CN110592644A - Method for auxiliary deposition of Cu-graphite composite coating on titanium alloy surface through nanocrystallization - Google Patents
Method for auxiliary deposition of Cu-graphite composite coating on titanium alloy surface through nanocrystallization Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 76
- 239000010439 graphite Substances 0.000 title claims abstract description 76
- 238000000576 coating method Methods 0.000 title claims abstract description 67
- 239000011248 coating agent Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000007709 nanocrystallization Methods 0.000 title claims abstract description 33
- 230000008021 deposition Effects 0.000 title claims abstract description 20
- 238000007747 plating Methods 0.000 claims abstract description 84
- 238000005422 blasting Methods 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000009713 electroplating Methods 0.000 claims abstract description 21
- 238000000151 deposition Methods 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 13
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 229940085605 saccharin sodium Drugs 0.000 claims abstract description 11
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 6
- 150000003608 titanium Chemical class 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000002086 nanomaterial Substances 0.000 claims abstract description 5
- HELHAJAZNSDZJO-UHFFFAOYSA-L sodium tartrate Chemical compound [Na+].[Na+].[O-]C(=O)C(O)C(O)C([O-])=O HELHAJAZNSDZJO-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000001433 sodium tartrate Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 9
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 8
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 7
- 238000005238 degreasing Methods 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 27
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001472 potassium tartrate Substances 0.000 description 4
- 229940111695 potassium tartrate Drugs 0.000 description 4
- 235000011005 potassium tartrates Nutrition 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004372 laser cladding Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005271 boronizing Methods 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000036964 tight binding Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a method for auxiliary deposition of a Cu-graphite composite coating on the surface of a titanium alloy through nanocrystallization, which comprises the following steps: carrying out high-strength shot blasting on the surface of the titanium alloy to obtain a surface nano structure, wherein the shot blasting strength of the high-strength shot on the surface is 0.1 mmA-0.4 mmA, and the shot blasting coverage rate is 100-200%; then sequentially carrying out surface oil removal, acid cleaning, alkali cleaning and activation treatment; using the activated titanium alloy as a cathode, a pure copper plate as an anode and adding CuSO4、CuCl2Sodium tartrate, H3BO3And performing electroplating treatment in the plating solution of saccharin sodium and graphite powder to obtain the Cu-graphite composite plating layer. The method can prepare the Cu-graphite composite coating with compact structure and close combination with the matrix on the surface of the titanium alloy, and the coating has excellent wear resistance, has the advantages of simple production process, environmental friendliness, no pollution, wide applicability and the like, and is suitable for production and application.
Description
Technical Field
The application relates to the field of surface modification of metal materials, in particular to a method for auxiliary deposition of a Cu-graphite composite coating through surface nanocrystallization.
Background
The poor wear resistance of titanium alloy is one of the main factors which hinder the application of titanium alloy in the fields of aerospace, traffic energy and the like. The titanium alloy has low hardness and high viscosity, so that under the action of friction load, the worn surface is easy to scratch or even stick to the surface, and the titanium alloy parts are easy to fail prematurely.
The preparation of the surface protective coating is an important means for improving the wear resistance of the titanium alloy. Therefore, researchers at home and abroad prepare various wear-resistant coatings on the surface of the titanium alloy by adopting various means such as surface chemical heat treatment, diffusion infiltration, micro-arc oxidation, laser cladding, plasma spraying and the like, such as aluminide coatings, silicide coatings, nitriding or boronizing coatings, ceramic coatings, multi-component composite coatings and the like. However, from the existing results, the defects of the preparation technology or the performance of the coating are limited, and the currently developed wear-resistant protective coating generally has the defects of poor impact resistance, weak combination with the matrix, obvious reduction of the fatigue performance of the matrix, complicated preparation process, low efficiency and the like. For example, nitriding the surface of titanium alloy can improve the hardness and wear resistance of the surface, but when the temperature exceeds 550 ℃, nitrogen and titanium react strongly, so that the brittleness of the matrix is increased; the coating prepared by adopting the plasma spraying or magnetron sputtering method is influenced by the activity of the titanium alloy matrix, so that the bonding strength of the coating and the matrix is not high; the coating prepared by the laser cladding method generally has the defects of large internal stress, more internal cracks or microcracks and the like. Therefore, the problem of friction wear protection of the titanium alloy is far from being solved, and the titanium alloy surface protection coating which is simple in process, high in production efficiency and excellent in friction wear protection effect and the preparation process thereof are lacked.
Electroplating is a coating preparation technology with simple process, low cost and high production efficiency. At present, the technologies of nickel plating, chromium plating and copper plating on the surfaces of iron-based alloys and aluminum alloys are mature, and the related composite plating process is also generally applied. Wherein, the copper plating layer has proper hardness, low friction coefficient and excellent wear resistance, and is an ideal surface friction protective coating of titanium alloy. However, for titanium alloy, because the surface activity is high, a layer of oxide or nitride is formed on the inner surface in a short time after oil removal, acid cleaning, alkali cleaning and activation, so that the bonding strength of the electroplated coating and the matrix is poor, and the preparation of the Cu coating with high bonding strength with the matrix by adopting an electroplating or composite plating process is difficult; in addition, the hardness of the pure Cu plating is low, leading to premature failure during rubbing with plastic deformation. The yao feijing and shengxizhi from northwest university adopt the electroplating method to prepare the Cu-plated layer on the surface of the TC4 alloy, which effectively reduces the friction coefficient of the TC4 alloy, but the Cu-plated layer fails after 5min and 20min abrasion, and the yao feijing and shengxizhi do not disclose specific electroplating processes.
Proper amount of graphite is added into the Cu-plated layer, and the excellent friction reducing and lubricating effects of the graphite are utilized, so that the friction protection performance of the plated layer can be greatly improved. However, the graphite particles have smooth surfaces and poor hydrophilicity, are not easy to prepare suspension plating solution, and are not easy to adsorb on the surface of the matrix alloy in the electroplating process, so that the preparation of the Cu-graphite composite coating with compact structure and tight combination with the matrix alloy is difficult. Longxili et al, a limited institute of advanced metal materials and technology, have disclosed a method for preparing a Cu-graphite coating on the surface of a TC4 alloy, wherein a TC4 alloy is subjected to conventional surface degreasing and pickling corrosion activation, and then is placed in a plating solution consisting of graphite particles ablated by copper sulfate, sulfuric acid and nitric acid to be electroplated to obtain the coating; but still does not solve the problem that the surface of the titanium alloy is easy to oxidize and is not firmly combined with the base alloy due to nitridation, and the actual protection effect is not ideal. The technology of preparing the Cu-graphite composite coating with compact structure and close combination with the matrix alloy on the surface of the titanium alloy is still blank.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, in particular to the problem of poor bonding force between a Cu-graphite composite coating on the surface of a titanium alloy and a matrix alloy. The key point of the invention is that high-density vacancy and dislocation are introduced on the surface of the titanium alloy by utilizing surface high-energy shot blasting nanocrystallization, the activity and the adsorption capacity of the surface of the titanium alloy are improved, and HF and a strong oxidant K are utilized simultaneously2Cr2O3The synergistic effect of the two components activates and passivates the surface structure of the titanium alloy, and the combination of the proper composite plating process effectively improves the binding force of the Cu-graphite composite plating layer and the titanium alloy matrix, can prepare the Cu-graphite composite plating layer with uniform and compact structure and tight binding with the matrix, and has the advantages of simple process,Low cost, wide adaptability, no pollution and the like, and is suitable for production and application.
The technical scheme is as follows: the method comprises the following steps: carrying out surface high-energy shot blasting on the titanium alloy to obtain a surface nano structure, wherein the shot blasting strength is 0.1 mmA-0.4 mmA, and the shot blasting coverage rate is 100-200%; then sequentially carrying out surface oil removal, acid cleaning, alkali cleaning and activation treatment; using the activated titanium alloy as a cathode, a pure copper plate as an anode and adding CuSO4、CuCl2Sodium tartrate, H3BO3And performing composite plating treatment in the plating solution of saccharin sodium and refined graphite powder to obtain the Cu-graphite composite plating layer.
Specifically, the surface high-energy shot blasting is carried out, the shot is a GCr15 ball with the diameter of 8mm, the GCr15 ball is used as the shot, so that the strong plastic deformation of the surface of the titanium alloy is effectively caused, the surface of the material is not scratched, the shot blasting strength is lower than the range, the surface nanocrystallized structure cannot be obtained, and the excessive plastic deformation of the surface of the titanium alloy is easily caused to crack above the range; the shot blasting coverage rate is too low to obtain complete surface nano-structure, and too high easily causes titanium alloy surface cracking. The surface nanocrystallization treatment is carried out on the titanium alloy before plating, so that high-density vacancies and dislocations are introduced on the surface of the titanium alloy, the surface activity of the titanium alloy is increased, the adsorption capacity of the titanium alloy is improved, and the bonding strength of the titanium alloy and the Cu-graphite composite plating layer is enhanced. Further, in the present invention, the shot strength is preferably 0.25mmA and the shot coverage is preferably 150%.
Specifically, the surface oil removal, acid washing, alkali washing and activation treatment respectively comprise: 1) surface degreasing: ultrasonically cleaning in an acetone solution for 5-10 min and then drying; 2) surface pickling: and (3) soaking the sample in 35% HF solution for 10-30 s, preferably 20 s. 3) Surface alkali washing: soaking the acid-washed sample in a (40-60) g/L NaOH solution for 20-40 s, preferably, the concentration of the NaOH solution is 50g/L, and the soaking time is 30 s; 4) surface activation: placing the sample in HF with the mass fraction of 35% and saturated K2Cr2O3Soaking the mixed solution for 30-50 min, preferably, the activation time is 40 min. Before platingThis treatment is carried out in order to clean the surface of the pre-titanized alloy sufficiently, while using HF and a strong oxidizing agent K2Cr2O3The synergistic effect of the components fully activates and passivates the surface structure of the titanium alloy, and enhances the bonding strength of the titanium alloy and the pre-plated Cu-graphite composite plating layer.
Specifically, the plating solution consists of (20-40) g/L of CuSO4(10-30) g/L of CuCl2120-200 g/L potassium tartrate and 20-40 g/L H3BO3(0.6-1) g/L saccharin sodium and 10-30 g/L graphite powder; CuSO in plating solution4And CuCl2The content of the element is higher than the range, so that the growth of the coating is too fast, the residual stress is increased, and the growth rate of the coating is slowed down and the production efficiency is reduced below the range; the potassium tartrate content is higher than the range, the complexing effect is too strong, the deposition rate of a plating layer is reduced, and the stability of the plating solution is poor below the range; h3BO3The content of the hydrogen-containing compound is higher than the range, so that hydrogen evolution reaction is caused, the current efficiency is reduced, and the deposition rate of a coating is too high and the internal stress of the coating is increased below the range; the saccharin sodium is higher than the plating layer prepared in the range, and the plating layer is easy to peel when the saccharin sodium is higher than the range; the graphite powder is higher than the range, the bonding strength of the coating and the matrix is easy to reduce, the graphite content in the coating is too low below the range, and the antifriction and lubrication effects are poor. Therefore, preferred in the present invention, CuSO is present in the plating bath430g/L of CuCl220g/L, 160g/L potassium tartrate, H3BO330g/L, 0.8g/L saccharin sodium and 20g/L graphite powder.
Specifically, the graphite powder is prepared by ball milling 200-mesh graphite powder in a planetary ball mill for 4 hours, and the rotating speed of the ball mill is 300 r/min; the treatment is to obtain refined graphite powder with high surface activity, so that the adsorption and deposition of graphite particles in the coating in the composite plating process are facilitated.
Specifically, the electroplating process comprises the following steps: the cathode current density is 1-6A/dm2The temperature of the plating solution is 20-40 ℃, the stirring speed is 200-400 r/min, and the electroplating time is 10-50 min; preferably, the cathodic current density is 4A/dm2The temperature of the plating solution is 30 ℃, the stirring speed is 300r/min, and the electroplating time is 30min; the process is adopted to obtain the Cu-graphite composite coating with compact structure, close combination with the matrix and proper deposition rate. The cathode current density is higher than the range, the erosion of the coating is easy to generate, and the deposition rate of the coating is slow below the range; the temperature above the range is easy to cause the coating to blister, and the bonding strength of the coating and the base alloy is reduced below the range; the stirring speed higher than the range can increase the surface roughness of the plating layer, and the stirring speed lower than the range can cause the graphite particles in the plating solution to sink, so that the composite plating effect is poor; too short electroplating time and too small thickness of the plating layer can result in increased internal stress of the plating layer and poor bonding strength. Further, the preferred process of the invention is a cathodic current density of 4A/dm2The temperature of the plating solution is 30 ℃, the stirring speed is 300r/min, and the electroplating time is 30 min.
Has the advantages that: the invention creatively utilizes the following 3 aspects of synergistic action to improve the binding force of the Cu-graphite composite plating layer and the titanium alloy matrix and obtain the Cu-graphite composite plating layer with uniform and compact structure and tightly bound with the matrix: 1) the surface high-energy shot blasting obtains a nano titanium alloy surface structure, introduces high-density vacancies and dislocations, improves the activity and adsorption capacity of the surface of the titanium alloy, and increases the bonding strength of the titanium alloy and the surface Cu-graphite composite coating; 2) using HF and a strong oxidizing agent K2Cr2O3The synergistic effect of the two components activates and passivates the surface structure of the titanium alloy, inhibits the formation of oxides and nitrides on the surface of the titanium alloy, and increases the bonding strength between the titanium alloy and the surface Cu-graphite composite coating; 3) and the bonding force between the titanium alloy substrate and the Cu-graphite composite coating and between the titanium alloy substrate is further improved by utilizing a proper composite plating process.
The method can prepare the Cu-graphite composite coating with uniform and compact structure and compact combination with the matrix on the surface of the titanium alloy, has the advantages of simple process, low cost, wide adaptability, greenness, no pollution and the like, and has very important significance for expanding the practical application of the titanium alloy.
Drawings
FIG. 1 shows a structure of a titanium alloy surface after high energy shot blasting.
FIG. 2 is a surface topography diagram of a Cu-graphite composite coating on the surface of a titanium alloy.
FIG. 3 is a sectional view of the Cu-graphite composite coating on the surface of the titanium alloy.
FIG. 4 is a comparison of the cross-sectional shapes of the Cu-graphite composite coating deposited with the aid of the nanocrystallization of the surface of the titanium alloy and the Cu-graphite composite coating prepared without the surface nanocrystallization treatment.
FIG. 5 is a comparison of scratch acoustic signal curves of a titanium alloy surface nanocrystallization assisted deposition Cu-graphite composite coating and a Cu-graphite composite coating prepared without surface nanocrystallization treatment.
FIG. 6 shows the appearance of grinding marks of a Cu-graphite composite coating and a pure Cu coating on the surface of a titanium alloy after being respectively subjected to butt grinding with a GCr15 ball for 30min under a load of 1N.
FIG. 7 is a graph comparing the wear rate of Cu-graphite composite plating and pure Cu plating on the surface of titanium alloy and GCr15 ball under 1N load.
Detailed Description
In order to make the technical solutions better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only partial embodiments of the present application, but not all embodiments.
Example 1
Preparing a sample: sequentially polishing the surfaces of the titanium alloy sample by using No. 80-2000 waterproof abrasive paper, and then placing the titanium alloy sample in an acetone solution for ultrasonic cleaning; high-energy shot blasting on the surface: carrying out high-energy shot blasting treatment on the surface of the sample, wherein the shot is a GCr15 ball with the diameter of 8mm, the shot strength is 0.1mmA, and the shot coverage rate is 100%; surface degreasing: placing the titanium alloy sample subjected to surface shot blasting nanocrystallization in an acetone solution for ultrasonic cleaning for 10 min; fourthly, surface acid washing: soaking the deoiled sample in 35% HF solution for 10 s; surface alkaline washing: soaking the acid-washed sample in 40g/L NaOH solution for 20 s; surface activation: placing the sample after alkaline washing in HF and saturated K with the mass fraction of 35%2Cr2O3Soaking in the mixed solution for 30 min; preparing a plating solution: get1L of distilled water, 20g of CuSO410g of CuCl2120g of potassium tartrate, 20g of H3BO30.6g of saccharin sodium and 10g of graphite powder are stirred uniformly; wherein the graphite powder is prepared by ball milling 200-mesh graphite powder for 4 hours at the rotating speed of 300r/min by a planetary ball mill; preparing a plating layer: placing the activated titanium alloy sample in a prepared plating solution for composite plating treatment, taking out and drying by cold air; the cathode current density adopted by electroplating is 1A/dm2The temperature of the plating solution is 20 ℃, the stirring speed is 200r/min, and the electroplating time is 10 min.
Example 2
Preparing a sample: sequentially polishing the surfaces of the titanium alloy sample by using No. 80-2000 waterproof abrasive paper, and then placing the titanium alloy sample in an acetone solution for ultrasonic cleaning; high-energy shot blasting on the surface: carrying out high-energy shot blasting treatment on the surface of the sample, wherein the shot is a GCr15 ball with the diameter of 8mm, the shot strength is 0.25mmA, and the shot coverage rate is 150%; surface degreasing: placing the titanium alloy sample subjected to surface shot blasting nanocrystallization in an acetone solution for ultrasonic cleaning for 10 min; fourthly, surface acid washing: soaking the deoiled sample in 35% HF solution for 20 s; surface alkaline washing: soaking the acid-washed sample in 50g/L NaOH solution for 30 s; surface activation: placing the sample after alkaline washing in HF and saturated K with the mass fraction of 35%2Cr2O3Soaking in the mixed solution for 40 min; preparing a plating solution: adding 30g of CuSO into 1L of distilled water420g of CuCl2160g of potassium tartrate, 30g of H3BO30.8g of saccharin sodium and 20g of graphite powder are stirred uniformly; wherein the graphite powder is prepared by ball milling 200-mesh graphite powder for 4 hours at the rotating speed of 300r/min by a planetary ball mill; preparing a plating layer: placing the activated titanium alloy sample in a prepared plating solution for composite plating treatment, taking out and drying by cold air; the cathode current density adopted by electroplating is 4A/dm2The temperature of the plating solution is 30 ℃, the stirring speed is 300r/min, and the electroplating time is 30 min.
Example 3
Preparing a sample: sequentially polishing the surfaces of the titanium alloy sample by using No. 80-2000 waterproof abrasive paper, and then placing the titanium alloy sample in acetoneUltrasonic cleaning in solution; high-energy shot blasting on the surface: carrying out high-energy shot blasting treatment on the surface of the sample, wherein the shot is a GCr15 ball with the diameter of 8mm, the shot strength is 0.4mmA, and the shot coverage rate is 200%; surface degreasing: placing the titanium alloy sample subjected to surface shot blasting nanocrystallization in an acetone solution for ultrasonic cleaning for 10 min; fourthly, surface acid washing: soaking the deoiled sample in 35% HF solution for 30 s; surface alkaline washing: soaking the acid-washed sample in 50g/L NaOH solution for 40 s; surface activation: placing the sample after alkaline washing in HF and saturated K with the mass fraction of 35%2Cr2O3Soaking in the mixed solution for 50 min; preparing a plating solution: adding 40g of CuSO into 1L of distilled water430g of CuCl2200g of potassium tartrate, 40g of H3BO31g of saccharin sodium and 30g of graphite powder are uniformly stirred; wherein the graphite powder is prepared by ball milling 200-mesh graphite powder for 4 hours at the rotating speed of 300r/min by a planetary ball mill; preparing a plating layer: placing the activated titanium alloy sample in a prepared plating solution for composite plating treatment, taking out and drying by cold air; the cathode current density adopted by electroplating is 6A/dm2The temperature of the plating solution is 40 ℃, the stirring speed is 400r/min, and the electroplating time is 50 min.
As shown in FIG. 1, the nano-structure of the titanium alloy surface after high energy shot blasting in examples 1 to 3 was compared.
Wherein the high energy peening conditions shown in FIG. 1(a) are: the shot material is GCr15 balls with the diameter of 8mm, the shot blasting strength of 0.1mmA and the shot blasting coverage rate of 100 percent;
the high energy peening conditions shown in FIG. 1(b) are: the shot material is GCr15 balls with the diameter of 8mm, the shot blasting strength of 0.25mmA and the shot blasting coverage rate of 150 percent;
the high energy peening conditions shown in FIG. 1(c) are: the shot material is GCr15 balls with the diameter of 8mm, the shot blasting intensity of 0.4mmA and the shot blasting coverage rate of 200 percent.
It can be seen that the nanocrystallized titanium alloy structure is obtained under all three peening parameters, wherein the nanocrystallized structures obtained in examples 2 and 3 are finer.
As shown in fig. 2, the surface morphology of the Cu-graphite composite plating layer obtained in examples 1 to 3 under different process conditions was compared.
Wherein FIG. 2(a) is prepared according to the conditions described in example 1;
FIG. 2(b) is prepared according to the conditions described in example 2;
FIG. 2(c) is prepared according to the conditions described in example 3.
It can be seen that the Cu-graphite composite plating layer with dense tissue was prepared in each of examples 1, 2 and 3; among them, the plating layers prepared in examples 1 and 2 had smoother surfaces, while the plating layers prepared in examples 2 and 3 had higher graphite contents.
As shown in fig. 3, the cross-sectional shapes of the Cu-graphite composite coatings obtained in examples 1 to 3 under different process conditions were compared.
Wherein FIG. 3(a) is prepared according to the conditions described in example 1;
FIG. 3(b) is prepared according to the conditions described in example 2;
FIG. 3(c) is prepared according to the conditions described in example 3.
It can be seen that the Cu-graphite composite plating layers with compact structures and tightly combined with the matrix titanium alloy are prepared in the embodiments 1, 2 and 3; the composite plating layer obtained in the embodiment 2 has moderate thickness, compact structure, uniform distribution of graphite particles and good combination state with the matrix.
Therefore, the Cu-graphite composite coating which is compact in structure and tightly combined with the matrix titanium alloy is prepared on the surface of the titanium alloy by utilizing surface high-energy shot blasting nanocrystallization and combining with a proper surface activation technology and an electroplating process.
Product performance testing
As shown in fig. 4, the cross-sectional shapes of the Cu-graphite composite plating layer on the surface of the titanium alloy obtained under the process conditions of example 2 and the Cu-graphite composite plating layer prepared without surface nanocrystallization treatment are compared.
Wherein FIG. 4(a) is a cross-sectional profile of a Cu-graphite composite coating on the surface of a titanium alloy prepared according to the conditions described in example 2;
FIG. 4(b) is a sectional view of a Cu-graphite composite plating layer prepared without surface nanocrystallization treatment.
It can be seen that the Cu-graphite composite coating sprayed with the nanocrystallization auxiliary deposition on the surface is tightly combined with the matrix, and the graphite particles in the interior and on the surface are uniformly distributed; the Cu-graphite composite plating layer prepared without surface nano treatment and the cross section of the matrix titanium alloy have larger cracks, and the graphite particles in the plating layer are less distributed.
As shown in fig. 5, scratch acoustic signal curves of the Cu-graphite composite plating layer on the surface of the titanium alloy obtained under the process conditions of example 2 and the Cu-graphite composite plating layer prepared without the surface nanocrystallization treatment were compared.
Wherein FIG. 5(a) is a scratch acoustic signal curve of a Cu-graphite composite coating on the surface of a titanium alloy prepared according to the conditions described in example 2;
FIG. 5(b) is a scratch acoustic signal curve of a Cu-graphite composite plating layer prepared without surface nanocrystallization.
It can be seen that the bonding force between the Cu-graphite composite coating which is subjected to the surface spraying and the nanocrystallization auxiliary deposition and the titanium alloy matrix is strong, and the bonding force calculated according to the scratch signal curve is about 168.2N; the Cu-graphite composite plating layer prepared without surface nanocrystallization treatment has small binding force with the matrix titanium alloy, and is only about 69.7N; the bonding force between the Cu-graphite composite coating deposited with the surface nanocrystallization assistance and the titanium alloy matrix is obviously superior to that of the Cu-graphite composite coating obtained without the surface nanocrystallization treatment.
As shown in fig. 6, the surface wear profiles of the Cu-graphite composite plating layer on the surface of the titanium alloy obtained under the process conditions of example 2 and the pure Cu plating layer were compared.
Wherein, FIG. 6(a) is the appearance of grinding marks of a Cu-graphite composite plating layer on the surface of a titanium alloy prepared according to the conditions of example 2 and a GCr15 ball after being subjected to counter-grinding for 30min under a load of 1N;
FIG. 6(b) is the appearance of grinding marks of a pure Cu plating layer on the surface of a titanium alloy and a GCr15 ball after being ground for 30min under a load of 1N.
It can be seen that the Cu-graphite composite plating layer on the surface of the titanium alloy prepared under the conditions described in example 2 has a narrow wear scar and a smooth wear surface, while the wear surface of the pure Cu plating layer has a severe plastic deformation and has been worn through to fail after 30 times of wear.
As shown in fig. 7, the wear rates of the Cu-graphite composite plating layer and the pure Cu plating layer on the surface of the titanium alloy obtained under the process conditions of example 2 were compared with the wear rates of the GCr15 ball under a load of 1N, respectively.
It can be seen that the wear rate of the Cu-graphite composite coating on the surface of the titanium alloy prepared according to the conditions described in example 2 is about one third of that of the pure Cu coating; the Cu-graphite composite plating layer prepared by the invention has better wear resistance.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application.
Claims (9)
1. A method for carrying out nanocrystallization assisted deposition on a Cu-graphite composite coating on the surface of a titanium alloy is characterized by comprising the following steps: carrying out high-strength shot blasting on the surface of the titanium alloy to obtain a surface nano structure, wherein the shot blasting strength of the high-strength shot on the surface is 0.1 mmA-0.4 mmA, and the shot blasting coverage rate is 100-200%; then sequentially carrying out surface oil removal, acid cleaning, alkali cleaning and activation treatment; using the activated titanium alloy as a cathode, a pure copper plate as an anode and adding CuSO4、CuCl2Sodium tartrate, H3BO3And performing electroplating treatment in the plating solution of saccharin sodium and graphite powder to obtain the Cu-graphite composite plating layer.
2. The method for the titanium alloy surface nanocrystallization assisted deposition of the Cu-graphite composite coating according to claim 1, wherein the surface high-strength shot blasting is adopted and is a GCr15 sphere with the diameter of 8 mm.
3. The method for the nanocrystallization assisted deposition of the Cu-graphite composite coating on the surface of the titanium alloy according to claim 1, wherein the surface degreasing is that the titanium alloy sample subjected to the surface nanocrystallization is placed in an acetone solution for ultrasonic cleaning for 5-10 min.
4. The method for depositing the Cu-graphite composite coating on the titanium alloy surface in the nanocrystallization-assisted mode according to claim 1, wherein the acid cleaning is to soak the sample in 35% by mass of HF solution for 10-30 s.
5. The method for the nanocrystallization assisted deposition of the Cu-graphite composite coating on the surface of the titanium alloy according to claim 1, wherein the alkali washing is to soak the acid-washed sample in a (40-60) g/L NaOH solution for 20-40 s.
6. The method for the nanocrystallization-assisted deposition of the Cu-graphite composite coating on the surface of the titanium alloy according to claim 1, wherein the activation is that a sample subjected to alkali washing is placed in 35% by mass of HF and saturated K2Cr2O3Soaking the mixed solution for 30-50 min.
7. The method for the nanocrystallization-assisted deposition of the Cu-graphite composite coating on the surface of the titanium alloy according to claim 1, wherein the formula of the plating solution is as follows: (20-40) g/L of CuSO4(10-30) g/L of CuCl2120-200 g/L potassium tartrate and 20-40 g/L H3BO3(0.6-1) g/L saccharin sodium and 10-30 g/L graphite powder.
8. The method for the nanocrystallization assisted deposition of the Cu-graphite composite coating on the surface of the titanium alloy according to claim 1, wherein the graphite powder is prepared by ball milling 200-mesh graphite powder in a planetary ball mill for 4 hours, and the rotating speed of the ball mill is 300 r/min.
9. The method for the nanocrystallization-assisted deposition of the Cu-graphite composite coating on the surface of the titanium alloy as claimed in claim 1, wherein the electroplating process comprises the following steps: the cathode current density is 1-6A/dm2The temperature of the plating solution is 20-40 ℃, the stirring speed is 200-400 r/min, and the electroplating time is 10-50 min.
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