium alloy capillary which can be prepared at present is more than 0.1mm, and the yield and the air tightness of the capillary with thinner wall thickness are individually reported to be very low, so that the capillary cannot be used on the device.
In the aspect of material manufacturing and processing, due to the complex composition and structure of palladium alloy, the hardness of alloy cast ingots is large, the plasticity is poor, the processing difficulty is very large, only reports of processing the palladium alloy into small-size and small-specification thick-wall pipes exist at home and abroad, the palladium alloy mostly adopts high-purity palladium powder and other added metal powder, the alloy cast ingots are prepared in a powder mixing mode, the problems of easy element burning loss, difficult component control and the like exist, a small amount of samples can be prepared by partially adopting modes of smelting cast ingots, drilling, rolling, drawing, combining small-processing-rate multi-pass annealing and the like, but the process is complex, the energy consumption is high, the yield is low, the comprehensive cost is high, and the alloy composition stability, the wall thickness, the length and the like of the obtained palladium alloy capillary tube.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a thin-diameter thin-wall capillary tube of palladium alloy, aiming at the defects of the prior art. The method ensures that the components of the cast ingot are uniform and the organization structure is compact through a duplex smelting process of vacuum induction smelting and vacuum consumable arc smelting, avoids the defect of breakage caused by thinner pipe wall thickness in the rolling and drawing processes, diffuses atoms in the cast ingot through diffusion annealing, ensures that all components in the cast ingot are uniformly distributed, further reduces the outer diameter and the wall thickness of the palladium alloy thin-diameter thin-wall capillary tube through controlling the size of a semi-finished pipe and the cooperative optimization among all steps, improves the size precision and the length of the palladium alloy thin-diameter thin-wall capillary tube, and gradually processes the cast ingot into the palladium alloy thin-diameter thin-wall capillary tube, thereby realizing the production of the palladium alloy thin-diameter thin-wall capillary tube with high precision, high density, high air tightness and smooth surface.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a palladium alloy thin-diameter thin-wall capillary tube is characterized by comprising the following steps:
step one, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out casting treatment to obtain an electrode;
step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot; the process of the diffusion annealing treatment comprises the following steps: heating the electrode subjected to vacuum consumable arc melting treatment to 1000-1100 ℃ in an argon atmosphere, and then preserving heat for 10 h;
step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks;
step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the outer diameter of the semi-finished pipe is 5.5 mm-6.0 mm, and the wall thickness is 0.15 mm-0.20 mm;
step six, drawing the semi-finished tube obtained in the step five to obtain the palladium alloy thin-diameter thin-wall capillary tube; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 1.8 mm-phi 3.0mm, and the wall thickness is 0.05 mm-0.10 mm.
The invention adopts the duplex smelting process of vacuum induction smelting and vacuum consumable arc smelting to the palladium alloy raw material, ensures that the components of the cast ingot are uniform and the tissue structure is compact, avoids the defect of cracking caused by thinner tube wall thickness in the rolling and drawing processes, combines the palladium alloy raw material into a whole, diffuses atoms in the cast ingot through diffusion annealing, ensures that all components in the cast ingot are uniformly distributed, thereby ensuring that the components of the palladium alloy thin-diameter thin-wall capillary tube are uniform and the tissue structure is compact, is beneficial to subsequent rolling and drawing, then carries out pipe preparation, extrusion, straightening, rolling and drawing on the cast ingot in sequence, further reduces the wall thickness size of the palladium alloy thin-diameter thin-wall capillary tube through the cooperative optimization among all the steps, improves the size precision and the length of the palladium alloy thin-diameter thin-wall capillary tube, and leads the cast ingot to be processed into the palladium alloy thin-diameter thin-wall capillary tube step by step, the production of the palladium alloy thin-diameter thin-wall capillary with high precision, high density and smooth surface is realized; according to the invention, by controlling the size of the semi-finished tube, the palladium alloy thin-diameter thin-wall capillary tube can be obtained by applying a proper drawing force to the semi-finished tube in the drawing process, and meanwhile, the size of the palladium alloy thin-diameter thin-wall capillary tube is ensured, so that the palladium alloy thin-diameter thin-wall capillary tube meets the requirements of thin diameter and thin wall, the defects that the drawing force is too large and the tube is easy to damage due to too thick wall thickness are avoided, and the defects that the tube is too low in strength and the tube is easy to damage due to too thin wall thickness are avoided; according to the invention, the size of the palladium alloy thin-diameter thin-wall capillary is controlled, so that the palladium alloy thin-diameter thin-wall capillary has optimal strength and hydrogen permeation performance, and can be applied to hydrogen purification, the palladium alloy thin-diameter thin-wall capillary has the highest cost performance, and the preparation cost of the palladium alloy thin-diameter thin-wall capillary is reduced.
The preparation method of the thin-wall capillary with the small diameter is characterized in that in the step one, the palladium alloy raw material consists of palladium and additive metal, the mass fraction of palladium in the palladium alloy raw material is 60-93.33%, and the additive metal is one, two or three of silver, copper, gold, yttrium and nickel; the palladium is a palladium ingot with the mass purity of not less than 99.95%, the silver is a silver ingot with the mass purity of not less than 99.99%, the copper is a copper ingot with the mass purity of not less than 99.95%, the gold is a gold ingot with the mass purity of not less than 99.95%, the yttrium is an yttrium ingot with the mass purity of not less than 99.9%, and the nickel is a nickel ingot with the mass purity of not less than 99.96%. According to the invention, other metal elements are added into palladium to form the palladium alloy, so that the phenomenon that pure metal palladium is subjected to phase change along with temperature change in a hydrogen atmosphere is inhibited, the cost of the palladium alloy raw material is reduced, the hydrogen permeability of the palladium alloy thin-diameter thin-wall capillary tube is improved, the hydrogen embrittlement phenomenon is inhibited, and the strength of the palladium alloy thin-diameter thin-wall capillary tube is improved; according to the invention, by controlling the purity of the palladium alloy raw material, the impurity content in the palladium alloy thin-diameter thin-wall capillary tube is reduced, so that the palladium alloy thin-diameter thin-wall capillary tube has the optimal hydrogen permeation performance and strength, and can be applied to hydrogen purification.
The preparation method of the palladium alloy thin-diameter thin-wall capillary tube is characterized in that the mass fraction of silver in the palladium alloy raw material is 14-25%, the mass fraction of copper is 20-40%, the mass fraction of gold is 2-4%, the mass fraction of yttrium is 2-6.77%, and the mass fraction of nickel is 0.2-0.5%. According to the invention, by controlling the mass fraction of the added metal, the phenomenon that pure metal palladium is subjected to phase change along with temperature change in a hydrogen atmosphere is inhibited, the cost of the palladium alloy raw material is reduced, the hydrogen permeation performance of the palladium alloy thin-diameter thin-wall capillary is improved, the hydrogen embrittlement phenomenon is inhibited, and the strength of the palladium alloy thin-diameter thin-wall capillary is improved.
The preparation method of the thin-wall capillary with the small diameter of the palladium alloy is characterized in that the vacuum induction melting treatment process in the step one is that the palladium alloy raw material is put into a crucible of a vacuum induction melting furnace, and then the vacuum degree in the furnace is kept to be not less than 1 × 10-2Pa, heating to 1500-1600 ℃ and smelting for 10-20 min; the crucible is a magnesium oxide crucible or a calcium oxide crucible; the above-mentionedThe electrodes are cylindrical. According to the invention, the palladium alloy raw material is just melted by controlling the parameters of vacuum induction melting, so that the uniform distribution of each component in the electrode and compact structure are ensured, the subsequent rolling and drawing processing are facilitated, and the volatilization loss of the palladium alloy raw material is reduced; according to the invention, by controlling the material of the crucible, the palladium alloy raw material is ensured not to react with the crucible in the vacuum induction melting process, and the crucible has the advantages of stable performance and no impurity introduction; the invention is beneficial to the subsequent vacuum consumable arc melting by controlling the shape of the electrode.
The preparation method of the thin-diameter thin-wall capillary tube of the palladium alloy is characterized in that the conditions of the vacuum consumable arc melting treatment in the step two are that the arcing voltage is 25V-30V, the arcing current is 800A-850A, the arc stabilizing current is 4A-5A, and the vacuum degree in the furnace is not lower than 1 × 10-1Pa. According to the invention, by controlling the parameters of vacuum consumable arc melting, the components in the ingot are uniformly distributed, the organization structure is compact, the subsequent rolling and drawing processing are facilitated, other impurities are not introduced in the reaction, and the quality and purity of the palladium alloy thin-diameter thin-wall capillary tube are improved.
The preparation method of the thin-walled capillary tube with the small diameter made of the palladium alloy is characterized in that the process of the pierced billet manufacturing treatment in the step three is as follows: and (4) sequentially carrying out head turning, tail removing and peeling on the cast ingot, and then drilling to obtain a pierced billet. According to the invention, the ingot casting is sequentially subjected to head turning, tail removing and peeling, so that the surface of the ingot casting has no macroscopic shrinkage cavity, inclusion, cold shut and other casting defects, the smooth proceeding of the subsequent rolling process is ensured, and the defect of pipe scrapping caused by the development of the casting defects into cracks in the rolling process is avoided; according to the invention, the cast ingot is enabled to have a tubular structure preliminarily through drilling, and the smooth proceeding of subsequent treatment is ensured.
The preparation method of the thin-walled capillary tube with the small diameter made of the palladium alloy is characterized in that the extrusion treatment process in the fourth step is as follows: coating the outer wall of the pierced billet with pure copper foil, and then performing extrusion treatment at the extrusion temperature of 800-850 ℃, wherein the extrusion ratio of the extrusion treatment is 3.5. The invention has the advantages that the pure copper foil is coated, so that the heat preservation effect is realized, the lubricating effect is provided for the extrusion process, the smooth extrusion is facilitated, the quality of the tube blank is improved, and the quality of the thin-diameter thin-wall capillary tube made of the palladium alloy is improved; the invention ensures that the crystal grains in the pierced billet are fully crushed by controlling the extrusion parameters, ensures that the inner surface and the outer surface of the tube billet are smooth and have no visible defects, and is beneficial to the smooth operation of subsequent rolling.
The preparation method of the palladium alloy thin-diameter thin-wall capillary tube is characterized in that the rolling treatment process in the fifth step is as follows: the tube blank is put into a three-roller rolling mill, the pass working ratio is controlled to be 20-30%, 5-7 passes of cold rolling are carried out, and when the cumulative working ratio reaches 40-60%, the tube blank is heated to 700-750 ℃ under the argon atmosphere and then is kept warm for 30 min. The invention controls the parameters of the rolling treatment to make the tube blank fully deform and process into a semi-finished tube, thereby inhibiting the growth of crystal grains in the rolling process, ensuring the quality of the semi-finished tube, preventing the semi-finished tube from cracking in the subsequent drawing treatment, and improving the yield and the length of the semi-finished tube; the invention carries out heating and heat preservation treatment in the rolling process, softens the hardened tube blank and ensures that the tube blank can not be cracked in the subsequent rolling process.
The preparation method of the thin-walled capillary tube with the small diameter is characterized in that the drawing treatment process in the sixth step is as follows: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 10% -20% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 700 ℃ -750 ℃ under the argon atmosphere when the cumulative processing rate reaches 30% -45%, and then preserving heat for 30 min; the lubricating oil is synthetic engine oil or mineral engine oil. By coating lubricating oil and controlling the type of the lubricating oil, the drawing force required in the drawing process is reduced, the surface of the semi-finished tube is kept smooth, the die and the semi-finished tube are prevented from being adhered in the drawing process, the friction heating phenomenon of the die and the tube in the drawing process is inhibited, and the quality of the palladium alloy thin-diameter thin-wall capillary tube is improved; according to the invention, through the matching of the air drawing and the long core rod drawing and the control of the drawing processing parameters, the outer diameter and the wall thickness of the semi-finished tube are reduced, and the stable drawing processing is ensured, so that the semi-finished tube is prevented from bending, deformation damage, grain growth and cracking in the drawing process, the palladium alloy thin-diameter thin-wall capillary tube has a proper size, and the production of the palladium alloy thin-diameter thin-wall capillary tube with high precision, high density and smooth surface is realized.
The preparation method of the thin-wall capillary with the small diameter is characterized in that the thin-wall capillary with the small diameter is made of PdAg20, PdAg25, PdCu40, PdY6.77, PdCuY34-6, PdCuAg20-20, PdAgY14-6, PdAuNi 23-2-0.3, PdAuY 23-3-2, PdAuNi 23-3-0.5 or PdAuNi 23-4-0.2. According to the invention, by controlling the material quality of the palladium alloy thin-diameter thin-wall capillary tube, the phenomenon that pure metal palladium is subjected to phase change along with temperature change in a hydrogen atmosphere is inhibited, the cost of the palladium alloy raw material is reduced, the palladium alloy thin-diameter thin-wall capillary tube has the optimal hydrogen permeation performance and strength, and the hydrogen embrittlement phenomenon is inhibited.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the duplex smelting process of vacuum induction smelting and vacuum consumable arc smelting, ensures that the components of the cast ingot are uniform and the organization structure is compact, is beneficial to subsequent rolling treatment and drawing treatment, and avoids the defect of cracking caused by thinner pipe wall thickness in the rolling treatment and drawing treatment processes.
2. The invention adopts the modes of producing pierced billets and extruding to obtain the tube billets, further refines the structure of the cast ingots, improves the plasticity of the cast ingots, and reduces the defect of cracking caused by thinner wall thickness of the tube stocks in the rolling treatment and drawing treatment processes.
3. The invention adopts diffusion annealing treatment under protective atmosphere to diffuse atoms in the ingot, and ensures that all components in the ingot are uniformly distributed, thereby ensuring that the components of the thin-walled capillary with the small diameter of the palladium alloy are uniform and the organization structure is compact, realizing organization and component homogenization by lower temperature and shorter time, and saving energy.
4. According to the invention, the purity of the palladium alloy raw material is controlled, so that the content of impurities in the palladium alloy thin-diameter thin-wall capillary tube is reduced, and the performance of the palladium alloy thin-diameter thin-wall capillary tube is ensured; according to the invention, by adding other metal elements, the hydrogen permeability of the palladium alloy thin-diameter thin-wall capillary is improved, the occurrence of hydrogen embrittlement is inhibited, and the strength of the palladium alloy thin-diameter thin-wall capillary is improved.
5. The invention adopts cold rolling and cold drawing to accurately control the quality of the palladium alloy thin-diameter thin-wall capillary tube, realizes the production of the thin-diameter thin-wall capillary tube with high precision, high density and smooth surface, ensures the quality of the palladium alloy thin-diameter thin-wall capillary tube and improves the yield.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
The present invention is described in detail in examples 1 to 11.
Example 1
The embodiment comprises the following steps:
the method comprises the following steps of firstly, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out casting treatment to obtain an electrode, wherein the mass fraction of palladium in the palladium alloy raw material is 80%, the mass fraction of silver is 20%, the palladium is a palladium ingot with the mass purity of 99.95%, and the silver is a silver ingot with the mass purity of 99.99%, and the vacuum induction melting treatment process comprises the steps of putting the palladium alloy raw material into a crucible of a vacuum induction melting furnace, and then keeping the vacuum degree of 1.5 × 10-2Pa, heating to 1500 ℃ and then smelting for 10 min; the crucible is a magnesium oxide crucible; the electrode is
A cylindrical shape (cross-sectional diameter × high);
step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot; the vacuum consumable arc melting treatment miningThe method is carried out by using a vacuum consumable arc furnace, wherein the conditions of the vacuum consumable arc melting treatment are that the arcing voltage is 25V, the arcing current is 850A, the arc stabilizing current is 5A, and the vacuum degree in the furnace is 1.5 × 10-1Pa; the diffusion annealing process comprises the following steps: and heating the electrode subjected to the vacuum consumable arc melting treatment to 1100 ℃ in an argon atmosphere, and then preserving heat for 10 hours to obtain an ingot.
Step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet; the pierced billet making treatment process comprises the following steps: sequentially carrying out headstock, tail removal and peeling treatment on the cast ingot, and then carrying out drilling treatment to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks; the extrusion treatment process comprises the following steps: coating the outer wall of the pierced billet with pure copper foil, and extruding at an extrusion temperature of 800 ℃ at an extrusion ratio of 3.5
Step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the rolling treatment process comprises the following steps: placing the tube blank into a three-roller rolling mill, controlling the pass processing rate to be 30%, carrying out 5-pass cold rolling, heating the tube blank to 700 ℃ under the argon atmosphere when the cumulative processing rate reaches 60%, and then preserving heat for 30 min; the outer diameter of the semi-finished pipe is 6.0mm, and the wall thickness is 0.20 mm.
Sixthly, drawing the semi-finished pipe obtained in the fifth step to obtain a PdAg20 palladium alloy thin-diameter thin-wall capillary; the drawing process comprises the following steps: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 20% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 700 ℃ in an argon atmosphere when the cumulative processing rate reaches 40%, and then preserving heat for 30 min; the lubricating oil is synthetic engine oil; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 3.0mm, the wall thickness is 0.05mm, and the length is 7.0 m.
Example 2
The embodiment comprises the following steps:
step one, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out vacuum induction melting treatment on the palladium alloy raw materialCarrying out pouring treatment to obtain an electrode, wherein the mass fraction of palladium in the palladium alloy raw material is 75%, the mass fraction of silver is 25%, the mass fraction of palladium is 99.95% palladium ingot, and the mass fraction of silver is 99.99% silver ingot, and the vacuum induction melting treatment process comprises the steps of putting the palladium alloy raw material into a crucible of a vacuum induction melting furnace, and then keeping the vacuum degree to be 1.7 × 10-2Pa, heating to 1500 ℃, and then smelting for 12 min; the crucible is a magnesium oxide crucible; the electrode is
A cylindrical shape (cross-sectional diameter × high);
and step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot, wherein the vacuum consumable arc melting treatment is carried out by adopting a vacuum consumable arc furnace, and the conditions of the vacuum consumable arc melting treatment comprise that the arcing voltage is 30V, the arcing current is 800A, the arc stabilizing current is 4A, the vacuum degree in the furnace is 1.8 × 10-1Pa; the diffusion annealing process comprises the following steps: and heating the electrode subjected to the vacuum consumable arc melting treatment to 1100 ℃ in an argon atmosphere, and then preserving heat for 10 hours to obtain an ingot.
Step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet; the pierced billet making treatment process comprises the following steps: sequentially carrying out headstock, tail removal and peeling treatment on the cast ingot, and then carrying out drilling treatment to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks; the extrusion treatment process comprises the following steps: coating the outer wall of the pierced billet with pure copper foil, and extruding at an extrusion temperature of 800 ℃ at an extrusion ratio of 3.5
Step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the rolling treatment process comprises the following steps: placing the tube blank into a three-roller rolling mill, controlling the pass processing rate to be 30%, carrying out 5-pass cold rolling, heating the tube blank to 700 ℃ under the argon atmosphere when the cumulative processing rate reaches 60%, and then preserving heat for 30 min; the outer diameter of the semi-finished pipe is 6.0mm, and the wall thickness is 0.18 mm.
Sixthly, drawing the semi-finished pipe obtained in the fifth step to obtain a PdAg25 palladium alloy thin-diameter thin-wall capillary; the drawing process comprises the following steps: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 20% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 700 ℃ in an argon atmosphere when the cumulative processing rate reaches 40%, and then preserving heat for 30 min; the lubricating oil is synthetic engine oil; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 2.5mm, the wall thickness is 0.10mm, and the length is 6.8 m.
Example 3
The embodiment comprises the following steps:
the method comprises the following steps of firstly, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out casting treatment to obtain an electrode, wherein the mass fraction of palladium in the palladium alloy raw material is 60%, the mass fraction of copper is 40%, the mass fraction of palladium is a palladium ingot with the mass purity of 99.95%, and the mass fraction of copper is a copper ingot with the mass purity of 99.99%, the vacuum induction melting treatment process is that the palladium alloy raw material is placed into a crucible of a vacuum induction melting furnace, and then the vacuum degree is kept at 1.9 × 10-2Pa, heating to 1550 ℃ and then smelting for 15 min; the crucible is a magnesium oxide crucible; the electrode is
A cylindrical shape (cross-sectional diameter × high);
and step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot, wherein the vacuum consumable arc melting treatment is carried out by adopting a vacuum consumable arc furnace, and the conditions of the vacuum consumable arc melting treatment comprise that the arcing voltage is 28V, the arcing current is 850A, the arc stabilizing current is 4.5A, and the vacuum degree in the furnace is 1.6 × 10-1Pa; the diffusion annealing process comprises the following steps: and heating the electrode subjected to the vacuum consumable arc melting treatment to 1000 ℃ in an argon atmosphere, and then preserving heat for 10 hours to obtain an ingot.
Step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet; the pierced billet making treatment process comprises the following steps: sequentially carrying out headstock, tail removal and peeling treatment on the cast ingot, and then carrying out drilling treatment to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks; the extrusion treatment process comprises the following steps: coating the outer wall of the pierced billet with pure copper foil, and extruding at an extrusion temperature of 820 ℃ at an extrusion ratio of 3.5
Step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the rolling treatment process comprises the following steps: placing the tube blank into a three-roller rolling mill, controlling the pass working rate to be 25%, carrying out 5-pass cold rolling, heating the tube blank to 700 ℃ under the argon atmosphere when the cumulative working rate reaches 50%, and then preserving heat for 30 min; the outer diameter of the semi-finished pipe is 5.7mm, and the wall thickness is 0.17 mm.
Sixthly, drawing the semi-finished tube obtained in the fifth step to obtain a PdCu40 palladium alloy thin-diameter thin-wall capillary tube; the drawing process comprises the following steps: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 20% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 750 ℃ in an argon atmosphere when the cumulative processing rate reaches 40%, and then preserving heat for 30 min; the lubricating oil is synthetic engine oil; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 2.0mm, the wall thickness is 0.08mm, and the length is 6.9 m.
Example 4
The embodiment comprises the following steps:
the method comprises the following steps of firstly, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out casting treatment to obtain an electrode, wherein the mass fraction of palladium in the palladium alloy raw material is 93.33%, the mass fraction of yttrium is 6.67%, the palladium is a palladium ingot with the mass purity of 99.95%, and the yttrium is an yttrium ingot with the mass purity of 99.99%, and the vacuum induction melting treatment process comprises the steps of putting the palladium alloy raw material into a crucible of a vacuum induction melting furnace, and then keeping the vacuum degree to be 1.4 × 10-2Pa, heating to 1600 ℃ and then smelting for 15 min; the crucible is a magnesium oxide crucible; the electrode is
A cylindrical shape (cross-sectional diameter × high);
and step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot, wherein the vacuum consumable arc melting treatment is carried out by adopting a vacuum consumable arc furnace, and the conditions of the vacuum consumable arc melting treatment comprise that the arcing voltage is 26V, the arcing current is 820A, the arc stabilizing current is 4.5A, and the vacuum degree in the furnace is 1.7 × 10-1Pa; the diffusion annealing process comprises the following steps: and heating the electrode subjected to the vacuum consumable arc melting treatment to 1050 ℃ in an argon atmosphere, and then preserving heat for 10 hours to obtain an ingot.
Step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet; the pierced billet making treatment process comprises the following steps: sequentially carrying out headstock, tail removal and peeling treatment on the cast ingot, and then carrying out drilling treatment to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks; the extrusion treatment process comprises the following steps: coating the outer wall of the pierced billet with pure copper foil, and extruding at an extrusion temperature of 850 ℃ at an extrusion ratio of 3.5
Step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the rolling treatment process comprises the following steps: placing the tube blank into a three-roller rolling mill, controlling the pass working ratio to be 20%, carrying out 7-pass cold rolling, heating the tube blank to 750 ℃ in an argon atmosphere when the cumulative working ratio reaches 40%, and then preserving heat for 30 min; the outer diameter of the semi-finished pipe is 6.0mm, and the wall thickness is 0.20 mm.
Sixthly, drawing the semi-finished tube obtained in the fifth step to obtain a PdY6.77 palladium alloy thin-diameter thin-wall capillary tube; the drawing process comprises the following steps: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 10% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 750 ℃ in an argon atmosphere when the cumulative processing rate reaches 30%, and then preserving heat for 30 min; the lubricating oil is mineral engine oil; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 1.8mm, the wall thickness is 0.05mm, and the length is 6.8 m.
Example 5
The embodiment comprises the following steps:
the method comprises the following steps of firstly, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out casting treatment to obtain an electrode, wherein the mass fraction of palladium in the palladium alloy raw material is 60%, the mass fraction of copper is 34%, and the mass fraction of yttrium is 6%, the palladium is a palladium ingot with the mass purity of 99.95%, the copper is a copper ingot with the mass purity of 99.99%, and the yttrium is an yttrium ingot with the mass purity of 99.99%, and the vacuum induction melting treatment process comprises the steps of putting the palladium alloy raw material into a crucible of a vacuum induction melting furnace, and then keeping the vacuum degree of 1.9 × 10-2Pa, heating to 1600 ℃ and then smelting for 15 min; the crucible is a magnesium oxide crucible; the electrode is
A cylindrical shape (cross-sectional diameter × high);
and step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot, wherein the vacuum consumable arc melting treatment is carried out by adopting a vacuum consumable arc furnace, and the conditions of the vacuum consumable arc melting treatment comprise that the arcing voltage is 29V, the arcing current is 810A, the arc stabilizing current is 5A, and the vacuum degree in the furnace is 1.7 × 10-1Pa; the diffusion annealing process comprises the following steps: and heating the electrode subjected to the vacuum consumable arc melting treatment to 1050 ℃ in an argon atmosphere, and then preserving heat for 10 hours to obtain an ingot.
Step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet; the pierced billet making treatment process comprises the following steps: sequentially carrying out headstock, tail removal and peeling treatment on the cast ingot, and then carrying out drilling treatment to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks; the extrusion treatment process comprises the following steps: coating the outer wall of the pierced billet with pure copper foil, and extruding at an extrusion temperature of 850 ℃ at an extrusion ratio of 3.5
Step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the rolling treatment process comprises the following steps: placing the tube blank into a three-roller rolling mill, controlling the pass working rate to be 20%, carrying out 7-pass cold rolling, heating the tube blank to 740 ℃ in an argon atmosphere when the cumulative working rate reaches 40%, and then preserving heat for 30 min; the outer diameter of the semi-finished pipe is 5.9mm, and the wall thickness is 0.18 mm.
Sixthly, drawing the semi-finished tube obtained in the fifth step to obtain a PdCuY34-6 palladium alloy thin-diameter thin-wall capillary tube; the drawing process comprises the following steps: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 10% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 750 ℃ in an argon atmosphere when the cumulative processing rate reaches 30%, and then preserving heat for 30 min; the lubricating oil is mineral engine oil; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 1.9mm, the wall thickness is 0.06mm, and the length is 6.9 m.
Example 6
The embodiment comprises the following steps:
the method comprises the following steps of firstly, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out casting treatment to obtain an electrode, wherein the mass fraction of palladium in the palladium alloy raw material is 60%, the mass fraction of copper is 20%, the mass fraction of silver is 20%, the palladium is a palladium ingot with the mass purity of 99.95%, the copper is a copper ingot with the mass purity of 99.99%, and the silver is a silver ingot with the mass purity of 99.99%, and the vacuum induction melting treatment process comprises the steps of putting the palladium alloy raw material into a crucible of a vacuum induction melting furnace, and then keeping the vacuum degree of 1.6 × 10-2Pa, heating to 1600 ℃ and then smelting for 15 min; the crucible is a magnesium oxide crucible; the electrode is
A cylindrical shape (cross-sectional diameter × high);
step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain the electrodeThe vacuum consumable electrode arc melting treatment is carried out by adopting a vacuum consumable electrode arc furnace, and the conditions of the vacuum consumable electrode arc melting treatment comprise that the arcing voltage is 25V, the arcing current is 850A, the arc stabilizing current is 4.5A, and the vacuum degree in the furnace is 1.7 × 10-1Pa; the diffusion annealing process comprises the following steps: and heating the electrode subjected to the vacuum consumable arc melting treatment to 1060 ℃ in an argon atmosphere, and then preserving heat for 10 hours to obtain an ingot.
Step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet; the pierced billet making treatment process comprises the following steps: sequentially carrying out headstock, tail removal and peeling treatment on the cast ingot, and then carrying out drilling treatment to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks; the extrusion treatment process comprises the following steps: coating the outer wall of the pierced billet with pure copper foil, and extruding at an extrusion temperature of 850 ℃ at an extrusion ratio of 3.5
Step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the rolling treatment process comprises the following steps: placing the tube blank into a three-roller rolling mill, controlling the pass working rate to be 20%, carrying out 7-pass cold rolling, heating the tube blank to 740 ℃ in an argon atmosphere when the cumulative working rate reaches 40%, and then preserving heat for 30 min; the outer diameter of the semi-finished pipe is 5.8mm, and the wall thickness is 0.18 mm.
Sixthly, drawing the semi-finished pipe obtained in the fifth step to obtain a PdCuAg20-20 palladium alloy thin-diameter thin-wall capillary; the drawing process comprises the following steps: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 10% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 750 ℃ in an argon atmosphere when the cumulative processing rate reaches 30%, and then preserving heat for 30 min; the lubricating oil is mineral engine oil; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 1.9mm, the wall thickness is 0.07mm, and the length is 6.7 m.
Example 7
The embodiment comprises the following steps:
step one, palladium is mixedThe method comprises the steps of carrying out vacuum induction melting treatment on an alloy raw material, and then carrying out pouring treatment to obtain an electrode, wherein the mass fraction of palladium in the palladium alloy raw material is 80%, the mass fraction of silver is 14%, and the mass fraction of yttrium is 6%, the palladium is a palladium ingot with the mass purity of 99.95%, the silver is a silver ingot with the mass purity of 99.99%, and the yttrium is an yttrium ingot with the mass purity of 99.99%, the vacuum induction melting treatment process comprises the steps of putting the palladium alloy raw material into a crucible of a vacuum induction melting furnace, and then keeping the vacuum degree of 1.2 × 10-2Pa, heating to 1600 ℃ and then smelting for 17 min; the crucible is a magnesium oxide crucible; the electrode is
A cylindrical shape (cross-sectional diameter × high);
and step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot, wherein the vacuum consumable arc melting treatment is carried out by adopting a vacuum consumable arc furnace, and the conditions of the vacuum consumable arc melting treatment comprise that the arcing voltage is 27V, the arcing current is 840A, the arc stabilizing current is 5A, the vacuum degree in the furnace is 1.5 × 10-1Pa; the diffusion annealing process comprises the following steps: and heating the electrode subjected to the vacuum consumable arc melting treatment to 1040 ℃ in an argon atmosphere, and then preserving heat for 10 hours to obtain an ingot.
Step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet; the pierced billet making treatment process comprises the following steps: sequentially carrying out headstock, tail removal and peeling treatment on the cast ingot, and then carrying out drilling treatment to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks; the extrusion treatment process comprises the following steps: coating the outer wall of the pierced billet with pure copper foil, and extruding at an extrusion temperature of 850 ℃ at an extrusion ratio of 3.5
Step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the rolling treatment process comprises the following steps: placing the tube blank into a three-roller rolling mill, controlling the pass working rate to be 20%, performing 6-pass cold rolling, heating the tube blank to 740 ℃ in an argon atmosphere when the cumulative working rate reaches 40%, and then preserving heat for 30 min; the outer diameter of the semi-finished pipe is 5.8mm, and the wall thickness is 0.18 mm.
Sixthly, drawing the semi-finished pipe obtained in the fifth step to obtain a PdAgY14-6 palladium alloy thin-diameter thin-wall capillary; the drawing process comprises the following steps: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 10% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 750 ℃ in an argon atmosphere when the cumulative processing rate reaches 30%, and then preserving heat for 30 min; the lubricating oil is mineral engine oil; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 2.0mm, the wall thickness is 0.07mm, and the length is 6.8 m.
Example 8
The embodiment comprises the following steps:
the method comprises the following steps of firstly, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out casting treatment to obtain an electrode, wherein the mass fraction of palladium in the palladium alloy raw material is 74.7%, the mass fraction of silver is 23%, the mass fraction of gold is 2%, the mass fraction of nickel is 0.3%, the mass fraction of palladium is a palladium ingot with the mass purity of 99.95%, the mass fraction of silver is a silver ingot with the mass purity of 99.99%, the mass fraction of gold is a gold ingot with the mass purity of 99.95%, and the mass fraction of nickel is a nickel ingot with the mass purity of 99.96%, the process of the vacuum induction melting treatment is that the palladium alloy raw material is placed into a crucible of a vacuum induction melting furnace, and then the vacuum degree is kept to be 1.6 × 10-2Pa, heating to 1500 ℃ and then smelting for 20 min; the crucible is a calcium oxide crucible; the electrode is
A cylindrical shape (cross-sectional diameter × high);
and step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot, wherein the vacuum consumable arc melting treatment is carried out by adopting a vacuum consumable arc furnace, and the conditions of the vacuum consumable arc melting treatment comprise that the arcing voltage is 26V, the arcing current is 850A, the arc stabilizing current is 4A, the vacuum degree in the furnace is 1.8 × 10-1Pa; the diffusion annealing process comprises the following steps: and heating the electrode subjected to the vacuum consumable arc melting treatment to 1100 ℃ in an argon atmosphere, and then preserving heat for 10 hours to obtain an ingot.
Step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet; the pierced billet making treatment process comprises the following steps: sequentially carrying out headstock, tail removal and peeling treatment on the cast ingot, and then carrying out drilling treatment to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks; the extrusion treatment process comprises the following steps: coating the outer wall of the pierced billet with pure copper foil, and extruding at an extrusion temperature of 820 ℃ at an extrusion ratio of 3.5
Step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the rolling treatment process comprises the following steps: placing the tube blank into a three-roller rolling mill, controlling the pass working rate to be 20%, performing 6-pass cold rolling, heating the tube blank to 730 ℃ under the argon atmosphere when the cumulative working rate reaches 40%, and then preserving heat for 30 min; the outer diameter of the semi-finished pipe is 5.6mm, and the wall thickness is 0.18 mm.
Sixthly, drawing the semi-finished pipe obtained in the fifth step to obtain a PdAuNi 23-2-0.3 palladium alloy thin-diameter thin-wall capillary; the drawing process comprises the following steps: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 15% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 730 ℃ under an argon atmosphere when the cumulative processing rate reaches 45%, and then preserving heat for 30 min; the lubricating oil is mineral engine oil; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 2.0mm, the wall thickness is 0.06mm, and the length is 6.8 m.
Example 9
The embodiment comprises the following steps:
step one, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out casting treatment to obtain an electrode; the mass fraction of palladium in the raw materials of the palladium alloy is 72%, the mass fraction of silver is 23%, the mass fraction of gold is 3%, and the mass fraction of yttrium is 2%; the above-mentionedThe method comprises the steps of putting a palladium alloy raw material into a crucible of a vacuum induction smelting furnace, and then maintaining the vacuum degree to be 2 × 10-2Pa, heating to 1580 ℃ and then smelting for 20 min; the crucible is a magnesium oxide crucible; the electrode is
A cylindrical shape (cross-sectional diameter × high);
and step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot, wherein the vacuum consumable arc melting treatment is carried out by adopting a vacuum consumable arc furnace, and the conditions of the vacuum consumable arc melting treatment comprise that the arcing voltage is 25V, the arcing current is 835A, the arc stabilizing current is 4.5A, and the vacuum degree in the furnace is 1.9 × 10-1Pa; the diffusion annealing process comprises the following steps: and heating the electrode subjected to the vacuum consumable arc melting treatment to 1100 ℃ in an argon atmosphere, and then preserving heat for 10 hours to obtain an ingot.
Step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet; the pierced billet making treatment process comprises the following steps: sequentially carrying out headstock, tail removal and peeling treatment on the cast ingot, and then carrying out drilling treatment to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks; the extrusion treatment process comprises the following steps: coating the outer wall of the pierced billet with pure copper foil, and extruding at an extrusion temperature of 850 ℃ at an extrusion ratio of 3.5
Step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the rolling treatment process comprises the following steps: placing the tube blank into a three-roller rolling mill, controlling the pass working ratio to be 20%, performing 6-pass cold rolling, heating the tube blank to 750 ℃ in an argon atmosphere when the cumulative working ratio reaches 40%, and then preserving heat for 30 min; the outer diameter of the semi-finished pipe is 5.5mm, and the wall thickness is 0.15 mm.
Sixthly, drawing the semi-finished pipe obtained in the fifth step to obtain a PdAuY 23-3-2 palladium alloy thin-diameter thin-wall capillary tube; the drawing process comprises the following steps: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 15% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 750 ℃ in an argon atmosphere when the cumulative processing rate reaches 30%, and then preserving heat for 30 min; the lubricating oil is mineral engine oil; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 1.8mm, the wall thickness is 0.05mm, and the length is 6.7 m.
Example 10
The embodiment comprises the following steps:
the method comprises the steps of firstly, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out casting treatment to obtain an electrode, wherein the mass fraction of palladium in the palladium alloy raw material is 73.5%, the mass fraction of silver is 23%, the mass fraction of gold is 3%, the mass fraction of nickel is 0.5%, the mass fraction of palladium is a palladium ingot with the mass purity of 99.95%, the mass fraction of silver is a silver ingot with the mass purity of 99.99%, the mass fraction of gold is a gold ingot with the mass purity of 99.95%, and the mass fraction of nickel is a nickel ingot with the mass purity of 99.96%, the process of the vacuum induction melting treatment is that the palladium alloy raw material is placed into a crucible of a vacuum induction melting furnace, and then the vacuum degree is kept to be 1.4 × 10-2Pa, heating to 1500 ℃ and then smelting for 20 min; the crucible is a calcium oxide crucible; the electrode is
A cylindrical shape (cross-sectional diameter × high);
and step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot, wherein the vacuum consumable arc melting treatment is carried out by adopting a vacuum consumable arc furnace, and the conditions of the vacuum consumable arc melting treatment comprise that the arcing voltage is 29V, the arcing current is 830A, the arc stabilizing current is 4A, the vacuum degree in the furnace is 1.7 × 10-1Pa; the diffusion annealing process comprises the following steps: and heating the electrode subjected to the vacuum consumable arc melting treatment to 1100 ℃ in an argon atmosphere, and then preserving heat for 10 hours to obtain an ingot.
Step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet; the pierced billet making treatment process comprises the following steps: sequentially carrying out headstock, tail removal and peeling treatment on the cast ingot, and then carrying out drilling treatment to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks; the extrusion treatment process comprises the following steps: coating the outer wall of the pierced billet with pure copper foil, and extruding at an extrusion temperature of 820 ℃ at an extrusion ratio of 3.5
Step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the rolling treatment process comprises the following steps: placing the tube blank into a three-roller rolling mill, controlling the pass processing rate to be 20%, performing 6-pass cold rolling, heating the tube blank to 730 ℃ in an argon atmosphere after performing 2-pass cold rolling, and then preserving heat for 30 min; the outer diameter of the semi-finished pipe is 5.8mm, and the wall thickness is 0.19 mm.
Sixthly, drawing the semi-finished pipe obtained in the fifth step to obtain a PdAuNi 23-3-0.5 palladium alloy thin-diameter thin-wall capillary; the drawing process comprises the following steps: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 15% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 730 ℃ under an argon atmosphere when the cumulative processing rate reaches 45%, and then preserving heat for 30 min; the lubricating oil is mineral engine oil; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 2.0mm, the wall thickness is 0.07mm, and the length is 6.7 m.
Example 11
The embodiment comprises the following steps:
step one, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out casting treatment to obtain an electrode; the mass fraction of palladium in the raw materials of the palladium alloy is 72.8%, the mass fraction of silver is 23%, the mass fraction of gold is 4%, and the mass fraction of nickel is 0.2%; the palladium is a palladium ingot with the mass purity of 99.95%, the silver is a silver ingot with the mass purity of 99.99%, the gold is a gold ingot with the mass purity of 99.95%, and the nickel is a nickel ingot with the mass purity of 99.96%; the shoe soleThe air induction smelting process comprises placing the raw material of palladium alloy into the crucible of a vacuum induction smelting furnace, and maintaining the vacuum degree at 1.7 × 10-2Pa, heating to 1500 ℃ and then smelting for 20 min; the crucible is a calcium oxide crucible; the electrode is
A cylindrical shape (cross-sectional diameter × high);
and step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot, wherein the vacuum consumable arc melting treatment is carried out by adopting a vacuum consumable arc furnace, and the conditions of the vacuum consumable arc melting treatment comprise that the arcing voltage is 26V, the arcing current is 845A, the arc stabilizing current is 5A, the vacuum degree in the furnace is 2 × 10- 1Pa; the diffusion annealing process comprises the following steps: and heating the electrode subjected to the vacuum consumable arc melting treatment to 1100 ℃ in an argon atmosphere, and then preserving heat for 10 hours to obtain an ingot.
Step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet; the pierced billet making treatment process comprises the following steps: sequentially carrying out headstock, tail removal and peeling treatment on the cast ingot, and then carrying out drilling treatment to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks; the extrusion treatment process comprises the following steps: coating the outer wall of the pierced billet with pure copper foil, and extruding at an extrusion temperature of 820 ℃ at an extrusion ratio of 3.5
Step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the rolling treatment process comprises the following steps: placing the tube blank into a three-roller rolling mill, controlling the pass processing rate to be 20%, performing 6-pass cold rolling, heating the tube blank to 730 ℃ in an argon atmosphere after performing 2-pass cold rolling, and then preserving heat for 30 min; the outer diameter of the semi-finished pipe is 5.5mm, and the wall thickness is 0.17 mm.
Sixthly, drawing the semi-finished pipe obtained in the fifth step to obtain a PdAuNi 23-4-0.2 palladium alloy thin-diameter thin-wall capillary; the drawing process comprises the following steps: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 15% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 730 ℃ under an argon atmosphere when the cumulative processing rate reaches 45%, and then preserving heat for 30 min; the lubricating oil is mineral engine oil; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 2.0mm, the wall thickness is 0.07mm, and the length is 6.8 m.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (10)
1. A preparation method of a palladium alloy thin-diameter thin-wall capillary tube is characterized by comprising the following steps:
step one, carrying out vacuum induction melting treatment on a palladium alloy raw material, and then carrying out casting treatment to obtain an electrode;
step two, sequentially carrying out vacuum consumable arc melting treatment and diffusion annealing treatment on the electrode obtained in the step one to obtain an ingot; the process of the diffusion annealing treatment comprises the following steps: heating the electrode subjected to vacuum consumable arc melting treatment to 1000-1100 ℃ in an argon atmosphere, and then preserving heat for 10 h;
step three, carrying out pierced billet manufacturing treatment on the cast ingot obtained in the step two to obtain a pierced billet;
step four, sequentially extruding and straightening the pierced billets obtained in the step three to obtain tube blanks;
step five, rolling the tube blank obtained in the step four to obtain a semi-finished tube; the outer diameter of the semi-finished pipe is 5.5 mm-6.0 mm, and the wall thickness is 0.15 mm-0.20 mm;
step six, drawing the semi-finished tube obtained in the step five to obtain the palladium alloy thin-diameter thin-wall capillary tube; the outer diameter of the palladium alloy thin-diameter thin-wall capillary tube is phi 1.8 mm-phi 3.0mm, and the wall thickness is 0.05 mm-0.10 mm.
2. The method for preparing the palladium alloy thin-diameter thin-wall capillary tube according to claim 1, wherein in the step one, the palladium alloy raw material consists of palladium and additive metals, the mass fraction of palladium in the palladium alloy raw material is 60-93.33%, and the additive metals are one, two or three of silver, copper, gold, yttrium and nickel; the palladium is a palladium ingot with the mass purity of not less than 99.95%, the silver is a silver ingot with the mass purity of not less than 99.99%, the copper is a copper ingot with the mass purity of not less than 99.95%, the gold is a gold ingot with the mass purity of not less than 99.95%, the yttrium is an yttrium ingot with the mass purity of not less than 99.9%, and the nickel is a nickel ingot with the mass purity of not less than 99.96%.
3. The method for preparing the thin-wall and small-diameter palladium alloy capillary tube as claimed in claim 2, wherein the mass fraction of silver in the raw material of the palladium alloy is 14-25%, the mass fraction of copper is 20-40%, the mass fraction of gold is 2-4%, the mass fraction of yttrium is 2-6.77%, and the mass fraction of nickel is 0.2-0.5%.
4. The method for preparing the thin-walled palladium alloy tube according to claim 1, wherein the vacuum induction melting treatment in the first step is carried out by putting a raw palladium alloy material into a crucible of a vacuum induction melting furnace and then maintaining the vacuum degree in the furnace to be not less than 1 × 10-2Pa, heating to 1500-1600 ℃ and smelting for 10-20 min; the crucible is a magnesium oxide crucible or a calcium oxide crucible; the electrodes are cylindrical.
5. The method for preparing the thin-diameter thin-wall capillary of the palladium alloy as claimed in claim 1, wherein the conditions of the vacuum consumable arc melting treatment in the second step are that the arc starting voltage is 25V-30V, the arc starting current is 800A-850A, the arc stabilizing current is 4A-5A, and the vacuum degree in the furnace is not lower than 1 × 10-1Pa。
6. The method for preparing the thin-walled palladium alloy capillary tube according to claim 1, wherein the pierced blank tube manufacturing process in the third step is as follows: and (4) sequentially carrying out head turning, tail removing and peeling on the cast ingot, and then drilling to obtain a pierced billet.
7. The method for preparing the thin-walled small-diameter palladium alloy capillary tube according to claim 1, wherein the extrusion treatment in the fourth step is as follows: coating the outer wall of the pierced billet with pure copper foil, and then performing extrusion treatment at the extrusion temperature of 800-850 ℃, wherein the extrusion ratio of the extrusion treatment is 3.5.
8. The method for preparing the palladium alloy thin-diameter thin-wall capillary tube according to claim 1, wherein the rolling process in the fifth step is as follows: the tube blank is put into a three-roller rolling mill, the pass working ratio is controlled to be 20-30%, 5-7 passes of cold rolling are carried out, and when the cumulative working ratio reaches 40-60%, the tube blank is heated to 700-750 ℃ under the argon atmosphere and then is kept warm for 30 min.
9. The method for preparing the thin-walled small-diameter palladium alloy capillary tube according to claim 1, wherein the drawing process in the sixth step is as follows: coating lubricating oil on the inner surface and the outer surface of a semi-finished pipe, controlling the pass processing rate to be 10% -20% by adopting a mode of combining air drawing and long core rod drawing, performing cold drawing, heating the semi-finished pipe to 700 ℃ -750 ℃ under the argon atmosphere when the cumulative processing rate reaches 30% -45%, and then preserving heat for 30 min; the lubricating oil is synthetic engine oil or mineral engine oil.
10. The method for preparing the thin-wall capillary with the small diameter of the palladium alloy as claimed in claim 3, wherein the thin-wall capillary with the small diameter of the palladium alloy is made of PdAg20, PdAg25, PdCu40, PDY6.77, PdCuY34-6, PdCuAg20-20, PdAgY14-6, PdAgNi 23-2-0.3, PdAgAuY23-3-2, PdAgAuNi23-3-0.5 or PdAgAuNi 23-4-0.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010668594.9A CN111778416A (en) | 2020-07-13 | 2020-07-13 | Preparation method of palladium alloy thin-diameter thin-wall capillary tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010668594.9A CN111778416A (en) | 2020-07-13 | 2020-07-13 | Preparation method of palladium alloy thin-diameter thin-wall capillary tube |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111778416A true CN111778416A (en) | 2020-10-16 |
Family
ID=72768478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010668594.9A Pending CN111778416A (en) | 2020-07-13 | 2020-07-13 | Preparation method of palladium alloy thin-diameter thin-wall capillary tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111778416A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113500097A (en) * | 2021-07-30 | 2021-10-15 | 王声兰 | Preparation method and application of alloy thin-wall capillary tube for hydrogen purification |
| CN114472580A (en) * | 2021-12-20 | 2022-05-13 | 上海海亮铜业有限公司 | Preparation method of high-strength super-long cupronickel alloy capillary tube |
| CN116618464A (en) * | 2023-03-13 | 2023-08-22 | 河北冀伽康新材料科技有限公司 | Production process of quantum platinum cobalt alloy fiber yarn |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6177602A (en) * | 1984-09-25 | 1986-04-21 | Ulvac Corp | Purification apparatus of hydrogen having high purity |
| CN101591001A (en) * | 2009-06-29 | 2009-12-02 | 西北有色金属研究院 | A kind of Pd doped Ti O 2The preparation method of nanotube array composite material |
| CN104835797A (en) * | 2015-03-23 | 2015-08-12 | 辽宁凯立尔电子科技有限公司 | Copper-palladium-silver alloy bonding wire and method for preparing same |
| CN104831108A (en) * | 2015-04-21 | 2015-08-12 | 常熟锐钛金属制品有限公司 | High hydrogen permeability antioxidant titanium palladium pipe |
| CN106555212A (en) * | 2015-09-25 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of preparation method of the controllable ultra-thin palladium film of thickness |
| CN108467963A (en) * | 2018-07-09 | 2018-08-31 | 广州宇智科技有限公司 | With big variable ability yellow jewellery palldium alloy and its processing technology |
-
2020
- 2020-07-13 CN CN202010668594.9A patent/CN111778416A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6177602A (en) * | 1984-09-25 | 1986-04-21 | Ulvac Corp | Purification apparatus of hydrogen having high purity |
| CN101591001A (en) * | 2009-06-29 | 2009-12-02 | 西北有色金属研究院 | A kind of Pd doped Ti O 2The preparation method of nanotube array composite material |
| CN104835797A (en) * | 2015-03-23 | 2015-08-12 | 辽宁凯立尔电子科技有限公司 | Copper-palladium-silver alloy bonding wire and method for preparing same |
| CN104831108A (en) * | 2015-04-21 | 2015-08-12 | 常熟锐钛金属制品有限公司 | High hydrogen permeability antioxidant titanium palladium pipe |
| CN106555212A (en) * | 2015-09-25 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of preparation method of the controllable ultra-thin palladium film of thickness |
| CN108467963A (en) * | 2018-07-09 | 2018-08-31 | 广州宇智科技有限公司 | With big variable ability yellow jewellery palldium alloy and its processing technology |
Non-Patent Citations (6)
| Title |
|---|
| 《稀有金属手册》编辑委员会: "《稀有金属手册 下册》", 31 December 1995, 冶金工业出版社 * |
| A.Π.格鲁捷夫等著，焦明山等译: "《金属压力加工中的摩擦和润滑手册》", 31 May 1990, 航空工业出版社 * |
| 时钧等: "《膜技术手册》", 31 January 2001, 化学工业出版社 * |
| 田广明等: ""钯钇合金毛细管的热处理制度和加工工艺"", 《中国有色金属学报》 * |
| 薛正良等: "《特种冶炼》", 31 October 2018, 冶金工业出版社 * |
| 马存真等: "《世界有色金属牌号手册》", 30 April 2017, 冶金工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113500097A (en) * | 2021-07-30 | 2021-10-15 | 王声兰 | Preparation method and application of alloy thin-wall capillary tube for hydrogen purification |
| CN113500097B (en) * | 2021-07-30 | 2023-03-03 | 李新中 | Preparation method and application of alloy thin-wall capillary tube for hydrogen purification |
| CN114472580A (en) * | 2021-12-20 | 2022-05-13 | 上海海亮铜业有限公司 | Preparation method of high-strength super-long cupronickel alloy capillary tube |
| CN114472580B (en) * | 2021-12-20 | 2024-04-02 | 上海海亮铜业有限公司 | Preparation method of high-strength ultra-long white copper alloy capillary |
| CN116618464A (en) * | 2023-03-13 | 2023-08-22 | 河北冀伽康新材料科技有限公司 | Production process of quantum platinum cobalt alloy fiber yarn |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111778416A (en) | Preparation method of palladium alloy thin-diameter thin-wall capillary tube | |
| CN110042273B (en) | High-strength high-conductivity copper alloy pipe and preparation method thereof | |
| CN112981335B (en) | Preparation method of high-purity copper tube target | |
| CN110468382B (en) | Large-diameter Ni-V rotary target containing trace elements and preparation method thereof | |
| CN111549244A (en) | Preparation method of Ti35 titanium alloy ingot | |
| CN112281032B (en) | Preparation method of aluminum alloy welding material | |
| WO2021046927A1 (en) | Nickel-rhenium alloy rotary tubular target material containing trace rare earth elements and preparation method therefor | |
| CN111411251B (en) | Anti-oxidation coating for rhenium spray pipe, preparation method of anti-oxidation coating and rhenium-anti-oxidation coating spray pipe | |
| CN107052075B (en) | Multimode is cold to swage and cold drawing processing AgSnO2The method of wire rod | |
| CN114381643B (en) | High-density tungsten alloy wire and preparation method thereof | |
| CN113481405B (en) | Preparation method of copper-iron alloy | |
| CN113500097B (en) | Preparation method and application of alloy thin-wall capillary tube for hydrogen purification | |
| CN1250352C (en) | Method for preparing superfine filament from metal and alloy material | |
| CN108273973B (en) | Method for producing tellurium bronze rod by adopting horizontal continuous casting process | |
| CN111299572A (en) | Production method of titanium and titanium alloy seamless tube | |
| CN109439955B (en) | Method for preparing high-strength and high-conductivity ultrafine-wire alloy material by adopting directional solidification | |
| CN109930016A (en) | A kind of preparation method of high-strength highly-conductive Kufil glass-coated microwire | |
| CN111451276A (en) | Preparation method of high-purity Gd/Tb/Dy/Y rare earth metal foil | |
| CN116275457A (en) | Friction stir additive manufacturing method of titanium alloy component with nanoscale fine grain structure | |
| CN111057862B (en) | Preparation method of high-purity rhodium wire for self-powered neutron detector | |
| CN114799738B (en) | Preparation method of TC4 titanium alloy thin-wall ring material | |
| CN113981268A (en) | Preparation method of brass wire | |
| CN113897494A (en) | Preparation method of electric stranded wire | |
| CN113351679A (en) | Preparation method of medical zinc alloy anastomosis nail | |
| CN111744984A (en) | Preparation method of tantalum alloy and niobium alloy tube blank |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |