CN111041275A - Method for preparing graphene reinforced titanium-based composite material through microwave sintering - Google Patents
Method for preparing graphene reinforced titanium-based composite material through microwave sintering Download PDFInfo
- Publication number
- CN111041275A CN111041275A CN202010040212.8A CN202010040212A CN111041275A CN 111041275 A CN111041275 A CN 111041275A CN 202010040212 A CN202010040212 A CN 202010040212A CN 111041275 A CN111041275 A CN 111041275A
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite material
- titanium
- based composite
- microwave sintering
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 133
- 239000010936 titanium Substances 0.000 title claims abstract description 56
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 55
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000009768 microwave sintering Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 45
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 55
- 238000000498 ball milling Methods 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000007747 plating Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 15
- 230000003068 static effect Effects 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 72
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000000707 layer-by-layer assembly Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 206010070834 Sensitisation Diseases 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 230000008313 sensitization Effects 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 27
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000000280 densification Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 238000000462 isostatic pressing Methods 0.000 abstract 1
- 238000009766 low-temperature sintering Methods 0.000 abstract 1
- 239000011812 mixed powder Substances 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 description 9
- 239000000956 alloy Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000007788 roughening Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000011156 metal matrix composite Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- 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
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1669—Agitation, e.g. air introduction
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- 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
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- 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
- B22F2003/1054—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by microwave
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention relates to a method for preparing a graphene reinforced titanium-based composite material by microwave sintering, and belongs to the technical field of preparation of metal-based composite materials. The composite material has high toughness, the self characteristic of graphene oxide is utilized for enhancing, the wettability of graphene in a titanium alloy matrix is improved by plating copper on the graphene, the uniform distribution of the graphene in the matrix is improved by a static combination and ball milling method, finally, the mixed powder is subjected to isostatic pressing and then subjected to microwave sintering, and meanwhile, the TiC phase is inhibited and reduced by utilizing microwave low-temperature rapid sintering, and finally, the high-toughness graphene-enhanced titanium-based composite material is obtained. The method has the advantages of simple process, high repeatability, high dispersion of graphene in the titanium matrix, rapid microwave low-temperature sintering for accelerating the densification of the block, effective inhibition and reduction of the generation of TiC phase, and high compactness and high toughness of the prepared titanium matrix composite.
Description
Technical Field
The invention relates to the technical field of metal matrix composite preparation, in particular to a method for preparing a graphene reinforced titanium matrix composite by microwave sintering.
Background
The titanium alloy has the characteristics of high specific strength, excellent corrosion resistance, high dimensional stability, good high-temperature mechanical property, good biocompatibility and the like, and can be widely applied to the fields of automobiles, aerospace, biomedicine and the like as a structural material. However, titanium alloy has the defects of lower hardness, poorer wear resistance and the like, the titanium-based composite material is a composite material which takes titanium, titanium alloy or intermetallic compounds of titanium as a matrix and contains a reinforcement, and the development of the titanium-based composite material provides a new direction for the fields of aerospace and automobiles. At present, ceramic particles (SiC, TiC and TiB), carbon nano tubes, carbon fibers, SiC fibers and other reinforcing materials are mainly adopted, and the strength of pure titanium and the strength of the alloy thereof are improved by a powder metallurgy method.
Graphene (Graphene) is a two-dimensional nanomaterial composed of carbon atoms, and has a single-layer sheet structure (with a thickness of only a few nanometers). Due to the unique two-dimensional honeycomb crystal structure and extremely high bond strength, graphene is the hardest nano material (with the breaking strength of 130 GPa) with the highest specific strength in the world. The specific surface area reaches 2630 m2The tensile strength and the elastic modulus can reach 125 GPa and 1100 GPa respectively. To take full advantage of its excellent properties, graphene is often present in a variety of matrices (ceramics, metals, and polymers). The graphene serving as a reinforcement of metals such as Al, Cu, Mg, Ti and the like can greatly improve the strength and toughness of the composite material and obtain good matching, so that the graphene becomes a favorable candidate material for reinforcing the titanium-based composite material.
However, the graphene-reinforced titanium-based composite material has a problem that the interface wettability of graphene and a titanium matrix is poor because the bonding between the reinforcing phase and the matrix is achieved through the interface, which transfers stress from the matrix to the reinforcing phase. The graphene and the carbon fiber are not wet with most metals, the thermal expansion coefficients of the graphene and the titanium matrix are greatly different, the two elements are insoluble, and the two components in the composite material are in thermodynamic equilibrium and have very slow two-phase dynamics at high temperature, so that the physical and chemical compatibility of the interface of the graphene and the titanium matrix is poor. Therefore, the graphene and the titanium matrix are difficult to form a firm bonding interface, thereby influencing the enhancement effect. Secondly, the graphene is unevenly distributed on the titanium matrix, and has a strong agglomeration tendency because of the nanoscale size, the large specific surface area and the high specific surface energy, and in the process of preparing the graphene reinforced metal matrix composite material, the key step is to uniformly and dispersedly disperse the graphene in the metal matrix, so that the reinforcing phase is prevented from agglomerating in the matrix to form a weak phase, the weak phase is easy to cause pores and cracks, and particularly when the graphene agglomerates at a crystal boundary, the crystal boundary strength is greatly reduced, so that the physical and mechanical properties of the composite material are greatly reduced. And thirdly, titanium has high activity and is easy to react with C to generate excessive TiC phases, and although the TiC phases have good compatibility with titanium alloy, the excessive TiC phases can influence the strengthening effect of the graphene.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for preparing a graphene reinforced titanium-based composite material by microwave sintering, which comprises the following steps:
s1, carrying out non-sensitization and non-activation copper plating on the graphene;
s2, uniformly mixing the copper-plated graphene and titanium alloy powder in the step S1 by adopting a static self-assembly combined ultrasonic auxiliary stirring process;
s3, placing the mixed solution of the copper-plated graphene powder and the titanium alloy powder prepared in the step S2 into a ball milling tank for ball milling;
s4, drying the mixed liquid ball-milled in the step S3 to obtain powder, and pressing the powder into a green body;
s5, placing the green body pressed in the step S4 in a microwave sintering furnace for sintering, and preparing the graphene reinforced titanium-based composite material.
The method comprises the following steps of carrying out copper plating on graphene, wherein the graphene is pretreated before being plated with copper, and the pretreatment is to remove impurities on the surface of the graphene through alkali washing and then coarsening the graphene through acid washing.
In step S1, the formula of the copper plating solution is: 15-30 g/L CuSO4∙5H2O、30-50g/LNa2EDTA、20-40g/L NaOH、0.1-0.3 g/L(C5H4N)2Wherein the treatment capacity of the graphene is 0.5-3 g/L.
Wherein the pH value is 12.5-13 and the temperature is 55-60 ℃ in the copper plating process, and magnetic stirring is carried out.
In step S2, the process of electrostatic self-assembly combined with ultrasonic-assisted stirring specifically includes:
(1) adding the copper-plated graphene oxide containing negative charges prepared in the step S1 into an acetone solution, and ultrasonically stirring;
(2) adding titanium alloy powder and a cationic surfactant into an acetone solution, and ultrasonically stirring to enable the surface of the titanium alloy powder to have positive charges;
(3) and (3) finally, mixing the two solutions obtained in the step (1) and the step (2), uniformly adsorbing graphene oxide on the surface of the titanium alloy powder in an electrostatic self-assembly mode, and ultrasonically stirring to obtain a mixed solution in which graphene is uniformly dispersed in the titanium alloy powder.
Wherein the ball milling tank adopted in the step S3 is a stainless steel ball milling tank, the ball milling medium is acetone, and the ball-to-material ratio is 3-6: 1.
Wherein, in the step S3, the ball milling rotation speed is 150-300 r/min, and the time is 6-12 h.
Wherein, in the step S4, the pressure of the press forming is 300-500 MPa.
Wherein, in the step S5, the vacuum degree of the microwave sintering furnace is 1 × 10-3Pa, output power of 1-3 KW, heating rate of 15-60 deg.C/min, sintering temperature of 1000-1250 deg.C, and heat preservation time of 10-30 min.
Wherein the sheet diameter of the graphene is 0.5-3 μm, the thickness is 0.6 nm, the single-layer rate is 70-80%, and the purity is 98-99.5%; the titanium alloy powder is flake powder with the particle size of less than 32 mu m, and the purity is 99-99.8%.
According to the preparation method, the compatibility and wettability of graphene and a matrix are increased by plating copper on the surface of the graphene, the graphene is uniformly dispersed in a titanium alloy matrix by adopting a method of combining electrostatic self-assembly with ultrasonic auxiliary stirring, the density of the prepared composite powder is improved by high-vacuum microwave low-temperature rapid sintering after the prepared composite powder is pressed, the reaction of the graphene and Ti is inhibited by combining with graphene plating copper, the TiC content is controlled, and the graphene strengthening effect is better exerted.
The microwave sintering adopted by the invention has the advantages of integral heating, low-temperature quick firing, selective heating, environmental protection, energy conservation and the like. At present, the research on microwave sintering is mostly carried out on materials such as oxide ceramics, hard alloys and the like, but the reports on the preparation of metal matrix composite materials are few, and the research on the preparation of titanium matrix composite materials by adopting high vacuum microwave sintering is hardly reported. In addition, the microwave low-temperature rapid sintering is adopted, not only can the densification of the block be accelerated, but also the TiC phase can be inhibited or reduced, because the sintering temperature is lower, the heat preservation time is short, and the normal atoms can not obtain enough energy to be converted into activated atoms, so the chemical reaction process can be inhibited, the TiC phase can be reduced, and the reinforcing effect of the graphene can be fully exerted.
The invention has the beneficial effects that:
1. the method comprises the steps of firstly, plating copper on the surface of graphene to increase the compatibility and wettability of the graphene and a titanium alloy matrix;
2. secondly, uniformly dispersing graphene in a titanium alloy matrix by adopting a method of combining electrostatic self-assembly with ultrasonic auxiliary stirring;
3. the microwave sintering provided by the invention can reduce the sintering temperature and shorten the sintering time, and the low-temperature rapid sintering can inhibit or reduce the TiC phase, so that the reinforcing effect of graphene is fully exerted;
4. the microwave sintering method provided by the invention has the advantages of convenience in operation, short sintering period and low energy consumption, saves the cost, remarkably improves the production efficiency, and can obtain the titanium-based composite material with high density, uniform tissue and good obdurability.
Detailed Description
The following is a preferred embodiment of the present invention, and it should be noted that it is obvious to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements are also considered to be within the scope of the present invention.
Example 1
The invention provides a method for preparing a graphene reinforced titanium-based composite material by microwave sintering, which comprises the following steps:
s1, firstly, removing impurities on the surface of the graphene through alkali washing, and then, passing throughCarrying out roughening treatment on graphene by acid washing; and then carrying out copper plating on the graphene, wherein the formula of the copper plating solution is as follows: 20 g/L CuSO4∙5H2O、40g/L Na2EDTA、30g/L NaOH、0.1 g/L(C5H4N)2Wherein the treatment amount of the graphene is 1 g/L; keeping the pH value at 12.5-13 and the temperature at 55-60 ℃ in the copper plating process, and carrying out magnetic stirring;
s2, adding the copper-plated graphene oxide containing a large number of negative charges, which is prepared in the step S1, into an acetone solution, and ultrasonically stirring, adding titanium alloy powder and a cationic surfactant (cetyl trimethyl ammonium bromide) into the acetone solution, and ultrasonically stirring to enable the surface of the titanium alloy powder to have positive charges; mixing the acetone solution containing graphene and the acetone solution containing titanium alloy powder, uniformly adsorbing graphene oxide on the surface of the titanium alloy powder in an electrostatic self-assembly mode, and ultrasonically stirring to obtain a mixed solution in which the graphene is uniformly dispersed in the titanium alloy powder;
s3, filling the mixed solution of the copper-plated graphene and the titanium alloy powder prepared in the step S2 into a ball milling tank according to a ball-to-material ratio of 5:1, controlling the ball milling rotation speed to be 200 r/min, and carrying out ball milling for 8 hours, wherein the ball milling tank is a stainless steel ball milling tank, and the ball milling medium is acetone;
s4, drying the mixed liquid ball-milled in the step S3 to obtain powder, screening the powder by 75 microns, and preparing the powder into a cylindrical blank under the pressure of 400MPa by using a unidirectional powder tablet press;
s5, placing the green body pressed in the step S4 into a microwave sintering furnace for sintering, wherein the vacuum degree of the microwave sintering furnace is 1 multiplied by 10-3Pa, the output power is 1 KW, the heating rate is 35 ℃/min, the sintering temperature is 1050 ℃, and the heat preservation time is 25min, so that the titanium-based composite material with 0.25% of graphene content is prepared.
Example 2
The invention provides a method for preparing a graphene reinforced titanium-based composite material by microwave sintering, which comprises the following steps:
s1, firstly, removing impurities on the surface of the graphene through alkali washing, and then carrying out roughening treatment on the graphene through acid washing; and then carrying out copper plating on the graphene, wherein the formula of the copper plating solution is as follows: 15 g/L CuSO4∙5H2O、45g/L Na2EDTA、25g/L NaOH、0.2 g/L(C5H4N)2Wherein the treatment amount of the graphene is 2 g/L; keeping the pH value at 12.5-13 and the temperature at 55-60 ℃ in the copper plating process, and carrying out magnetic stirring;
s2, adding the copper-plated graphene oxide containing a large number of negative charges, which is prepared in the step S1, into an acetone solution, and ultrasonically stirring, adding titanium alloy powder and a cationic surfactant (cetyl trimethyl ammonium bromide) into the acetone solution, and ultrasonically stirring to enable the surface of the titanium alloy powder to have positive charges; mixing the acetone solution containing graphene and the acetone solution containing titanium alloy powder, uniformly adsorbing graphene oxide on the surface of the titanium alloy powder in an electrostatic self-assembly mode, and ultrasonically stirring to obtain a mixed solution in which the graphene is uniformly dispersed in the titanium alloy powder;
s3, filling the mixed solution of the copper-plated graphene and the titanium alloy powder prepared in the step S2 into a ball milling tank according to a ball-to-material ratio of 3:1, controlling the ball milling rotation speed to be 250 r/min, and carrying out ball milling for 10 hours, wherein the ball milling tank is a stainless steel ball milling tank, and the ball milling medium is acetone;
s4, drying the mixed liquid ball-milled in the step S3 to obtain powder, screening the powder by 75 microns, and preparing the powder into a cylindrical blank under the pressure of 350 MPa by using a one-way powder tablet press;
s5, placing the green body pressed in the step S4 into a microwave sintering furnace for sintering, wherein the vacuum degree of the microwave sintering furnace is 1 multiplied by 10-3Pa, the output power is 2 KW, the heating rate is 25 ℃/min, the sintering temperature is 1150 ℃, the heat preservation time is 15min, and the titanium-based composite material with 0.5 percent of graphene content is prepared.
Example 3
The invention provides a method for preparing a graphene reinforced titanium-based composite material by microwave sintering, which comprises the following steps:
s1, firstly, removing impurities on the surface of the graphene through alkali washing, and then carrying out roughening treatment on the graphene through acid washing; and then carrying out copper plating on the graphene, wherein the formula of the copper plating solution is as follows: 25 g/L CuSO4∙5H2O、35g/L Na2EDTA、35g/L NaOH、0.3 g/L(C5H4N)2Wherein the treatment amount of the graphene is 1.5 g/L; keeping the pH value at 12.5-13 and the temperature at 55-60 ℃ in the copper plating process, and carrying out magnetic stirring;
s2, adding the copper-plated graphene oxide containing a large number of negative charges, which is prepared in the step S1, into an acetone solution, and ultrasonically stirring, adding titanium alloy powder and a cationic surfactant (cetyl trimethyl ammonium bromide) into the acetone solution, and ultrasonically stirring to enable the surface of the titanium alloy powder to have positive charges; mixing the acetone solution containing graphene and the acetone solution containing titanium alloy powder, uniformly adsorbing graphene oxide on the surface of the titanium alloy powder in an electrostatic self-assembly mode, and ultrasonically stirring to obtain a mixed solution in which the graphene is uniformly dispersed in the titanium alloy powder;
s3, filling the mixed solution of the copper-plated graphene and the titanium alloy powder prepared in the step S2 into a ball milling tank according to a ball-to-material ratio of 4:1, controlling the ball milling rotation speed to be 280 r/min, and performing ball milling for 6 hours, wherein the ball milling tank is a stainless steel ball milling tank, and the ball milling medium is acetone;
s4, drying the mixed liquid ball-milled in the step S3 to obtain powder, screening the powder by 75 microns, and preparing the powder into a cylindrical blank under the pressure of 450 MPa by using a unidirectional powder tablet press;
s5, placing the green body pressed in the step S4 into a microwave sintering furnace for sintering, wherein the vacuum degree of the microwave sintering furnace is 1 multiplied by 10-3Pa, the output power is 3 KW, the heating rate is 50 ℃/min, the sintering temperature is 1250 ℃, and the heat preservation time is 30min, so that the titanium-based composite material with the graphene content of 1% is prepared.
Example 4
The invention provides a method for preparing a graphene reinforced titanium-based composite material by microwave sintering, which comprises the following steps:
s1, firstly, removing impurities on the surface of the graphene through alkali washing, and then carrying out roughening treatment on the graphene through acid washing; and then carrying out copper plating on the graphene, wherein the formula of the copper plating solution is as follows: 20 g/L CuSO4∙5H2O、50g/L Na2EDTA、35g/L NaOH、0.2 g/L(C5H4N)2Wherein the treatment amount of the graphene is 3 g/L; the pH is maintained during the copper plating process12.5-13 ℃ and the temperature is 55-60 ℃, and magnetic stirring is carried out;
s2, adding the copper-plated graphene oxide containing a large number of negative charges, which is prepared in the step S1, into an acetone solution, and ultrasonically stirring, adding titanium alloy powder and a cationic surfactant (cetyl trimethyl ammonium bromide) into the acetone solution, and ultrasonically stirring to enable the surface of the titanium alloy powder to have positive charges; mixing the acetone solution containing graphene and the acetone solution containing titanium alloy powder, uniformly adsorbing graphene oxide on the surface of the titanium alloy powder in an electrostatic self-assembly mode, and ultrasonically stirring to obtain a mixed solution in which the graphene is uniformly dispersed in the titanium alloy powder;
s3, filling the mixed solution of the copper-plated graphene and the titanium alloy powder prepared in the step S2 into a ball milling tank according to a ball-to-material ratio of 6:1, controlling the ball milling rotation speed to be 250 r/min, and carrying out ball milling for 12 hours, wherein the ball milling tank is a stainless steel ball milling tank, and the ball milling medium is acetone;
s4, drying the mixed liquid ball-milled in the step S3 to obtain powder, screening the powder by 75 microns, and preparing the powder into a cylindrical blank under the pressure of 500 MPa by using a unidirectional powder tablet press;
s5, placing the green body pressed in the step S4 into a microwave sintering furnace for sintering, wherein the vacuum degree of the microwave sintering furnace is 1 multiplied by 10-3Pa, the output power is 2 KW, the heating rate is 45 ℃/min, the sintering temperature is 1000 ℃, and the heat preservation time is 15min, so that the titanium-based composite material with the graphene content of 1.5% is prepared.
In examples 1 to 4, the graphene used had a sheet diameter of 0.5 to 3 μm, a thickness of 0.6 nm, a monolayer rate of 70 to 80%, and a purity of 98 to 99.5%; the titanium alloy powder is flaky powder with the grain diameter of less than 32 mu m, and the purity is 99-99.8%.
Comparative example 1
In order to verify the performances of the graphene-based composite materials with different contents, the graphene-based composite materials with different contents are prepared by taking the example 1 as reference and controlling other process conditions to be unchanged and adjusting the mass ratio of the graphene to the titanium alloy powder, and comparative tests 1-5 are set.
To verify the properties of the titanium alloy material without graphene, with reference to example 1, set up comparative test 6, the preparation method of the titanium alloy material comprises the following steps:
s1, adding titanium alloy powder into an acetone solution, ultrasonically stirring, filling into a ball milling tank according to a ball-material ratio of 5:1, controlling the ball milling rotation speed to be 200 r/min, and carrying out ball milling for 8 hours, wherein the ball milling tank is a stainless steel ball milling tank, and the ball milling medium is acetone;
s2, drying the ball-milled solution to obtain powder, screening the powder by 75 microns, and preparing the powder into a cylindrical blank by a unidirectional powder tablet press under the pressure of 400 MPa;
s3, finally, placing the pressed green body into a microwave sintering furnace for sintering, wherein the vacuum degree of the microwave sintering furnace is 1 multiplied by 10-3Pa, output power of 1 KW, heating rate of 35 ℃/min, sintering temperature of 1050 ℃ and heat preservation time of 25min to prepare the titanium alloy material.
The performance parameters of the titanium-based composite material prepared in comparative tests 1 to 5 and the titanium alloy material prepared in comparative test 6 are shown in table 1:
as can be seen from Table 1, the relative density of the graphene titanium-based composite material is slowly reduced, but the microhardness, the tensile strength and the compressive strength of the graphene titanium-based composite material are increased and then reduced along with the increase of the addition amount of the graphene, and when the addition amount is 0.75%, the microhardness, the tensile strength and the compressive strength of the composite material reach the maximum, namely 568 HV0.11320 MPa and 1898MPa, respectively, which are improved by 37.0%, 25.7% and 22.5% compared with the titanium matrix without added graphene.
Therefore, the mechanical property of the titanium alloy can be obviously improved by adding a certain amount of graphene. The graphene prepared by the invention is uniformly dispersed and distributed on the grain boundary of the titanium alloy matrix, and is used as an effective reinforcing phase, thereby bringing a remarkable reinforcing effect to the titanium-based composite material. In addition, the compatibility between the interface bonding of the copper-plated graphene and the titanium matrix is good, so that the load can be effectively transferred from the titanium matrix to the high-strength graphene, the strength of the titanium matrix composite is further improved, in addition, the densification process of the titanium matrix composite is accelerated by rapid short-time heating in microwave sintering, the mechanical property of the titanium matrix composite is further remarkably improved, and the TiC phase can be inhibited or reduced by the microwave sintering, so that the reinforcing effect of the graphene is fully exerted.
Comparative example 2
In order to verify the mechanical property difference between the microwave sintering process provided by the invention and the conventional vacuum sintering process, a comparison test is set, and table 2 shows the comparison between the microwave sintering process and the conventional vacuum sintering process of the titanium-based composite material with 0.75% of graphene content.
As can be seen from table 2, the microwave sintering compares with the conventional vacuum sintering: the temperature is 200 ℃ lower, the time is 155 min shorter, but the relative density, the hardness, the tensile strength and the bending strength are all greatly improved compared with the conventional vacuum sintering. The microwave sintering can improve the uniformity of temperature distribution in an object, reduce the sintering temperature, shorten the heat preservation time, simultaneously enable a sintered body to have fine and uniform grain structure, and enable a product to have more excellent physical and mechanical properties. In addition, the microwave sintering technology has heating behavior and temperature gradient which are completely different from the conventional sintering mode, avoids the defects of high surface temperature of a heated object, large sintering driving force loss and the like in the conventional heating, has the advantages of selective heating of a phase, accelerated heating speed above a critical temperature, easy control of a microwave heating area, low sintering temperature, short production period, high energy utilization rate, safety, no pollution and the like, and becomes an important technical means for quickly preparing a high-quality new material and a traditional material with new performance.
The above examples only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the present invention. It should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the spirit of the present invention, and these changes and modifications are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for preparing a graphene reinforced titanium-based composite material by microwave sintering is characterized by comprising the following steps:
s1, carrying out non-sensitization and non-activation copper plating on the graphene;
s2, uniformly mixing the copper-plated graphene and titanium alloy powder in the step S1 by adopting a static self-assembly combined ultrasonic auxiliary stirring process;
s3, placing the mixed solution of the copper-plated graphene powder and the titanium alloy powder prepared in the step S2 into a ball milling tank for ball milling;
s4, drying the mixed liquid ball-milled in the step S3 to obtain powder, and pressing the powder into a green body;
s5, placing the green body pressed in the step S4 in a microwave sintering furnace for sintering, and preparing the graphene reinforced titanium-based composite material.
2. The method for preparing the graphene reinforced titanium-based composite material by microwave sintering according to claim 1, wherein the method comprises the following steps: the method comprises the steps of pretreating graphene before copper plating of the graphene, wherein the pretreatment is to remove impurities on the surface of the graphene through alkali washing, and then coarsening the graphene through acid washing.
3. The method for preparing the graphene-reinforced titanium-based composite material by microwave sintering according to claim 1 or 2, wherein in the step S1, the formula of the copper plating solution is as follows: 15-30 g/L CuSO4∙5H2O、30-50g/L Na2EDTA、20-40g/L NaOH、0.1-0.3 g/L(C5H4N)2Wherein the treatment capacity of the graphene is 0.5-3 g/L.
4. The method for preparing the graphene reinforced titanium-based composite material by microwave sintering according to claim 3, wherein the method comprises the following steps: the pH value is 12.5-13 and the temperature is 55-60 ℃ in the copper plating process, and magnetic stirring is carried out.
5. The method for preparing the graphene-reinforced titanium-based composite material through microwave sintering according to claim 1 or 2, wherein in the step S2, the process of electrostatic self-assembly combined with ultrasonic-assisted stirring specifically comprises:
(1) adding the copper-plated graphene oxide containing negative charges prepared in the step S1 into an acetone solution, and ultrasonically stirring;
(2) adding titanium alloy powder and a cationic surfactant into an acetone solution, and ultrasonically stirring to enable the surface of the titanium alloy powder to have positive charges;
(3) and (3) finally, mixing the two solutions obtained in the step (1) and the step (2), uniformly adsorbing graphene oxide on the surface of the titanium alloy powder in an electrostatic self-assembly mode, and ultrasonically stirring to obtain a mixed solution in which graphene is uniformly dispersed in the titanium alloy powder.
6. The method for preparing the graphene reinforced titanium-based composite material by microwave sintering according to claim 1 or 2, wherein: the ball milling tank adopted in the step S3 is a stainless steel ball milling tank, the ball milling medium is acetone, and the ball-material ratio is 3-6: 1.
7. The method for preparing the graphene reinforced titanium-based composite material by microwave sintering according to claim 1 or 2, wherein: in the step S3, the ball milling speed is 150-300 r/min, and the time is 6-12 h.
8. The method for preparing the graphene reinforced titanium-based composite material by microwave sintering according to claim 1 or 2, wherein: in the step S4, the pressure for press forming is 300-500 MPa.
9. The method for preparing the graphene reinforced titanium-based composite material by microwave sintering according to claim 1 or 2, wherein: in the step S5, the vacuum degree of the microwave sintering furnace is 1 × 10-3Pa, output power of 1-3 KW,the heating rate is 15-60 ℃/min, the sintering temperature is 1000-1250 ℃, and the heat preservation time is 10-30 min.
10. The method for preparing the graphene reinforced titanium-based composite material by microwave sintering according to claim 1 or 2, wherein: the sheet diameter of the graphene is 0.5-3 mu m, the thickness of the graphene is 0.6 nm, the single-layer rate is 70-80%, and the purity of the graphene is 98-99.5%; the titanium alloy powder is flake powder with the particle size of less than 32 mu m, and the purity is 99-99.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010040212.8A CN111041275A (en) | 2020-01-15 | 2020-01-15 | Method for preparing graphene reinforced titanium-based composite material through microwave sintering |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010040212.8A CN111041275A (en) | 2020-01-15 | 2020-01-15 | Method for preparing graphene reinforced titanium-based composite material through microwave sintering |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111041275A true CN111041275A (en) | 2020-04-21 |
Family
ID=70244646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010040212.8A Pending CN111041275A (en) | 2020-01-15 | 2020-01-15 | Method for preparing graphene reinforced titanium-based composite material through microwave sintering |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111041275A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111945027A (en) * | 2020-07-29 | 2020-11-17 | 北京理工大学 | Method for strengthening GNPs/Ti composite material interface combination by directional growth of TiBw |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105081310A (en) * | 2015-08-31 | 2015-11-25 | 哈尔滨理工大学 | Method for preparing grapheme reinforced aluminum matrix composite material |
| CN105861865A (en) * | 2016-06-03 | 2016-08-17 | 南昌航空大学 | Method for preparing graphene reinforced aluminum matrix composite material by microwave sintering |
| CN110144536A (en) * | 2019-06-06 | 2019-08-20 | 南昌航空大学 | A kind of processing method of the TiAl-base alloy with tiny lamellar structure |
-
2020
- 2020-01-15 CN CN202010040212.8A patent/CN111041275A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105081310A (en) * | 2015-08-31 | 2015-11-25 | 哈尔滨理工大学 | Method for preparing grapheme reinforced aluminum matrix composite material |
| CN105861865A (en) * | 2016-06-03 | 2016-08-17 | 南昌航空大学 | Method for preparing graphene reinforced aluminum matrix composite material by microwave sintering |
| CN110144536A (en) * | 2019-06-06 | 2019-08-20 | 南昌航空大学 | A kind of processing method of the TiAl-base alloy with tiny lamellar structure |
Non-Patent Citations (6)
| Title |
|---|
| XIN GAO, 等: "Mechanical properties and thermal conductivity of graphene reinforced copper matrix composites", 《POWDER TECHNOLOGY》 * |
| XIN GAO,等: "Preparation and tensile properties of homogeneously dispersed graphene reinforced aluminum matrix composites", 《MATERIALS AND DESIGN》 * |
| 付长璟等: "《石墨烯的制备、结构及应用》", 30 June 2017, 哈尔滨工业大学出版社 * |
| 吴小红: "微波烧结制备钛基复合材料及表面微弧氧化改性研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 罗军明，等: "石墨烯-Cu/Ti6Al4V 复合材料的制备及力学性能", 《中国有色金属学报》 * |
| 陈文革等: "《粉末冶金工艺及材料》", 31 July 2011, 冶金工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111945027A (en) * | 2020-07-29 | 2020-11-17 | 北京理工大学 | Method for strengthening GNPs/Ti composite material interface combination by directional growth of TiBw |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111644615B (en) | Preparation method for realizing high strength and toughness of TC4 titanium alloy by co-strengthening method | |
| CN109554565B (en) | Interface optimization method of carbon nanotube reinforced aluminum matrix composite | |
| US11731178B2 (en) | Rolled (FeCoNiCrRn/Al)-2024Al composite panel and fabrication method thereof | |
| CN108165901B (en) | Preparation method of carbon fiber reinforced metal matrix composite based on chemical plating | |
| CN110331318B (en) | Graphene and carbon nanotube reinforced aluminum-based composite material and preparation method thereof | |
| CN111270101B (en) | Microalloying cooperative strengthening graphene titanium-based composite material and preparation method thereof | |
| CN109487181B (en) | Aluminum oxide reinforced copper-based composite material and preparation method thereof | |
| CN110172603B (en) | Preparation method of modified carbon nanotube reinforced titanium-based composite material | |
| CN112899531B (en) | High-entropy alloy particle reinforced aluminum-based composite material and magnetic field auxiliary preparation method | |
| CN104911381B (en) | A kind of Ti2AlC/TiAl based composites and preparation method thereof | |
| CN109338168B (en) | Preparation method of complex-phase reinforced aluminum-based composite material | |
| CN112853142B (en) | Graphene-modified metal composite material | |
| CN109338134A (en) | A kind of preparation method of nickel-plating carbon nanotube reinforced aluminum matrix composites | |
| CN110735064A (en) | High-temperature-resistant high-strength TiC-reinforced titanium-based composite material generated by solid-phase in-situ reaction and preparation method thereof | |
| CN109554564B (en) | Preparation method of amorphous alloy particle and carbon nano tube reinforced aluminum matrix composite material | |
| CN114293051B (en) | Preparation method of high-temperature softening resistant high-strength high-conductivity copper-based composite material formed part | |
| CN111041275A (en) | Method for preparing graphene reinforced titanium-based composite material through microwave sintering | |
| CN105154724A (en) | Carbon nano tube reinforced aluminum-based composite material and preparation method thereof | |
| CN115074566B (en) | Method for improving performance of titanium-based composite material through modified and dispersed oxygen-containing graphene | |
| CN109652679B (en) | Carbon nanotube and endogenous nano TiC particle mixed reinforced aluminum-based composite material and preparation method thereof | |
| CN115747552B (en) | Preparation method of nano-copper modified carbon nano-tube reinforced titanium-based composite material | |
| CN115259859B (en) | Boron carbide bulletproof ceramic material and preparation method thereof | |
| CN112281009B (en) | Method for preparing titanium-based composite material by sintering pre-dispersed graphite composite titanium hydride | |
| CN116463523A (en) | In-situ self-generated nano oxide carbide synergistic toughening fine-grain molybdenum alloy and preparation method thereof | |
| Zhiming et al. | Interface optimization and mechanical properties of Cu-coated carbon fiber cloth/titanium alloy composite |
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: 20200421 |