CN110578159A - Tungsten-chromium-zirconium-copper pipe penetrating structure connecting method based on tungsten ring inner surface nano porosification - Google Patents
Tungsten-chromium-zirconium-copper pipe penetrating structure connecting method based on tungsten ring inner surface nano porosification Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P11/00—Connecting or disconnecting metal parts or objects by metal-working techniques not otherwise provided for
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/04—Tubes; Rings; Hollow bodies
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Abstract
The invention discloses a tungsten-chromium-zirconium-copper through pipe structure connecting method based on tungsten ring inner surface nano-porosification, which comprises the steps of tungsten ring inner surface anodic oxidation porosification, tungsten ring inner surface copper electroplating, tungsten ring and chromium-zirconium copper pipe connection and the like, wherein the tungsten ring inner surface is subjected to anodic oxidation treatment to prepare a nano-porous structure; placing the tungsten ring with the nano-porous inner surface into an electroplating solution containing copper sulfate, disodium ethylene diamine tetraacetate, sodium hydroxide, potassium sodium tartrate, potassium nitrate and ultrapure water for copper electroplating, and performing diffusion annealing at high temperature to obtain a tungsten ring copper-plated block; assembling a tungsten ring copper-plated block, a middle layer or brazing filler metal and a chromium-zirconium copper pipe, performing high-temperature heating connection, rapidly cooling and performing aging treatment to recover the mechanical property of the chromium-zirconium copper pipe. The preparation method has the advantages of simple preparation process, stable and pollution-free electroplating solution and low production cost, and the tungsten ring and the chromium-zirconium copper pipe have good bonding strength and are suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of metal compounding/connection, in particular to a tungsten/chromium zirconium copper through pipe structure connection method based on tungsten ring inner surface nano porosification.
Background
The controlled thermonuclear fusion energy is expected to become one of the main energy sources in the new century, and an international thermonuclear fusion experimental reactor (ITER) device is a superconducting Tokamak which can generate large-scale nuclear fusion reaction and is commonly called as an artificial sun. Divertors are a very important part of ITER devices whose main function in the fusion reactor is to shield impurities, to remove particle flow and heat flow from the center of the fusion reactor and helium ash from nuclear fusion reactions. The divertor has special and severe working environment, and the heat flux on the surface can reach 5-20 MW/m when facing plasma with the temperature of hundreds of millions of degrees2. To solve the above problems, the divertors of ITER are often designed as modular structures, with tungsten/chromium zirconium copper feedthroughs being used for the target portion.
the tungsten/chromium zirconium copper pipe penetrating structure is a pipe penetrating structure with a tungsten ring at the outer part and a chromium zirconium copper pipe at the inner part. The outer tungsten ring faces to high-temperature plasma, and the inner chromium-zirconium copper pipe is used for water supply and heat removal. Obviously, the preparation of the tungsten/chromium zirconium copper pipe penetrating structure relates to a connection process of tungsten and chromium zirconium copper. At present, the preparation process of the tungsten/chromium zirconium copper pipe penetrating structure mainly comprises the methods of hot isostatic pressing, pipe expanding and hot diffusion welding and the like. However, the two methods have low production efficiency, complex equipment and process, poor bonding strength and high rejection rate, which causes high preparation cost, and a preparation method with high efficiency and simple equipment and process needs to be developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a tungsten/chromium zirconium copper through pipe structure connecting method based on the nano porous inner surface of a tungsten ring.
The technical purpose of the invention is realized by the following technical scheme:
A tungsten-chromium-zirconium-copper pipe penetrating structure connecting method based on tungsten ring inner surface nano-porosification is carried out according to the following steps:
Step 1, arranging a nano porous tungsten structure on the inner surface of a tungsten ring
Taking a tungsten ring with a protected outer surface as an anode, carrying out anodic oxidation in electrolyte of sodium fluoride and hydrofluoric acid to form nano-porous tungsten oxide on the inner surface of the tungsten ring, and carrying out deoxidation treatment on the tungsten ring in a hydrogen atmosphere to form a nano-porous tungsten structure on the inner surface of the tungsten ring;
In step 1, a platinum sheet was used as the cathode.
In the step 1, in the electrolyte, water or ultrapure water is used as a solvent, sodium fluoride (NaF) and hydrofluoric acid (HF) are used as solutes, and the mass percent of the sodium fluoride is 0.1-0.5%, preferably 0.2-0.4%; the hydrofluoric acid is present in an amount of 0.1 to 0.5% by volume, preferably 0.2 to 0.4% by volume.
In step 1, when anodic oxidation is performed, the process parameters are as follows: oxidizing at room temperature under 60 + -5V for 30-90 min, preferably 60-80 min; then continuously oxidizing for 30-90 min, preferably 60-80 min under the voltage of 40 +/-5V; the distance between the cathode and the anode is 1-5 cm, preferably 3-5 cm.
In the step 1, in the deoxidation treatment, the tungsten ring after the anodic oxidation treatment is heated to 600-700 ℃ from room temperature at a speed of 5-10 ℃ per minute in a hydrogen atmosphere, the heat preservation time is 1-5 h, the tungsten ring is cooled along with a furnace, and the heat preservation time is preferably 650-700 ℃ for 3-5 h.
Step 2, plating copper on the inner surface of the tungsten ring
Taking the tungsten ring treated in the step 1 as a cathode for copper plating, and then carrying out high-temperature diffusion annealing to realize alloying between tungsten and copper to form a tungsten ring copper plating block
In step 2, a pure copper plate is used as an anode in the copper plating.
In step 2, the composition of the cyanide-free electrolytic copper plating solution used in copper plating is: 25-45 g/L of copper sulfate, 120-170 g/L of disodium ethylene diamine tetraacetate, 20-40 g/L of potassium sodium tartrate, 4-8 g/L of potassium nitrate, 20-40 g/L of sodium hydroxide and ultrapure water, wherein the pH value of the cyanide-free copper electroplating solution is controlled to be 12-13.
In the step 2, when copper plating is carried out, the technological parameters of electroplating are as follows: at 40 +/-5 deg.C, current density is 1-5A/dm2Electroplating for 10-40 min, with a cathode-anode spacing of 5-10 cm, preferably at a current density of 1-3A/dm2Electroplating for 20-30 min.
In step 2, when high-temperature diffusion annealing is performed, the process parameters are as follows: raising the temperature from room temperature of 20-25 ℃ to annealing temperature of 950-1000 ℃ at the speed of 5-10 ℃ per minute in hydrogen atmosphere, preserving the heat for 1-5 h, cooling along with the furnace, and taking out.
Step 3, connecting the tungsten ring copper-plated block with the chromium-zirconium copper pipe
Placing a chromium-zirconium copper pipe into a hole of a tungsten ring copper plating block and keeping the chromium-zirconium copper pipe coaxial, arranging an intermediate layer in a gap between the chromium-zirconium copper pipe and the tungsten ring copper plating block, assembling a connection sample, and sequentially performing high-temperature heating connection and aging treatment to realize the connection of the tungsten ring copper plating block and the chromium-zirconium copper pipe;
High-temperature heating connection: raising the temperature from room temperature to 900-950 ℃ at the speed of 5-10 ℃/min under the hydrogen atmosphere, then raising the temperature to 960-1000 ℃ at the speed of 1-5 ℃/min, preserving the temperature for 0.5-5 h, and then taking out the steel plate to be immersed in deionized water at the temperature of 20-30 ℃ for quenching treatment.
aging treatment: under the atmosphere of hydrogen, the temperature is increased from room temperature 20-25 ℃ to 400 +/-10 ℃ at the speed of 5-10 ℃/min, then the temperature is increased to 460-480 ℃ at the speed of 1-5 ℃/min, the heat preservation and aging treatment is carried out for 1-5 h, and the sample is taken out after furnace cooling.
In step 3, high temperature heating connection: raising the temperature from room temperature to 920-950 ℃ at the speed of 5-10 ℃/min, then raising the temperature to 960-980 ℃ at the speed of 1-5 ℃/min, preserving the temperature for 3-5 h, and then taking out the steel plate to be immersed in deionized water at the temperature of 20-30 ℃ for quenching treatment.
In step 3, aging treatment: raising the temperature from room temperature 20-25 ℃ to 400 +/-10 ℃ at the speed of 5-10 ℃/min, then raising the temperature to 470-480 ℃ at the speed of 1-5 ℃/min, carrying out heat preservation and aging treatment for 2.5-3.5 h, cooling along with the furnace, and taking out the sample.
In the step 3, the middle layer is oxygen-free copper foil, the purity is not less than 99.99 wt%, and the thickness is 80-100 μm, or the Cu-Al-Ni brazing filler metal comprises 88.75Cu-10.95Al-0.3Ni (the sum of the mass of copper, aluminum and nickel is 100 wtt%), and the thickness is 80-100 μm.
In step 3, because the dispersion strengthening phase in the chromium zirconium copper can be dissolved into the matrix when the temperature is higher than 480 ℃, so that the chromium zirconium copper is softened, the chromium zirconium copper needs to be quenched and aged again after high-temperature connection to recover the performance.
in above-mentioned technical scheme, polish tungsten ring internal surface and chromium zirconium copper pipe, deoil and ultrasonic cleaning, put into vacuum drying oven after the washing and dry, if polish tungsten ring internal surface and chromium zirconium copper pipe, polish and adopt metallographic abrasive paper to go on, the precedence of the specification of the metallographic abrasive paper that uses is: 400#, 800# and 1500 #.
in the technical scheme, the AB glue is coated on the outer surface of the tungsten ring for protection, the tungsten ring is placed to be completely dried, the tungsten ring can be completely solidified after being placed for more than 36 hours at room temperature (20-35 ℃), the outer surface of the whole tungsten ring is protected, and the inner surface of the tungsten ring (namely the part in contact with the chromium-zirconium-copper pipe) is reserved for next treatment.
The invention also discloses a tungsten-chromium-zirconium-copper pipe penetrating structure prepared by the method.
According to the technical scheme, the nano porous structure is prepared on the inner surface of the tungsten ring, the surface of tungsten is porous, the surface activity of tungsten metal can be improved, the mutual insolubility between tungsten and copper is overcome, and the tungsten-copper alloying is realized, so that the compounding/connection of the inner surface of the tungsten ring and the copper can be realized by adopting a surface nanocrystallization method in the preparation process of the tungsten/chromium-zirconium-copper tube penetrating structure, then the inner surface of the tungsten ring is electroplated with copper to obtain a tungsten ring copper-plated block, and the metallurgical bonding between tungsten and copper is realized through high-temperature diffusion annealing. And finally, the connection of the tungsten ring copper-plated block and the chromium-zirconium copper pipe is completed by using a brazing or diffusion welding method, the extreme technological parameters required by hot isostatic pressing and tube expansion thermal diffusion and complex and expensive equipment are not required, the cost is reduced, and the yield is improved. In addition, the tungsten surface nanocrystallization technology is not only suitable for regular planes, but also suitable for complex curved surfaces, and is beneficial to the design of a divertor with a novel structure in the future. In the preparation process, the nano porous structure on the inner surface of the tungsten ring not only increases the contact area and improves the surface activity, but also can play a role in mechanical meshing on a copper layer and improve the strength. The invention carries out the shear strength test on the tungsten/chromium zirconium copper pipe penetrating structure, and the result shows that the tungsten ring copper plating block and the chromium zirconium copper pipe have higher bonding strength.
Compared with the prior art, the invention has the following beneficial effects: (1) the invention provides a tungsten/chromium zirconium copper through pipe structure connecting method based on inner surface nano-porous of a tungsten ring, which comprises the steps of improving the surface activity of the inner surface of the tungsten ring through the inner surface nano-porous of the tungsten ring, then electroplating copper on the inner surface of the tungsten ring and alloying tungsten and copper at high temperature diffusion annealing to obtain a tungsten ring copper-plated block, finally completing the connection of the tungsten ring copper-plated block and a chromium zirconium copper pipe through a brazing or diffusion welding method, and finally realizing the connection of the tungsten/chromium zirconium copper through pipe structure; (2) the method is suitable for complex curved surfaces, and can form a nano porous structure on the inner surface of the tungsten ring. Extreme process parameters (including temperature and pressure) are not needed in the connection process, complex and expensive equipment is not needed to be designed and used, and the preparation process is simple, low in production cost, low in rejection rate and good in repeatability. The test result shows that the tungsten ring and the chromium-zirconium copper pipe have higher binding force.
drawings
FIG. 1(a) is an SEM photograph of an anodized nanoporous layer on the inner surface of a tungsten ring in accordance with the present invention.
FIG. 1(b) is an SEM photograph of the inner surface of the tungsten ring after deoxidation treatment in the present invention.
fig. 2(a) is a corresponding energy spectrum diagram of fig. 1 (a).
Fig. 2(b) is a corresponding energy spectrum diagram of fig. 1 (b).
FIG. 3 is an assembly diagram of the components of the W/Cr-Zr-Cu pipe penetrating structure of the present invention, in which 1-W ring copper plating block, 2-middle layer (brazing filler metal), and 3-Cr-Zr-Cu pipe.
FIG. 4(a) is a graph of high temperature heating bonding temperature versus time used in the present invention.
FIG. 4(b) is a temperature-time graph of the aging treatment employed in the present invention.
FIG. 5 is a photograph of a tungsten/chromium zirconium copper through pipe structure connecting member prepared in the present invention.
FIG. 6 is a schematic diagram of an interlaminar (interface) shear test device of a tungsten/chromium zirconium copper through-tube structure, wherein 1-chromium zirconium copper tube, 2-interlayer (brazing filler metal), 3-tungsten ring copper-plated block, 4-shear test fixture and P is external force.
FIG. 7(a) is a load-displacement plot of an interlaminar shear test of a tungsten/chromium zirconium copper feed-through structure of example 1.
FIG. 7(b) is a load-displacement plot of an interlaminar shear test of the W/Cr-Zr-Cu feedthru structure of example 2.
Detailed Description
the technical solutions of the present invention are further described in detail with reference to the accompanying drawings and specific embodiments, which are only illustrative of the present invention and are not intended to limit the present invention. The sample is from a fertilizer plasma station, a tungsten ring: xiamen tungsten industries ltd, chromium zirconium copper tube: shandong Lubao Metallurgical Co., Ltd; ab glue is commercially available from ailette.
Embodiment 1, a tungsten/chromium zirconium copper through pipe structure connection method based on tungsten ring inner surface nano-porous, comprising the following steps:
Step 1, pretreatment of a tungsten ring and a chromium-zirconium copper pipe:
And (6) polishing the surface. Polishing and flattening the inner surface of the tungsten ring and the chromium-zirconium copper pipe by using metallographic abrasive paper of No. 400, No. 800 and No. 1500 in sequence; and (4) ultrasonic cleaning. And (3) soaking the polished tungsten ring and the chromium-zirconium copper pipe in absolute ethyl alcohol for ultrasonic cleaning for 15min, and airing for later use. And (5) gluing the surface. And then coating AB glue on the outer surface of the tungsten ring, and standing at room temperature (20-35 ℃) for 36 hours until the tungsten ring is completely dried, namely protecting the outer surface of the whole tungsten ring, and reserving the inner surface of the tungsten ring (namely the part contacted with the chromium-zirconium-copper tube) for next treatment.
Step 2, anodizing the inner surface of the tungsten ring:
And preparing an anodic oxidation electrolyte. Adding 0.4g of sodium fluoride into 250mL of ultrapure water, stirring and dissolving, then adding 1.34mL of hydrofluoric acid, adding ultrapure water, fixing the volume to 400mL, stirring for 1h on a magnetic stirrer, and uniformly mixing to obtain the electrolyte. The mass percent of the sodium fluoride in the mixed solution is 0.2 percent, and the volume percent of the hydrofluoric acid is 0.3 percent.
And (4) anodizing. Taking the tungsten ring treated in the step 1) as an anode and a platinum sheet as a cathode, oxidizing for 60min at room temperature of 20-25 ℃ under 60V voltage, and then continuously oxidizing for 60min under 40V voltage, wherein the distance between the cathode and the anode is 3 cm. After the anodic oxidation, the inner surface of the tungsten ring generates a nano-porous tungsten oxide layer as shown in figure 1(a), and the energy spectrum thereof is shown in figure 2 (a).
And (5) performing deoxidation treatment on the tungsten ring. Putting the sample into an annealing furnace, discharging oxygen (air) by using inert protective gas, then adding hydrogen in the temperature rise process to achieve hydrogen atmosphere for treatment, heating the tungsten ring subjected to anodic oxidation treatment from room temperature to 700 ℃ at the speed of 5 ℃ per minute, keeping the temperature for 3h, cooling along with the furnace, and taking out. The nano-porous tungsten metal layer obtained after the deoxidation treatment is shown in figure 1(b), and the energy spectrum diagram is shown in figure 2 (b).
Step 3, preparation of tungsten ring copper-plated block
Preparing the cyanide-free copper electroplating solution. Adding 25g of copper sulfate, 170g of disodium ethylene diamine tetraacetate, 20g of potassium sodium tartrate, 4g of potassium nitrate and 40g of sodium hydroxide into 500mL of ultrapure water, stirring and dissolving, then adding ultrapure water to a constant volume of 1000mL, stirring for 12h on a magnetic stirrer, and uniformly mixing to obtain the electrolyte. The pH value of the cyanide-free copper electroplating solution is 12-13.
And (4) copper plating. Taking the tungsten ring treated in the step 2 as a cathode, taking a pure copper plate as an anode at room temperature, and controlling the current density to be 1A/dm at 40 DEG C2electroplating for 30min in a cyanide-free copper electroplating solution under the condition that the distance between a cathode and an anode is 10 cm.
And (5) high-temperature diffusion annealing. And putting the electroplating sample into acetone for 15min, and removing the AB glue. Putting the sample into an annealing furnace, exhausting oxygen (air) by using inert protective gas, then adding hydrogen in the temperature rise process to achieve hydrogen atmosphere for treatment, heating from room temperature to the annealing temperature of 980 ℃ at the speed of 5 ℃ per minute, keeping the temperature for 3 hours, cooling along with the furnace, and taking out. At this time, copper plating was completed on the inner surface of the tungsten ring (i.e., the portion in contact with the chromium zirconium copper pipe).
Step 4, connecting the tungsten ring copper-plated block with the chromium-zirconium copper pipe
And (6) assembling. According to the assembly diagram shown in fig. 3, the chromium-zirconium copper pipe is placed in the hole of the tungsten ring copper plating block and keeps coaxial, the inner surface of the hole of the tungsten ring copper plating block is plated with copper through the steps, and the gap between the chromium-zirconium copper pipe and the tungsten ring copper plating block is filled to assemble a connection sample by taking the oxygen-free copper foil with the purity of more than 99.99 wt.% as an intermediate layer.
and (4) heating and connecting at high temperature. The high temperature heating joining was performed according to the temperature-time curve shown in fig. 4 (a). Putting the sample into an annealing furnace, discharging oxygen (air) by using inert protective gas, then adding hydrogen in the temperature rising process, and forming hydrogen atmosphere in the annealing furnace before the temperature reaches 900 ℃; firstly, heating from room temperature to 900 ℃ at the speed of 10 ℃/min, then heating to 980 ℃ at the speed of 5 ℃/min, preserving the heat for 3h at 980 ℃ in the atmosphere of hydrogen protection, and then taking out the steel plate to be immersed in deionized water at the temperature of 25 ℃ for quenching treatment.
And carrying out aging treatment after the high-temperature heating connection. The aging treatment was carried out according to the temperature-time curve shown in FIG. 4 (b). Putting the sample into an annealing furnace, discharging oxygen (air) by using inert protective gas, then adding hydrogen in the temperature rising process, and forming hydrogen atmosphere in the annealing furnace before the temperature reaches 900 ℃; firstly, heating from room temperature to 400 ℃ at the speed of 10 ℃/min, then heating to 475 ℃ at the speed of 5 ℃/min, carrying out aging treatment for 3h at the temperature of 475 ℃ in a hydrogen protective atmosphere, cooling along with a furnace, and taking out a sample.
After the steps are finished, the tungsten/chromium zirconium copper through pipe structure connecting piece is prepared, and the prepared object is shown in figure 5.
FIG. 7(a) is a load-displacement curve for interlaminar shear testing of the W/Cr-Zr-Cu feedthru structural connection of example 1 at a maximum load of 6.8 kN.
Example 2, the tungsten/chromium zirconium copper through pipe structure connecting method based on tungsten ring inner surface nano-porous, the steps are basically the same as example 1, only step 4 is changed into:
And (6) assembling. The chromium-zirconium copper pipe is placed in a hole of a tungsten ring copper-plated block and keeps coaxial, 88.75Cu-10.95Al-0.3Ni (the sum of the mass of the copper, the aluminum and the nickel is 100 wtt%) foil with the thickness of 100 mu m is used as brazing filler metal, and a gap between the chromium-zirconium copper pipe and the tungsten ring copper-plated block is filled to assemble a connecting sample.
And (4) heating and connecting at high temperature. The high temperature heating joining was performed according to the temperature-time curve shown in fig. 4 (a). Putting the sample into an annealing furnace, firstly heating to 950 ℃ at a speed of 10 ℃/min, then heating to 980 ℃ at a speed of 5 ℃/min, preserving the heat for 0.5h at 980 ℃ under the hydrogen protection atmosphere, and then taking out the sample to be immersed in deionized water at 25 ℃ for quenching treatment.
FIG. 7(b) is a load-displacement curve for interlaminar shear testing of the W/Cr-Zr-Cu feedthru structural connection of example 2, having a maximum load of 18.3 kN.
the interfacial shear force test process of the tungsten/chromium zirconium copper through pipe structure connecting piece obtained in the embodiments 1 and 2 of the invention is as follows.
The interlaminar shear testing of the tungsten/chromium zirconium copper through-tube structural joint was carried out in an electronic universal tester (model MTS-E45), the test schematic being shown in fig. 6. The test parameters are: the test speed is 0.200 mm/min; the preload force speed is 2.000 mm/min; the stress end point is 0.020 mm/min; test stress Rate 0.005 (kN/mm)2) S; the preload force is 0.050 kN; the temperature was 25.0 ℃. The maximum load force F is obtained when the oxygen-free copper/chromium zirconium copper interface breaks. The load-displacement curve obtained in example 1 is shown in fig. 7(a), and the load-displacement curve obtained in example 2 is shown in fig. 7 (b). As can be seen from fig. 7, the maximum shear loads of examples 1 and 2 were 6.8kN and 18.3kN, respectively, and the bonding force was good.
The effective connection of the tungsten ring and the chromium-zirconium copper pipe can be realized by adjusting the technological parameters according to the content of the invention, the oxygen-free copper foil is used as the intermediate layer, the maximum shearing load can reach 6.5-7.2 kN, 88.75Cu-10.95Al-0.3Ni foil is used as the brazing filler metal, and the maximum shearing load can reach 18-18.8 kN. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. a tungsten-chromium-zirconium-copper pipe penetrating structure connecting method based on tungsten ring inner surface nano-porosification is characterized by comprising the following steps:
Step 1, arranging a nano porous tungsten structure on the inner surface of a tungsten ring
Taking a tungsten ring with a protected outer surface as an anode, carrying out anodic oxidation in electrolyte of sodium fluoride and hydrofluoric acid to form nano-porous tungsten oxide on the inner surface of the tungsten ring, and carrying out deoxidation treatment on the tungsten ring in a hydrogen atmosphere to form a nano-porous tungsten structure on the inner surface of the tungsten ring;
Step 2, plating copper on the inner surface of the tungsten ring
Taking the tungsten ring treated in the step 1 as a cathode for copper plating, and then carrying out high-temperature diffusion annealing to realize alloying between tungsten and copper so as to form a tungsten ring copper plating block;
Step 3, connecting the tungsten ring copper-plated block with the chromium-zirconium copper pipe
Placing a chromium-zirconium copper pipe into a hole of a tungsten ring copper plating block and keeping the chromium-zirconium copper pipe coaxial, arranging an intermediate layer in a gap between the chromium-zirconium copper pipe and the tungsten ring copper plating block, assembling a connection sample, and sequentially performing high-temperature heating connection and aging treatment to realize the connection of the tungsten ring copper plating block and the chromium-zirconium copper pipe;
High-temperature heating connection: under the atmosphere of hydrogen, raising the temperature from room temperature to 900-950 ℃ at the speed of 5-10 ℃/min, then raising the temperature to 960-1000 ℃ at the speed of 1-5 ℃/min, preserving the temperature for 0.5-5 h, and then taking out the steel plate to be immersed in deionized water at the temperature of 20-30 ℃ for quenching treatment;
Aging treatment: under the atmosphere of hydrogen, the temperature is increased from room temperature 20-25 ℃ to 400 +/-10 ℃ at the speed of 5-10 ℃/min, then the temperature is increased to 460-480 ℃ at the speed of 1-5 ℃/min, the heat preservation and aging treatment is carried out for 1-5 h, and the sample is taken out after furnace cooling.
2. The method for connecting the tungsten-chromium-zirconium-copper through pipe structure based on the nano-porosity of the inner surface of the tungsten ring according to the claim 1, wherein in the step 1, in the electrolyte, water or ultrapure water is used as a solvent, sodium fluoride (NaF) and hydrofluoric acid (HF) are used as solutes, and the mass percent of the sodium fluoride is 0.1-0.5%, preferably 0.2-0.4%; the hydrofluoric acid is present in an amount of 0.1 to 0.5% by volume, preferably 0.2 to 0.4% by volume.
3. the method for connecting the tungsten-chromium-zirconium-copper through pipe structure based on the nano-porosification of the inner surface of the tungsten ring as claimed in claim 1, wherein in the step 1, when the anodic oxidation is performed, the process parameters are as follows: oxidizing at room temperature under 60 + -5V for 30-90 min, preferably 60-80 min; then continuously oxidizing for 30-90 min, preferably 60-80 min under the voltage of 40 +/-5V; the distance between the cathode and the anode is 1-5 cm, preferably 3-5 cm.
4. The method for connecting the tungsten-chromium-zirconium-copper through pipe structure based on the nano-porosification of the inner surface of the tungsten ring according to the claim 1, wherein in the step 1, in the deoxidation treatment, the tungsten ring after the anodic oxidation treatment is heated to 600-700 ℃ from the room temperature at the speed of 5-10 ℃ per minute in the hydrogen atmosphere, the holding time is 1-5 h, and the tungsten ring is cooled with the furnace, preferably, the holding time is 3-5 h at 650-700 ℃.
5. The method for connecting the tungsten-chromium-zirconium-copper pipe penetrating structure based on the nano-porosification of the inner surface of the tungsten ring according to claim 1, wherein in the step 2, the copper plating is performed by using a pure copper plate as an anode and using a cyanide-free copper electroplating solution having the following composition: 25-45 g/L of copper sulfate, 120-170 g/L of disodium ethylene diamine tetraacetate, 20-40 g/L of potassium sodium tartrate, 4-8 g/L of potassium nitrate, 20-40 g/L of sodium hydroxide and ultrapure water, wherein the pH value of the cyanide-free copper electroplating solution is controlled to be 12-13.
6. The method for connecting the tungsten-chromium-zirconium-copper through pipe structure based on the nano-porosification of the inner surface of the tungsten ring as claimed in claim 1, wherein in the step 2, the copper plating is performed according to the following process parameters: at 40 +/-5 deg.C, current density is 1-5A/dm2Electroplating for 10-40 min, with the cathode and anode spaced by 5-10 cm, and preferably with current density of1—3A/dm2Electroplating for 20-30 min.
7. The method for connecting the tungsten-chromium-zirconium-copper through pipe structure based on the nano-porosification of the inner surface of the tungsten ring as claimed in claim 1, wherein in the step 2, when the high-temperature diffusion annealing is performed, the process parameters are as follows: raising the temperature from room temperature of 20-25 ℃ to annealing temperature of 950-1000 ℃ at the speed of 5-10 ℃ per minute in hydrogen atmosphere, preserving the heat for 1-5 h, cooling along with the furnace, and taking out.
8. The method for connecting the tungsten-chromium-zirconium-copper through pipe structure based on the nano-porosification of the inner surface of the tungsten ring as claimed in claim 1, wherein in the step 3, the high-temperature heating is performed for connecting: heating to 920-950 ℃ from room temperature at a speed of 5-10 ℃/min, then heating to 960-980 ℃ at a speed of 1-5 ℃/min, preserving heat for 3-5 h, and then taking out to dip into deionized water with a temperature of 20-30 ℃ for quenching treatment; aging treatment: raising the temperature from room temperature 20-25 ℃ to 400 +/-10 ℃ at the speed of 5-10 ℃/min, then raising the temperature to 470-480 ℃ at the speed of 1-5 ℃/min, carrying out heat preservation and aging treatment for 2.5-3.5 h, cooling along with the furnace, and taking out the sample.
9. The connection method of the tungsten-chromium-zirconium-copper through pipe structure based on the nano-porosification of the inner surface of the tungsten ring as claimed in claim 1, wherein the intermediate layer is an oxygen-free copper foil with a purity of not less than 99.99 wt.% and a thickness of 80 to 100 μm, or a Cu-Al-Ni solder with a composition of 88.75Cu-10.95Al-0.3Ni (the sum of the mass of Cu, Al and Ni is 100 wtt%) and a thickness of 80 to 100 μm.
10. a tungsten-chromium zirconium copper feed-through structure produced by the method of any one of claims 1 to 9.
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