CN112144046A - Co @ graphene-titanium-based composite material and preparation method thereof - Google Patents
Co @ graphene-titanium-based composite material and preparation method thereof Download PDFInfo
- Publication number
- CN112144046A CN112144046A CN202011008341.5A CN202011008341A CN112144046A CN 112144046 A CN112144046 A CN 112144046A CN 202011008341 A CN202011008341 A CN 202011008341A CN 112144046 A CN112144046 A CN 112144046A
- Authority
- CN
- China
- Prior art keywords
- graphene
- titanium
- powder
- solution
- composite material
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 132
- 239000010936 titanium Substances 0.000 title claims abstract description 92
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 174
- 239000000843 powder Substances 0.000 claims abstract description 163
- 239000000243 solution Substances 0.000 claims abstract description 126
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000006185 dispersion Substances 0.000 claims abstract description 71
- 239000011259 mixed solution Substances 0.000 claims abstract description 69
- 239000007788 liquid Substances 0.000 claims abstract description 59
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 48
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 44
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000007747 plating Methods 0.000 claims abstract description 44
- 239000000126 substance Substances 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 33
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 150000001868 cobalt Chemical class 0.000 claims abstract description 16
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 51
- 239000002244 precipitate Substances 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 29
- 238000001291 vacuum drying Methods 0.000 claims description 28
- 238000003760 magnetic stirring Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 24
- 239000011159 matrix material Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 229940011182 cobalt acetate Drugs 0.000 claims description 18
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 16
- 230000010355 oscillation Effects 0.000 claims description 16
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical group [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 16
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 11
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 2
- 238000007772 electroless plating Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 14
- 238000005054 agglomeration Methods 0.000 abstract description 12
- 230000002776 aggregation Effects 0.000 abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 abstract description 10
- 239000010941 cobalt Substances 0.000 abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 230000003111 delayed effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 101000686227 Homo sapiens Ras-related protein R-Ras2 Proteins 0.000 description 18
- 102100025003 Ras-related protein R-Ras2 Human genes 0.000 description 18
- 239000000203 mixture Substances 0.000 description 12
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 239000001476 sodium potassium tartrate Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000001934 delay Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011156 metal matrix composite Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a Co @ graphene-titanium-based composite material, which comprises the following steps: firstly, preparing graphene dispersion liquid and titanium-based powder mixed liquid; mixing and insulating metal cobalt salt, a complexing agent and hydrazine hydrate to obtain a chemical plating solution, and adding a graphene dispersion solution to prepare a mixed solution; thirdly, preparing Co @ graphene powder from the mixed solution; preparing Co @ graphene dispersion liquid and adding the Co @ graphene dispersion liquid into the titanium-based powder mixed liquid to obtain semi-solid slurry; fifthly, drying and grinding to obtain Co @ graphene-titanium-based composite powder; and sixthly, performing spark plasma sintering to obtain the Co @ graphene-titanium-based composite material. According to the invention, cobalt particles are mixed and coated on the surface of graphene, so that the agglomeration of large graphene sheets is reduced, the contact area between graphene and titanium-based powder is increased, the wettability between graphene and titanium-based powder is improved, the in-situ self-generated interface reaction between the graphene and the titanium-based powder is delayed, and the mechanical property of the Co @ graphene-titanium-based composite material is improved.
Description
Technical Field
The invention belongs to the technical field of metal matrix composite preparation, and particularly relates to a Co @ graphene-titanium matrix composite and a preparation method thereof.
Background
Titanium and titanium alloy are used as structural materials, have the characteristics of high strength, high fracture toughness, excellent crack expansion resistance and corrosion resistance and the like, and are widely used in the fields of aerospace, automobiles, biomedical treatment and the like. In recent years, with the rapid development of the aerospace industry, higher use requirements are put forward on the performance of titanium alloys, and metal matrix composite materials receive wide attention due to excellent mechanical properties. The metal-based composite material is used for replacing the traditional metal alloy and is used as a main bearing structural member of the aerospace engine, and the metal-based composite material has important significance for improving the thrust-weight ratio and the reliability of the aerospace craft. The titanium-based composite material becomes one of the main materials of the ultra-high sound speed aerospace craft and the next generation advanced aeroengine due to the high specific strength, specific rigidity and high temperature resistance of the titanium-based composite material.
Graphene is a two-dimensional carbon nanomaterial, is a hexagonal honeycomb lattice consisting of carbon atoms of s hybrid orbitals, and has ultrahigh specific strength, high toughness and excellent electric and heat conduction properties. The graphene is used as a reinforcement, the mechanical property of the material can be well improved due to the super-specific strength of the graphene, a compact interface can be formed between the graphene and a matrix due to the large specific surface area, the growth of crystal grains is well hindered, and the stress load transfer is facilitated. Meanwhile, the flaky special folding structure of the graphene layer can also play a role in buffering, so that the strength and toughness of the composite material are improved. At present, graphene is widely used as a reinforcing material of a metal matrix (such as titanium, aluminum, magnesium and copper), and the mechanical property of the metal matrix is effectively improved. However, the graphene titanium-based composite material still has problems which need to be solved urgently at present, such as poor dispersibility, poor wettability, poor bonding performance and the like of graphene in a titanium matrix. These result in easy agglomeration during composite preparation, often with less than desirable performance results.
The problems of poor wettability between graphene and the titanium matrix composite material, poor graphene dispersion effect and interface bonding between graphene and the titanium matrix are solved. Therefore, how to effectively control the combination between the graphene and the titanium matrix and the uniform dispersion of the graphene in the matrix are the key for realizing the performance optimization of the graphene titanium matrix composite material and are also important problems in the industrialization of the graphene titanium matrix composite material.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a Co @ graphene-titanium-based composite material aiming at the defects of the prior art. According to the method, cobalt particles are mixed and coated on the surface of the graphene, so that the agglomeration of a large layer of graphene is reduced, the contact area of the graphene and titanium-based powder is increased, the agglomeration phenomenon of the graphene on the surface of the titanium-based powder is inhibited, the wettability between the graphene and the titanium-based powder is improved, the in-situ self-generated interface reaction between the titanium-based powder and the graphene is delayed, and the mechanical property of the Co @ graphene-titanium-based composite material is improved.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a Co @ graphene-titanium matrix composite is characterized by comprising the following steps:
step one, adding graphene into ethanol for dispersion under the ultrasonic oscillation condition to obtain graphene dispersion liquid, adding titanium powder or titanium alloy powder into a surfactant solution under the magnetic stirring condition, and performing magnetic stirring to obtain a titanium-based powder mixed solution;
step two, mixing metal cobalt salt, a complexing agent and hydrazine hydrate, then preserving heat for 5-20 min under the condition of a water bath at 50-70 ℃ to obtain a chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution for mechanical stirring, adding alkali liquor until wine red precipitate is generated and disappears, continuing to add the alkali liquor until the solution is purple, and then mechanically stirring for 10-30 min to obtain a mixed solution; the content of metal cobalt salt in the chemical plating solution is 0.1-0.2 mol/L, the content of complexing agent is 0.1-0.2 mol/L, the content of hydrazine hydrate is 40-100 mL/L, and the mass concentration of hydrazine hydrate is 50%;
step three, precipitating and filtering the mixed solution obtained in the step two for more than 12 hours, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution, sequentially repeating the washing and centrifuging processes for 3 to 5 times on the precipitate obtained by centrifuging the last time, placing the precipitate obtained by centrifuging the last time into a vacuum drying oven, and drying the precipitate for 10 to 12 hours at the temperature of between 60 and 80 ℃ to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the titanium-based powder mixed liquid obtained in the step one, and mechanically stirring at a stirring speed of 300-500 rpm in a water bath condition of 50-70 ℃ to obtain semi-solid slurry;
putting the semi-solid slurry obtained in the fourth step into a vacuum drying oven for drying, and grinding to obtain Co @ graphene-titanium base composite powder; the drying temperature is 60-80 ℃, and the drying time is more than 12 h;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-titanium-based composite powder obtained in the fifth step to obtain a Co @ graphene-titanium-based composite material; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 900-1100 ℃, the sintering time is 5-10 min, and the sintering pressure is more than 40 MPa.
According to the preparation method, firstly, a chemical plating method is adopted to reduce metal cobalt salt into cobalt particles, the cobalt particles are mixed and coated on the surface of graphene to obtain Co @ graphene powder, the graphene with a layered structure is expanded by the cobalt particles to form a three-dimensional structure of a cobalt and graphene mixed body, the space ratio of the graphene is increased, the specific surface area of the graphene is enlarged, the dispersion effect of the graphene is improved, the dispersion of the graphene is enhanced, and thus the agglomeration of large-sheet graphene is reduced; and then, coating the Co @ graphene powder on the surface of titanium or titanium alloy powder by mixing and stirring to obtain Co @ graphene-titanium-based composite powder with a discontinuous core-shell structure, wherein the Co @ graphene is used as a shell, the titanium or titanium alloy powder is used as a core, and the Co @ graphene-titanium-based composite material is obtained by sintering. In conclusion, the method improves the dispersion uniformity of the graphene in the titanium matrix, improves the wettability between the graphene and the titanium matrix, and delays the in-situ self-generated interface reaction between the titanium matrix and the graphene, thereby improving the mechanical property of the Co @ graphene-titanium matrix composite material.
The preparation method of the Co @ graphene-titanium-based composite material is characterized in that in the first step, the surfactant solution is a polyvinylpyrrolidone solution, a polyvinyl alcohol solution or a cetyl trimethyl ammonium bromide solution. The preferable surfactant solution has a good modification effect on the surfaces of titanium powder or titanium alloy powder particles, so that the dispersity of Co @ graphene powder on the surfaces of titanium-based powder is enhanced, and the cost is low.
The preparation method of the Co @ graphene-titanium-based composite material is characterized in that the mass concentration of the surfactant solution is 3%. The mass concentration of the preferable surfactant solution can realize a good modification effect on the surface of the titanium powder or the titanium alloy powder, avoid the adhesion phenomenon of Co @ graphene powder on the titanium-based powder caused by overhigh mass concentration, and avoid the waste of the surfactant.
The preparation method of the Co @ graphene-titanium-based composite material is characterized in that in the second step, the mechanical stirring speed is 300 rpm-400 rpm, the time is 10 min-20 min, and the temperature is 60-80 ℃. The preferred mechanical stirring process parameters achieve sufficient dispersion of Co @ graphene in a hybrid structure in titanium powder or titanium alloy powder.
The preparation method of the Co @ graphene-titanium-based composite material is characterized in that in the second step, the metal cobalt salt is cobalt acetate or cobalt sulfate, and the complexing agent is potassium sodium tartrate or sodium citrate. The preferable types of the metal cobalt salt and the complexing agent are favorable for obtaining high-purity Co particles through reduction, do not introduce redundant impurities, are relatively easy to obtain and have low cost.
The preparation method of the Co @ graphene-titanium-based composite material is characterized in that the molar ratio of the metal cobalt salt to the complexing agent in the chemical plating solution in the second step is 1: (1-1.5), the molar ratio of hydrazine hydrate to metal cobalt salt is 1:3, the alkali liquor is 6mol/L sodium hydroxide solution, and the pH value of the mixed solution is 11-14. The molar ratio of hydrazine hydrate to metallic cobalt salt is 1:2 as calculated from the chemical reaction equation, but considering that hydrazine hydrate is easily volatilized, the molar ratio of hydrazine hydrate to metallic cobalt salt is 1: 3. The consumption in the reaction process is fully considered by the optimal molar ratio of the raw materials, the proportion of each raw material is properly improved on the basis of the molar ratio of each raw material required by a chemical reaction equation, and the smooth generation of Co particles is ensured; the optimized alkali liquor type, concentration and pH of the mixed solution ensure that Co ions in the chemical plating solution are fully reduced, and the Co ions are mixed and coated on the surface of graphene to form Co @ graphene powder with a better ratio, so that the production of impurities and the waste of Co ions and graphene are reduced.
The preparation method of the Co @ graphene-titanium-based composite material is characterized in that the centrifugal rotating speed in the third step is 8000 rpm-10000 rpm, and the time is 5 min-10 min. The optimized centrifugal technological parameters enable impurities in the mixed solution to be fully separated and removed, the centrifugal time is shortened, and the purity of the Co @ graphene powder is guaranteed.
The preparation method of the Co @ graphene-titanium-based composite material is characterized in that the Co @ graphene-titanium-based composite material is ground in the fifth step to obtain uniform Co @ graphene-titanium-based composite powder without agglomeration. The Co @ graphene-titanium-based composite powder is obtained through sieving after grinding, so that the Co @ graphene-titanium-based composite powder is uniformly dispersed, and the subsequent sintering process is facilitated.
The preparation method of the Co @ graphene-titanium-based composite material is characterized in that the technological parameters of spark plasma sintering in the sixth step are as follows: the sintering temperature is 900-1000 ℃, the sintering time is 5-10 min, and the sintering pressure is 40-100 MPa. The optimized discharge plasma sintering process parameters are beneficial to obtaining the Co @ graphene-titanium-based composite material with higher density.
In addition, the invention also provides the Co @ graphene-titanium-based composite material prepared by the method.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts chemical plating to obtain cobalt particles and enables the cobalt particles to be mixed and coated on the surface of graphene to form Co @ graphene powder, the graphene with the layered structure is spread and dispersed, the space ratio of the graphene is increased, the agglomeration of large-sheet graphene is reduced, and then, the Co @ graphene-titanium-based composite material with a discontinuous core-shell structure and taking the Co @ graphene as a shell and titanium or titanium alloy powder, namely titanium-based powder as a core is obtained by combining mechanical stirring, and the Co @ graphene-titanium-based composite material is obtained by sintering, so that the contact area of the graphene and the titanium-based powder is increased, the agglomeration phenomenon of the graphene on the surface of the titanium-based powder is inhibited, the wettability between the graphene and the titanium-based body is improved, the in-situ self-generated interface reaction between the titanium-based body and the graphene is delayed, and the mechanical property of the Co @ graphene-titanium-based composite material is improved.
2. According to the invention, the Co particles are mixed and coated on the surface of the graphene by adopting a chemical plating method to obtain Co @ graphene powder, so that the treatment processes of sensitization and activation of the graphene are omitted, the process is simple, the operability is strong, and the coating effect is better.
3. The strength of the Co @ graphene-titanium-based composite material is obviously improved.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1a is an SEM image of Co @ graphene-TC 21 composite powder prepared in example 1 of the present invention.
FIG. 1b is an enlarged view of area A in FIG. 1 a.
Fig. 2a is an SEM image of the graphene-TC 21 composite powder prepared in comparative example 1 of the present invention.
Fig. 2b is an enlarged view of the area a in fig. 2 a.
Fig. 3 is a graph showing the tensile profiles of the Co @ graphene-TC 21 composite material prepared in example 1 of the present invention and the graphene-TC 21 composite material prepared in comparative example 1.
Fig. 4 is a graph showing the tensile profiles of the Co @ graphene-TC 4 composite material prepared in example 2 of the present invention and the graphene-TC 4 composite material prepared in comparative example 2.
Detailed Description
In view of the volatility of hydrazine hydrate, the amounts of hydrazine hydrate used in examples 1 to 10 of the present invention were increased as compared with the actual amounts.
Example 1
The embodiment comprises the following steps:
step one, under the ultrasonic oscillation condition, 0.2g of graphene powder is added into 200mL of ethanol for dispersing for 60min to obtain graphene dispersion liquid, under the magnetic stirring condition, 100g of spherical TC21 powder is added into 200mL of 3% polyvinyl alcohol solution, and the mixture is magnetically stirred for 2h to obtain TC21 powder mixed liquid;
step two, mixing cobalt acetate, sodium potassium tartrate and hydrazine hydrate, then preserving heat for 5min under the condition of a water bath at 60 ℃ to obtain a chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution, mechanically stirring for 10min at the temperature of 60 ℃ at the rotating speed of 300rpm, then adding 6mol/L sodium hydroxide solution until wine red precipitate is generated and disappears, continuously adding 6mol/L sodium hydroxide solution until the solution is purple, and stirring for 30min again to obtain a mixed solution with the pH value of 11; the content of cobalt acetate in the chemical plating solution is 0.1mol/L, the content of potassium sodium tartrate is 0.1mol/L, the content of hydrazine hydrate is 40mL/L, and the mass concentration of hydrazine hydrate is 50%;
thirdly, precipitating and filtering the mixed solution obtained in the second step for 12 hours, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution for 5 minutes at the rotating speed of 8000rpm, sequentially repeating the washing and centrifuging processes for 3 times on the precipitate obtained by centrifuging the last time, placing the precipitate obtained by centrifuging the last time in a vacuum drying box, and drying the precipitate for 8 hours at the temperature of 80 ℃ to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol, performing ultrasonic treatment for 1h to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the TC21 powder mixed liquid obtained in the step one, and mechanically stirring at the stirring speed of 300rpm in a water bath condition of 50 ℃ to obtain semi-solid slurry;
step five, placing the semi-solid slurry obtained in the step four in a vacuum drying oven, drying for 12 hours at 60 ℃, and grinding to obtain non-caking and uniform Co @ graphene-TC 21 composite powder;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-TC 21 composite powder obtained in the fifth step to obtain a block Co @ graphene-TC 21 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 1000 ℃, the sintering time is 5min, and the sintering pressure is 45 MPa.
The microstructure of the Co @ graphene-TC 21 composite powder prepared in this example was analyzed by scanning electron microscope observation, and the results are shown in fig. 1a and 1 b.
Fig. 1a is an SEM image of the Co @ graphene-TC 21 composite powder prepared in this embodiment, and fig. 1b is an enlarged view of a region a in fig. 1a, and as can be seen from fig. 1a and fig. 1b, the Co @ graphene is uniformly distributed on the surface of the spherical TC21 powder, and Co particles are mixed and coated on the surface of the graphene to form a discontinuous mixed and coated state structure, so that the agglomeration phenomenon of the graphene on the surface of the spherical TC21 powder is suppressed.
Comparative example 1
This comparative example comprises the following steps:
step one, under the ultrasonic oscillation condition, 0.2g of graphene powder is added into 200mL of ethanol for dispersing for 60min to obtain graphene dispersion liquid, under the magnetic stirring condition, 100g of spherical TC21 powder is added into 200mL of 3% polyvinyl alcohol solution, and the mixture is magnetically stirred for 2h to obtain TC21 powder mixed liquid;
step two, mixing the graphene dispersion liquid obtained in the step one with a TC21 powder mixed solution, and placing the mixture at 50 ℃ and mechanically stirring the mixture at a rotating speed of 300rpm to obtain semi-solid slurry;
step three, placing the semi-solid slurry obtained in the step two in a vacuum drying oven, drying for 12 hours at 60 ℃, and grinding to obtain non-caking and uniform graphene-TC 21 composite powder;
step four, carrying out spark plasma sintering molding on the graphene-TC 21 composite powder obtained in the step three to obtain a block graphene-TC 21 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 1000 ℃, the sintering time is 5min, and the sintering pressure is 45 MPa.
Fig. 2a is an SEM image of the graphene-TC 21 composite powder prepared in the present comparative example, and fig. 2b is an enlarged view of a region a in fig. 2a, and it can be seen from fig. 2a and 2b that graphene in the graphene-TC 21 composite powder is uniformly distributed on the surface of TC21 spherical powder and is tightly attached, and local agglomeration phenomenon of graphene occurs on the surface of TC21 spherical powder.
A Co @ graphene-TC 21-based composite material prepared in example 1 of the present invention and a graphene-TC 21-based composite material prepared in comparative example 1 were subjected to uniaxial tensile test (with an extensometer) using a universal material testing machine model Instron598X, and a tensile rate was set to 1X 10-3s-1The results are shown in FIG. 3.
Fig. 3 is a tensile curve diagram of the Co @ graphene-TC 21-based composite material prepared in example 1 and the graphene-TC 21-based composite material prepared in comparative example 1, and it can be seen from fig. 3 that the yield strength of the Co @ graphene-TC 21-based composite material prepared in example 1 is 1144MPa, the tensile strength is 1282MPa, which is significantly higher than the yield strength 1001MPa and the tensile strength 1161MPa of the graphene-TC 21-based composite material prepared in comparative example 1, which illustrates that the mechanical properties of the Co @ graphene-TC 21-based composite material are improved by the process of plating cobalt on the surface of graphene in the present invention.
Example 2
The embodiment comprises the following steps:
step one, under the ultrasonic oscillation condition, adding 0.2g of graphene powder into 100mL of ethanol for dispersing for 120min to obtain a graphene dispersion solution, adding 100g of spherical TC4 powder into 200mL of 3% polyvinyl alcohol solution under the magnetic stirring condition, and performing magnetic stirring for 2.5h to obtain a TC4 powder mixed solution;
step two, mixing cobalt sulfate, sodium potassium tartrate and hydrazine hydrate, then preserving heat for 10min under the condition of a water bath at 60 ℃ to obtain a chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution, mechanically stirring for 10min at the rotation speed of 300rpm at 60 ℃, then adding 6mol/L sodium hydroxide solution until wine red precipitate is generated and disappears, continuing to add 6mol/L sodium hydroxide solution until the solution is purple, and stirring for 30min again to obtain a mixed solution with the pH value of 13; the content of cobalt sulfate in the chemical plating solution is 0.15mol/L, the content of potassium sodium tartrate is 0.15mol/L, the content of hydrazine hydrate is 60mL/L, and the mass concentration of hydrazine hydrate is 50%;
step three, precipitating and filtering the mixed solution obtained in the step two for 20 hours, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution for 5 minutes at the rotating speed of 8000rpm, sequentially repeating washing and centrifuging processes on the precipitate obtained by centrifuging the mixed solution for 5 times, placing the precipitate obtained by centrifuging the last time into a vacuum drying oven, and drying the precipitate at 80 ℃ for 10 hours to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol, performing ultrasonic treatment for 2 hours to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the TC4 powder mixed liquid obtained in the step one, and mechanically stirring at a stirring speed of 450rpm in a water bath condition of 60 ℃ to obtain semi-solid slurry;
step five, placing the semi-solid slurry obtained in the step four in a vacuum drying oven, drying at 80 ℃ for 12 hours, and grinding to obtain non-caking and uniform Co @ graphene-TC 4 composite powder;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-TC 4 composite powder obtained in the fifth step to obtain a block Co @ graphene-TC 4 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 1000 ℃, the sintering time is 6min, and the sintering pressure is 45 MPa.
Comparative example 2
This comparative example comprises the following steps:
step one, under the ultrasonic oscillation condition, adding 0.2g of graphene powder into 100mL of ethanol for dispersing for 120min to obtain a graphene dispersion solution, adding 100g of spherical TC4 powder into 200mL of 3% polyvinyl alcohol solution under the magnetic stirring condition, and performing magnetic stirring for 2h to obtain a TC4 powder mixed solution;
step two, mixing the graphene oxide dispersion liquid obtained in the step one with a TC4 powder mixed solution, and placing the mixture at 60 ℃ and mechanically stirring the mixture at a rotating speed of 450rpm to obtain semi-solid slurry;
step three, placing the semi-solid slurry obtained in the step two in a vacuum drying oven, drying for 12 hours at 80 ℃, and grinding to obtain non-caking and uniform graphene-TC 4 composite powder;
step four, performing discharge plasma sintering molding on the Co @ graphene-TC 4 composite powder obtained in the step three to obtain a block graphene-TC 4 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 1000 ℃, the sintering time is 6min, and the sintering pressure is 45 MPa.
The Co @ graphene-TC 21-based composite material prepared in example 1 of the invention and the graphene-TC prepared in comparative example 1 were tested in a universal material testing machine of Instron598X typeThe 21-base composite was subjected to uniaxial tensile test (with extensometer) to set the tensile rate at 1X 10-3s-1The results are shown in FIG. 4.
Fig. 4 is a tensile curve diagram of the Co @ graphene-TC 4-based composite material prepared in example 2 and the graphene-TC 4-based composite material prepared in comparative example 2, and it can be seen from fig. 4 that the yield strength of the Co @ graphene-TC 4-based composite material prepared in example 2 is 1035MPa, the tensile strength of the Co @ graphene-TC 4-based composite material is 1163MPa, which is obviously higher than the yield strength of the graphene-TC 4-based composite material prepared in comparative example 2, which is 950MPa and the tensile strength of the graphene-TC 352 MPa, which indicates that the mechanical properties of the Co @ graphene-TC 4-based composite material are improved by the process of plating cobalt on the surface of graphene.
Example 3
The embodiment comprises the following steps:
step one, under the ultrasonic oscillation condition, 0.2g of graphene powder is added into 100mL of ethanol for dispersing for 60min to obtain graphene dispersion liquid, under the magnetic stirring condition, 100g of spherical TA1 powder is added into 200mL of 3% polyvinyl alcohol solution, and the mixture is magnetically stirred for 2h to obtain TA1 powder mixed liquid;
step two, mixing cobalt acetate, sodium potassium tartrate and hydrazine hydrate, then preserving heat for 5min under the condition of a water bath at 60 ℃ to obtain a chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution, mechanically stirring at the rotating speed of 300rpm at 60 ℃ for 10min, then adding 6mol/L sodium hydroxide solution until wine red precipitate is generated and disappears, continuing to add 6mol/L sodium hydroxide solution until the solution is purple, and stirring for 30min again to obtain a mixed solution with the pH value of 13; the content of cobalt acetate in the chemical plating solution is 0.15mol/L, the content of potassium sodium tartrate is 0.15mol/L, the content of hydrazine hydrate is 60mL/L, and the mass concentration of hydrazine hydrate is 50%;
step three, precipitating and filtering the mixed solution obtained in the step two for 12 hours, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution for 5 minutes at the rotating speed of 8000rpm, sequentially repeating the washing and centrifuging processes for 3 times on the precipitate obtained by centrifuging the last time, placing the precipitate obtained by centrifuging the last time in a vacuum drying oven, and drying the precipitate at 70 ℃ for 10 hours to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol, performing ultrasonic treatment for 2 hours to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the TA1 powder mixed liquid obtained in the step one, and mechanically stirring at a stirring speed of 400rpm in a water bath condition of 70 ℃ to obtain semi-solid slurry;
placing the semi-solid slurry obtained in the fourth step into a vacuum drying oven, drying at 80 ℃ for 12 hours, and grinding to obtain non-caking and uniform Co @ graphene-TA 1 composite powder;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-TA 1 composite powder obtained in the fifth step to obtain a block Co @ graphene-TA 1 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 950 ℃, the sintering time is 6min, and the sintering pressure is 45 MPa.
Through detection, the yield strength of the Co @ graphene-TA 1 composite material prepared in the embodiment is 1087MPa, and the tensile strength is 1203 MPa.
Comparative example 3
This comparative example comprises the following steps:
step one, under the ultrasonic oscillation condition, 0.2g of graphene powder is added into 100mL of ethanol for dispersing for 60min to obtain graphene dispersion liquid, under the magnetic stirring condition, 100g of spherical TA1 powder is added into 200mL of 3% polyvinyl alcohol solution, and the mixture is magnetically stirred for 2h to obtain TA1 powder mixed liquid;
step two, mixing the graphene oxide dispersion liquid obtained in the step one with a TA1 powder mixed liquid, and mechanically stirring the mixture at the rotation speed of 400rpm at 70 ℃ to obtain semi-solid slurry;
step three, placing the semi-solid slurry obtained in the step two in a vacuum drying oven, drying for 12 hours at 80 ℃, and grinding to obtain non-caking and uniform graphene-TA 1 composite powder;
step four, carrying out discharge plasma sintering molding on the graphene-TA 1 composite powder obtained in the step three to obtain a block Co @ graphene-TA 1 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 950 ℃, the sintering time is 6min, and the sintering pressure is 45 MPa.
Through detection, the yield strength of the Co @ graphene-TA 1 composite material prepared by the comparative example is 967MPa, and the tensile strength is 1091 MPa.
Example 4
The embodiment comprises the following steps:
step one, under the ultrasonic oscillation condition, adding 0.2g of graphene powder into 100mL of ethanol for dispersing for 60min to obtain a graphene dispersion solution, adding 100g of spherical TC18 powder into 200mL of polyvinylpyrrolidone solution with the mass concentration of 3% under the magnetic stirring condition, and performing magnetic stirring for 2h to obtain a TC18 powder mixed solution;
step two, mixing cobalt acetate, sodium citrate and hydrazine hydrate, then preserving heat for 5min under the condition of water bath at 60 ℃ to obtain chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution, mechanically stirring for 10min at the rotation speed of 300rpm at 60 ℃, then adding 6mol/L sodium hydroxide solution until wine red precipitate is generated and disappears, continuing to add 6mol/L sodium hydroxide solution until the solution is purple, and stirring for 30min to obtain mixed solution with pH of 13; the content of cobalt acetate in the chemical plating solution is 0.15mol/L, the content of sodium citrate is 0.15mol/L, the content of hydrazine hydrate is 60mL/L, and the mass concentration of hydrazine hydrate is 50%;
step three, precipitating and filtering the mixed solution obtained in the step two for 15 hours, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution for 5 minutes at the rotating speed of 8500rpm, sequentially repeating the washing and centrifuging processes for 3 times on the precipitate obtained by centrifuging the last time, placing the precipitate obtained by centrifuging the last time in a vacuum drying oven, and drying the precipitate at the temperature of 60 ℃ for 12 hours to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol, performing ultrasonic treatment for 1h to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the TC18 powder mixed liquid obtained in the step one, and mechanically stirring at a stirring speed of 400rpm in a water bath condition of 60 ℃ to obtain semi-solid slurry;
step five, placing the semi-solid slurry obtained in the step four in a vacuum drying oven, drying for 12 hours at 60 ℃, and grinding to obtain non-caking and uniform Co @ graphene-TC 18 composite powder;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-TC 18 composite powder obtained in the fifth step to obtain a block Co @ graphene-TC 18 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 1000 ℃, the sintering time is 7min, and the sintering pressure is 45 MPa.
Through detection, the yield strength of the Co @ graphene-TA 1 composite material prepared in the embodiment is 1121MPa, and the tensile strength is 1189 MPa.
Comparative example 4
This comparative example comprises the following steps:
step one, under the ultrasonic oscillation condition, adding 0.2g of graphene powder into 100mL of ethanol for dispersing for 60min to obtain a graphene dispersion solution, adding 100g of spherical TC18 powder into 200mL of 3% polyvinyl alcohol solution under the magnetic stirring condition, and performing magnetic stirring for 2h to obtain a TC18 powder mixed solution;
step two, mixing the graphene oxide dispersion liquid obtained in the step one with a TC18 powder mixed liquid, and mechanically stirring the mixture at a temperature of 60 ℃ at a rotating speed of 400rpm to obtain semi-solid slurry;
step three, placing the semi-solid slurry obtained in the step two in a vacuum drying oven, drying for 12 hours at 60 ℃, and grinding to obtain non-caking and uniform graphene-TC 18 composite powder;
step four, carrying out spark plasma sintering molding on the graphene-TC 18 composite powder obtained in the step three to obtain a block graphene-TC 18 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 1000 ℃, the sintering time is 7min, and the sintering pressure is 45 MPa.
Through detection, the yield strength of the Co @ graphene-TA 1 composite material prepared in the embodiment is 1019MPa, and the tensile strength is 1080 MPa.
The detection results of the embodiments 1 to 4 and the corresponding comparative examples 1 to 4 show that the yield strength of the Co @ graphene titanium-based composite material prepared in the embodiments 1 to 4 is increased by 85MPa to 143MPa and the tensile strength is increased by nearly 101MPa to 121MPa compared with the titanium-based material prepared in the comparative examples 1 to 4, which indicates that the Co @ graphene titanium-based composite material of the present invention coats graphene by using Co particles mixed, inhibits the agglomeration phenomenon of graphene on the surface of the titanium substrate, improves the wettability between the graphene and the titanium substrate, delays the in-situ self-generated interfacial reaction between the titanium substrate and the graphene, reduces the generation amount of TiC and the strengthening effect of the in-situ self-generated intermetallic compound particle phase, and improves the mechanical properties of the Co @ graphene-titanium-based composite material.
Example 5
The embodiment comprises the following steps:
step one, under the ultrasonic oscillation condition, 0.2g of graphene powder is added into 200mL of ethanol for dispersion for 120min to obtain a graphene dispersion solution, 100g of spherical TC21 powder is added into 200mL of 3% polyvinyl alcohol solution under the magnetic stirring condition, and the mixture is magnetically stirred for 2.5h to obtain a TC21 powder mixed solution;
step two, mixing cobalt sulfate, sodium citrate and hydrazine hydrate, then preserving heat for 10min under the condition of water bath at 50 ℃ to obtain chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution, mechanically stirring for 20min at the temperature of 80 ℃ at the rotating speed of 400rpm, then adding 6mol/L sodium hydroxide solution until wine red precipitate is generated and disappears, continuing to add 6mol/L sodium hydroxide solution until the solution is purple, and stirring for 30min to obtain mixed solution with the pH value of 13; the content of cobalt sulfate in the chemical plating solution is 0.12mol/L, the content of sodium citrate is 0.2mol/L, the content of hydrazine hydrate is 40mL/L, and the mass concentration of hydrazine hydrate is 50%;
step three, precipitating and filtering the mixed solution obtained in the step two for 24 hours, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution for 10 minutes at the rotating speed of 10000rpm, sequentially repeating washing and centrifuging processes on the precipitate obtained by centrifuging for 5 times, placing the precipitate obtained by centrifuging the last time in a vacuum drying box, and drying the precipitate at 80 ℃ for 8 hours to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol, performing ultrasonic treatment for 1h to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the TC21 powder mixed liquid obtained in the step one, and mechanically stirring at a stirring speed of 500rpm in a water bath condition of 70 ℃ to obtain semi-solid slurry;
placing the semi-solid slurry obtained in the fourth step into a vacuum drying oven, drying for 16 hours at the temperature of 80 ℃, and grinding to obtain uniform Co @ graphene-TC 21 composite powder without agglomeration;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-TC 21 composite powder obtained in the fifth step to obtain a block Co @ graphene-TC 21 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 900 ℃, the sintering time is 10min, and the sintering pressure is 100 MPa.
Example 6
The embodiment comprises the following steps:
step one, under the ultrasonic oscillation condition, adding 0.2g of graphene powder into 200mL of ethanol for dispersion for 80min to obtain a graphene dispersion solution, adding 100g of spherical TC21 powder into 200mL of a hexaalkyltrimethylammonium bromide solution with the mass concentration of 3% under the magnetic stirring condition, and performing magnetic stirring for 2h to obtain a TC21 powder mixed solution;
step two, mixing cobalt acetate, sodium potassium tartrate and hydrazine hydrate, then preserving heat for 20min under the condition of 70 ℃ water bath to obtain chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution, mechanically stirring for 15min at 70 ℃ at the rotating speed of 350rpm, then adding 6mol/L sodium hydroxide solution until wine red precipitate is generated and disappears, continuing to add 6mol/L sodium hydroxide solution until the solution is purple, and stirring for 20min again to obtain mixed solution with the pH value of 14; the content of cobalt acetate in the chemical plating solution is 0.15mol/L, the content of potassium sodium tartrate is 0.15mol/L, the content of hydrazine hydrate is 100mL/L, and the mass concentration of hydrazine hydrate is 50%;
step three, precipitating and filtering the mixed solution obtained in the step two for 15 hours, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution for 6 minutes at the rotating speed of 8500rpm, sequentially repeating the washing and centrifuging processes for 4 times on the precipitate obtained by centrifuging the last time, placing the precipitate obtained by centrifuging the last time in a vacuum drying box, and drying the precipitate for 8 hours at the temperature of 80 ℃ to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol, performing ultrasonic treatment for 1h to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the TC21 powder mixed liquid obtained in the step one, and mechanically stirring at a stirring speed of 450rpm in a water bath condition of 50 ℃ to obtain semi-solid slurry;
step five, placing the semi-solid slurry obtained in the step four in a vacuum drying oven, drying for 24 hours at 70 ℃, and grinding to obtain non-caking and uniform Co @ graphene-TC 21 composite powder;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-TC 21 composite powder obtained in the fifth step to obtain a block Co @ graphene-TC 21 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 950 ℃, the sintering time is 6min, and the sintering pressure is 40 MPa.
Example 7
The embodiment comprises the following steps:
step one, under the ultrasonic oscillation condition, adding 0.2g of graphene powder into 100mL of ethanol for dispersing for 60min to obtain a graphene dispersion solution, adding 100g of spherical TC4 powder into 200mL of 3% polyvinyl alcohol solution under the magnetic stirring condition, and performing magnetic stirring for 2h to obtain a TC21 powder mixed solution;
step two, mixing cobalt acetate, sodium potassium tartrate and hydrazine hydrate, then preserving heat for 5min under the condition of a water bath at 60 ℃ to obtain a chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution, mechanically stirring at the rotating speed of 300rpm at 60 ℃ for 10min, then adding 6mol/L sodium hydroxide solution until wine red precipitate is generated and disappears, continuing to add 6mol/L sodium hydroxide solution until the solution is purple, and stirring for 10min again to obtain a mixed solution with the pH value of 11; the content of cobalt acetate in the chemical plating solution is 0.1mol/L, the content of potassium sodium tartrate is 0.1mol/L, the content of hydrazine hydrate is 40mL/L, and the mass concentration of hydrazine hydrate is 50%;
step three, precipitating and filtering the mixed solution obtained in the step two for 12 hours, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution for 5 minutes at the rotating speed of 8000rpm, sequentially repeating the washing and centrifuging processes for 3 times on the precipitate obtained by centrifuging the last time, placing the precipitate obtained by centrifuging the last time in a vacuum drying oven, and drying the precipitate at the temperature of 80 ℃ for 11 hours to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol, performing ultrasonic treatment for 1h to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the TC21 powder mixed liquid obtained in the step one, and mechanically stirring at a stirring speed of 350rpm in a water bath condition of 50 ℃ to obtain semi-solid slurry;
placing the semi-solid slurry obtained in the fourth step into a vacuum drying oven, drying for 12 hours at 60 ℃, and grinding to obtain non-caking and uniform Co @ graphene-TC 21 composite powder;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-TC 21 composite powder obtained in the fifth step to obtain a block Co @ graphene-TC 4 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 1100 ℃, the sintering time is 5min, and the sintering pressure is 45 MPa.
Example 8
The embodiment comprises the following steps:
step one, under the ultrasonic oscillation condition, adding 0.2g of graphene powder into 100mL of ethanol for dispersing for 100min to obtain a graphene dispersion solution, adding 100g of spherical TC4 powder into 200mL of 3% polyvinyl alcohol solution under the magnetic stirring condition, and performing magnetic stirring for 2.5h to obtain a TC4 powder mixed solution;
step two, mixing cobalt acetate, sodium potassium tartrate and hydrazine hydrate, then preserving heat for 10min under the condition of a water bath at 60 ℃ to obtain a chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution, mechanically stirring for 20min at 80 ℃ at the rotating speed of 350rpm, then adding 6mol/L sodium hydroxide solution until wine red precipitate is generated and disappears, continuing to add 6mol/L sodium hydroxide solution until the solution is purple, and stirring for 20min again to obtain a mixed solution with the pH value of 14; the content of cobalt acetate in the chemical plating solution is 0.2mol/L, the content of potassium sodium tartrate is 0.2mol/L, the content of hydrazine hydrate is 100mL/L, and the mass concentration of hydrazine hydrate is 50%;
step three, precipitating and filtering the mixed solution obtained in the step two for 24 hours, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution for 6 minutes at the rotating speed of 8500rpm, sequentially repeating the washing and centrifuging processes for 4 times on the precipitate obtained by centrifuging the last time, placing the precipitate obtained by centrifuging the last time in a vacuum drying oven, and drying the precipitate at 80 ℃ for 12 hours to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol, performing ultrasonic treatment for 1h to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the TC4 powder mixed liquid obtained in the step one, and mechanically stirring at a stirring speed of 400rpm in a water bath condition of 60 ℃ to obtain semi-solid slurry;
step five, placing the semi-solid slurry obtained in the step four in a vacuum drying oven, drying for 14 hours at the temperature of 80 ℃, and grinding to obtain non-caking and uniform Co @ graphene-TC 4 composite powder;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-TC 4 composite powder obtained in the fifth step to obtain a block Co @ graphene-TC 4 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 950 ℃, the sintering time is 5min, and the sintering pressure is 45 MPa.
Example 9
The embodiment comprises the following steps:
step one, under the ultrasonic oscillation condition, 0.2g of graphene powder is added into 100mL of ethanol for dispersion for 120min to obtain graphene dispersion liquid, under the magnetic stirring condition, 100g of spherical TA1 powder is added into 200mL of 3% polyvinyl alcohol solution, and the mixture is magnetically stirred for 3h to obtain TA1 powder mixed liquid;
step two, mixing cobalt acetate, sodium potassium tartrate and hydrazine hydrate, then preserving heat for 20min under the condition of a water bath at 60 ℃ to obtain a chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution, mechanically stirring for 20min at the temperature of 80 ℃ at the rotating speed of 400rpm, then adding 6mol/L sodium hydroxide solution until wine red precipitate is generated and disappears, continuously adding 6mol/L sodium hydroxide solution until the solution is purple, and stirring for 30min again to obtain a mixed solution with the pH value of 13; the content of cobalt acetate in the chemical plating solution is 0.15mol/L, the content of potassium sodium tartrate is 0.15mol/L, the content of hydrazine hydrate is 60mL/L, and the mass concentration of hydrazine hydrate is 50%;
step three, precipitating and filtering the mixed solution obtained in the step two for 18h, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution for 5min at the rotating speed of 8000rpm, sequentially repeating the washing and centrifuging processes for 4 times on the precipitate obtained by centrifuging the last time, placing the precipitate obtained by centrifuging the last time in a vacuum drying oven, and drying the precipitate at 70 ℃ for 10h to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol, performing ultrasonic treatment for 2 hours to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the TA1 powder mixed liquid obtained in the step one, and mechanically stirring at a stirring speed of 400rpm in a water bath condition of 70 ℃ to obtain semi-solid slurry;
step five, placing the semi-solid slurry obtained in the step four in a vacuum drying oven, drying at 80 ℃ for 12 hours, and grinding to obtain non-caking and uniform Co @ graphene-TA 1 composite powder;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-TA 1 composite powder obtained in the fifth step to obtain a block Co @ graphene-TA 1 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 950 ℃, the sintering time is 6min, and the sintering pressure is 45 MPa.
Example 10
The embodiment comprises the following steps:
step one, under the ultrasonic oscillation condition, adding 0.2g of graphene powder into 100mL of ethanol for dispersing for 120min to obtain a graphene dispersion solution, adding 100g of spherical TC18 powder into 200mL of polyvinylpyrrolidone solution with the mass concentration of 3% under the magnetic stirring condition, and performing magnetic stirring for 3h to obtain a TC18 powder mixed solution;
step two, mixing cobalt acetate, sodium citrate and hydrazine hydrate, then preserving heat for 20min under the condition of water bath at 60 ℃ to obtain chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution, mechanically stirring for 20min at the temperature of 80 ℃ at the rotating speed of 400rpm, then adding 6mol/L sodium hydroxide solution until wine red precipitate is generated and disappears, continuing to add 6mol/L sodium hydroxide solution until the solution is purple, and stirring for 30min to obtain mixed solution with the pH value of 13; the content of cobalt acetate in the chemical plating solution is 0.2mol/L, the content of sodium citrate is 0.2mol/L, the content of hydrazine hydrate is 60mL/L, and the mass concentration of hydrazine hydrate is 50%;
step three, precipitating and filtering the mixed solution obtained in the step two for 20 hours, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution for 5 minutes at the rotating speed of 8500rpm, sequentially repeating washing and centrifuging processes on the precipitate obtained by centrifuging the mixed solution for 5 times, placing the precipitate obtained by centrifuging the last time into a vacuum drying oven, and drying the precipitate at 80 ℃ for 20 hours to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol, performing ultrasonic treatment for 1h to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the TC18 powder mixed liquid obtained in the step one, and mechanically stirring at a stirring speed of 300rpm in a water bath condition of 70 ℃ to obtain semi-solid slurry;
step five, placing the semi-solid slurry obtained in the step four in a vacuum drying oven, drying for 10 hours at 80 ℃, and grinding to obtain non-caking and uniform Co @ graphene-TC 18 composite powder;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-TC 18 composite powder obtained in the fifth step to obtain a block Co @ graphene-TC 18 composite material with the diameter of 50mm and the height of 15 mm; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 950 ℃, the sintering time is 6min, and the sintering pressure is 45 MPa.
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 Co @ graphene-titanium matrix composite is characterized by comprising the following steps:
step one, adding graphene into ethanol for dispersion under the ultrasonic oscillation condition to obtain graphene dispersion liquid, adding titanium powder or titanium alloy powder into a surfactant solution under the magnetic stirring condition, and performing magnetic stirring to obtain a titanium-based powder mixed solution;
step two, mixing metal cobalt salt, a complexing agent and hydrazine hydrate, then preserving heat for 5-20 min under the condition of a water bath at 50-70 ℃ to obtain a chemical plating solution, then adding the graphene dispersion solution obtained in the step one into the chemical plating solution for mechanical stirring, adding alkali liquor until wine red precipitate is generated and disappears, continuing to add the alkali liquor until the solution is purple, and mechanically stirring again for 10-30 min to obtain a mixed solution; the content of metal cobalt salt in the chemical plating solution is 0.1-0.2 mol/L, the content of complexing agent is 0.1-0.2 mol/L, the content of hydrazine hydrate is 40-100 mL/L, and the mass concentration of hydrazine hydrate is 50%;
step three, precipitating and filtering the mixed solution obtained in the step two for more than 12 hours, washing the mixed solution to be neutral by using deionized water, centrifuging the mixed solution, sequentially repeating the washing and centrifuging processes for 3 to 5 times on the centrifuged precipitate, placing the precipitate obtained in the last centrifugation in a vacuum drying oven, and drying the precipitate at the temperature of between 60 and 80 ℃ for 10 to 12 hours to obtain Co @ graphene powder;
dispersing the Co @ graphene powder obtained in the step three in ethanol to obtain Co @ graphene dispersion liquid, then adding the Co @ graphene dispersion liquid into the titanium-based powder mixed liquid obtained in the step one, and mechanically stirring at a stirring speed of 300-500 rpm in a water bath condition of 50-70 ℃ to obtain semi-solid slurry;
putting the semi-solid slurry obtained in the fourth step into a vacuum drying oven for drying, and grinding to obtain Co @ graphene-titanium base composite powder; the drying temperature is 60-80 ℃, and the drying time is more than 12 h;
sixthly, performing discharge plasma sintering molding on the Co @ graphene-titanium-based composite powder obtained in the fifth step to obtain a Co @ graphene-titanium-based composite material; the technological parameters of the spark plasma sintering are as follows: the sintering temperature is 900-1100 ℃, the sintering time is 5-10 min, and the sintering pressure is more than 40 MPa.
2. The method for preparing a Co @ graphene-titanium based composite material as claimed in claim 1, wherein the surfactant solution in the first step is a polyvinylpyrrolidone solution, a polyvinyl alcohol solution or a cetyl trimethyl ammonium bromide solution.
3. The method for preparing a Co @ graphene-titanium matrix composite according to claim 2, wherein the mass concentration of the surfactant solution is 3%.
4. The preparation method of the Co @ graphene-titanium matrix composite material according to claim 1, wherein the speed of the mechanical stirring in the second step is 300rpm to 400rpm, the time is 10min to 20min, and the temperature is 60 ℃ to 80 ℃.
5. The preparation method of the Co @ graphene-titanium based composite material as claimed in claim 1, wherein in the second step, the metal cobalt salt is cobalt acetate or cobalt sulfate, and the complexing agent is potassium sodium tartrate or sodium citrate.
6. The method for preparing a Co @ graphene-titanium based composite material according to claim 1, wherein the molar ratio of the metal cobalt salt to the complexing agent in the electroless plating solution in the second step is 1: (1-1.5), the molar ratio of hydrazine hydrate to metal cobalt salt is 1:3, the alkali liquor is 6mol/L sodium hydroxide solution, and the pH value of the mixed solution is 11-14.
7. The preparation method of the Co @ graphene-titanium matrix composite material according to claim 1, wherein the rotation speed of the centrifugation in the third step is 8000rpm to 10000rpm, and the time is 5min to 10 min.
8. The method for preparing the Co @ graphene-titanium-based composite material according to claim 1, wherein the Co @ graphene-titanium-based composite powder which is not agglomerated and is uniform is obtained through grinding in the step five.
9. The preparation method of the Co @ graphene-titanium-based composite material according to claim 1, wherein the technological parameters of the spark plasma sintering in the sixth step are as follows: the sintering temperature is 900-1000 ℃, the sintering time is 5-10 min, and the sintering pressure is 40-100 MPa.
10. Co @ graphene-titanium based composite material prepared by the method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011008341.5A CN112144046A (en) | 2020-09-23 | 2020-09-23 | Co @ graphene-titanium-based composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011008341.5A CN112144046A (en) | 2020-09-23 | 2020-09-23 | Co @ graphene-titanium-based composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112144046A true CN112144046A (en) | 2020-12-29 |
Family
ID=73897670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011008341.5A Pending CN112144046A (en) | 2020-09-23 | 2020-09-23 | Co @ graphene-titanium-based composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112144046A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110512109A (en) * | 2019-09-20 | 2019-11-29 | 西安稀有金属材料研究院有限公司 | A kind of preparation method of graphene enhancing titanium composite material |
| CN113070471A (en) * | 2021-03-24 | 2021-07-06 | 东北大学 | Preparation method of titanium-graphene composite material with strong plasticity matching |
| CN113414394A (en) * | 2021-08-23 | 2021-09-21 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene titanium-based composite material with spiral structure |
| CN113634744A (en) * | 2021-07-13 | 2021-11-12 | 中北大学 | Preparation method of graphene surface cobalt-plated reinforced cobalt-based alloy composite powder for selective laser melting forming |
| CN115072810A (en) * | 2022-07-28 | 2022-09-20 | 西安稀有金属材料研究院有限公司 | Method for green synthesis of nano ruthenium oxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106623899A (en) * | 2016-12-19 | 2017-05-10 | 西安欧中材料科技有限公司 | Preparation method of graphene-enhanced titanium-based material |
| WO2017161993A1 (en) * | 2016-03-21 | 2017-09-28 | 中南大学 | Foam skeleton reinforced composite, preparation method therefor, and application thereof |
| CN108330312A (en) * | 2018-03-06 | 2018-07-27 | 昆明理工大学 | A kind of preparation method of the graphene reinforced metal-matrix composite of metallic cover |
| CN110586938A (en) * | 2019-10-21 | 2019-12-20 | 西安稀有金属材料研究院有限公司 | Nano carbon-titanium-based composite powder with network structure and application thereof |
-
2020
- 2020-09-23 CN CN202011008341.5A patent/CN112144046A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017161993A1 (en) * | 2016-03-21 | 2017-09-28 | 中南大学 | Foam skeleton reinforced composite, preparation method therefor, and application thereof |
| CN106623899A (en) * | 2016-12-19 | 2017-05-10 | 西安欧中材料科技有限公司 | Preparation method of graphene-enhanced titanium-based material |
| CN108330312A (en) * | 2018-03-06 | 2018-07-27 | 昆明理工大学 | A kind of preparation method of the graphene reinforced metal-matrix composite of metallic cover |
| CN110586938A (en) * | 2019-10-21 | 2019-12-20 | 西安稀有金属材料研究院有限公司 | Nano carbon-titanium-based composite powder with network structure and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| X.N. MU ET AL.: "Uniform dispersion and interface analysis of nickel coated grapheme nanoflakes/ pure titanium matrix composites", 《CARBON》 * |
| 周超兰等: "化学镀法制备钴包覆碳化硅复合粉末的研究", 《武汉理工大学学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110512109A (en) * | 2019-09-20 | 2019-11-29 | 西安稀有金属材料研究院有限公司 | A kind of preparation method of graphene enhancing titanium composite material |
| CN113070471A (en) * | 2021-03-24 | 2021-07-06 | 东北大学 | Preparation method of titanium-graphene composite material with strong plasticity matching |
| CN113634744A (en) * | 2021-07-13 | 2021-11-12 | 中北大学 | Preparation method of graphene surface cobalt-plated reinforced cobalt-based alloy composite powder for selective laser melting forming |
| CN113414394A (en) * | 2021-08-23 | 2021-09-21 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene titanium-based composite material with spiral structure |
| CN113414394B (en) * | 2021-08-23 | 2021-11-09 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene titanium-based composite material with spiral structure |
| CN115072810A (en) * | 2022-07-28 | 2022-09-20 | 西安稀有金属材料研究院有限公司 | Method for green synthesis of nano ruthenium oxide |
| CN115072810B (en) * | 2022-07-28 | 2023-12-22 | 西安稀有金属材料研究院有限公司 | Green synthesis method of nano ruthenium oxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112144046A (en) | Co @ graphene-titanium-based composite material and preparation method thereof | |
| CN111378888B (en) | Nano particle interface reinforced Ti (C, N) -based metal ceramic material with high nitrogen content and preparation method thereof | |
| CN111363945B (en) | Preparation and interface optimization method of modified graphene nanosheet magnesium-aluminum material | |
| CN110172603B (en) | Preparation method of modified carbon nanotube reinforced titanium-based composite material | |
| CN111270101B (en) | Microalloying cooperative strengthening graphene titanium-based composite material and preparation method thereof | |
| CN111560535A (en) | Preparation method of high-strength graphene/copper composite material | |
| CN108889959B (en) | rGO/Cu composite material and preparation method thereof | |
| CN110434347B (en) | Preparation method of graphene-rare earth mixed microstructure titanium-based composite material | |
| CN113070471A (en) | Preparation method of titanium-graphene composite material with strong plasticity matching | |
| CN111151765B (en) | Preparation method of three-dimensional structure nano carbon material reinforced copper-based composite material | |
| CN111910114A (en) | Endogenous nano carbide reinforced multi-scale FCC high-entropy alloy-based composite material and preparation method thereof | |
| CN108772569B (en) | Hydrothermal preparation method of superfine nano tungsten powder | |
| CN108941547B (en) | Preparation method of copper-doped graphene reinforced aluminum-based composite material | |
| CN110117732A (en) | A method of MgO protective layer is coated on cenosphere surface | |
| CN112008087A (en) | Method for improving comprehensive performance of carbon nano material reinforced nickel-based high-temperature alloy | |
| CN109848406B (en) | Powder metallurgy preparation method of titanium-based composite material and product | |
| CN108165791B (en) | Preparation method of binderless superfine tungsten carbide hard alloy | |
| CN113005320B (en) | Method for preparing carbon nanotube/copper composite material through interface regulation | |
| CN110295298B (en) | Preparation method of graphene-aluminum composite material | |
| CN112391549A (en) | Preparation method of reduced graphene oxide and aluminum oxide co-reinforced copper-based composite material | |
| CN115747552B (en) | Preparation method of nano-copper modified carbon nano-tube reinforced titanium-based composite material | |
| CN113618068B (en) | Laser additive manufacturing method of high-performance GH3536 nickel-based superalloy without thermal cracks | |
| CN112222420B (en) | Nano tungsten powder doped with metal oxide nano particles and preparation method thereof | |
| CN115070042A (en) | Rare earth oxide modified hard alloy turning tool blade and preparation method thereof | |
| CN111292910B (en) | Rapid preparation method of Co/SmCo composite magnetic material with special structure |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201229 |