CN113070471A - Preparation method of titanium-graphene composite material with strong plasticity matching - Google Patents
Preparation method of titanium-graphene composite material with strong plasticity matching Download PDFInfo
- Publication number
- CN113070471A CN113070471A CN202110316328.4A CN202110316328A CN113070471A CN 113070471 A CN113070471 A CN 113070471A CN 202110316328 A CN202110316328 A CN 202110316328A CN 113070471 A CN113070471 A CN 113070471A
- Authority
- CN
- China
- Prior art keywords
- titanium
- graphene
- composite material
- rgo
- powder
- 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
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 112
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000000843 powder Substances 0.000 claims abstract description 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010936 titanium Substances 0.000 claims abstract description 34
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000006185 dispersion Substances 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 239000011858 nanopowder Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229960000583 acetic acid Drugs 0.000 claims description 12
- 239000012362 glacial acetic acid Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910000883 Ti6Al4V Inorganic materials 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical class O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical class Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 10
- 238000005728 strengthening Methods 0.000 abstract description 4
- 239000011156 metal matrix composite Substances 0.000 abstract description 3
- 239000002052 molecular layer Substances 0.000 abstract description 3
- 238000000280 densification Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000956 alloy Substances 0.000 description 8
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910004353 Ti-Cu Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000000713 high-energy ball milling Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CYKMNKXPYXUVPR-UHFFFAOYSA-N [C].[Ti] Chemical compound [C].[Ti] CYKMNKXPYXUVPR-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 aluminum metals Chemical class 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Images
Classifications
-
- 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
-
- B22F1/0003—
-
- 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
- B22F1/16—Metallic particles coated with a non-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
- B22F3/02—Compacting only
-
- 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
- B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
-
- 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
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
-
- 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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
-
- 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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Optics & Photonics (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to the technical field of advanced metal matrix composite material preparation, and particularly relates to a preparation method of a titanium-graphene composite material with strong plasticity matching. And sintering the composite powder, and performing subsequent hot working deformation densification to obtain the high-strength plastic-matched titanium-graphene composite material plate or bar. According to the method, eutectoid elements in the titanium alloy are adopted to modify graphene to form metal nano-layer particles. The load transfer strengthening effect of the graphene is enhanced, and the plasticity of the graphene-reinforced titanium-based composite material is improved.
Description
Technical Field
The invention belongs to the technical field of advanced metal matrix composite material preparation, and particularly relates to a method for preparing a titanium-graphene composite material with strong plasticity matching by regulating and controlling interface morphology.
Background
Titanium is an important metal in industrial production in the early 50 s of the 20 th century. The metal is excellent in property and rich in reserves, and is known as a third metal which is rising from iron and aluminum metals. The titanium and titanium alloy material can be used as a high-quality light corrosion-resistant structural material, a novel functional material and an important biomedical material due to the excellent structural characteristics and functional characteristics of the titanium and titanium alloy materials. In a plurality of application fields, the titanium alloy is taken as a typical representative material with light weight and high strength, and has wide application in selection of important components such as aerospace, conventional weapons, national defense equipment and the like. However, the requirements of the aviation industry field on the performance of the traditional metal and the alloy material thereof cannot be met by the 'first generation material and the first generation equipment', so that the requirements of composite materials are increased in China from 1970 to now, particularly the consumption of the titanium alloy material, such as the rear fuselage of an F-22 fighter plane, is almost made of the titanium alloy and the composite materials.
One of the key issues facing metal matrix composites for structural applications is the inverse relationship between strength and plasticity, and titanium matrix composites are no exception. For example, titanium-based composites reinforced with TiB whiskers in situ have high room temperature strength and high heat resistance, but room temperature plasticity of such titanium-based composites is poor due to quasi-continuous distribution of reinforcement at grain boundaries. At present, the performance of the titanium-based composite material has no special breakthrough, and the selection of the reinforcement is mainly limited. In recent years, carbon nanomaterials are increasingly considered to be one of the most potential nanoreinforcements in titanium-based composites, compared to traditional ceramics or whiskers. Generally, high-energy ball milling is adopted to improve the dispersion effect of graphene in a matrix (Carbon 99(2016) 384-. However, although the high-energy ball milling process can improve the dispersibility of graphene, the activity of the surface of titanium powder is increased to a great extent at the same time, and even a titanium carbide phase is formed in the high-energy ball milling process (Journal of Materials Engineering and Performance 26(2017) 6047-6056). On the other hand, the interface structure is important for the mechanical property of the titanium-based composite material, the temperature is a key parameter for preparing the titanium-based composite material by powder metallurgy, and researches show that high-activity titanium and graphene can generate in-situ reaction at high temperature to generate titanium carbide particles in a short time. These results all contribute to a large extent to the strength of the composite material, but at the severe sacrifice of plasticity, and even exhibit the characteristic brittle fracture characteristics, especially at high graphene contents.
Disclosure of Invention
The invention provides a method for preparing a titanium-graphene composite material with strong plasticity matching in order to solve the technical problems. Firstly, the surface of graphene is modified by selecting proper metal nano particles or nano layers (namely M @ rGO) to prepare metal modified reduced graphene oxide nano powder, so that the specific gravity of the graphene nano powder can be improved, and the dispersibility of graphene in titanium alloy powder is increased. On the other hand, the metal nanoparticles or the nano-layer on the surface of the graphene is used for improving the wettability adsorption between the nonmetal graphene and the metal titanium. Then, ultrasonically dispersing metal modified graphene in a mixed solution of alcohol and deionized water, dropwise adding glacial acetic acid to improve the dispersibility to prepare M @ rGO dispersion liquid, then slowly adding a proper amount of titanium alloy powder into the M @ rGO dispersion liquid under the assistance of continuous mechanical stirring, and stirring and separating at the water bath temperature of 80 DEG CAnd (4) uniformly dispersing to obtain M @ rGO/Ti composite powder. In order to further improve the dispersibility of the M @ rGO nano powder in the titanium matrix powder and keep the integrity of the graphene structure, the M @ rGO/Ti composite powder is subjected to short-time low-energy ball milling. And sintering the M @ rGO/Ti composite powder and performing subsequent hot working deformation densification to obtain the high-strength plastic titanium-graphene composite material plate or bar. In the sintering process, the metal particles or layers on the surface of the graphene effectively prevent the graphene from contacting with the titanium matrix, so that the graphene is protected, and the reaction at high temperature is slowed down. The load transfer strengthening effect of the graphene is enhanced, and the plasticity of the graphene-reinforced titanium-based composite material is improved. Meanwhile, the selected metals Cu, Ag, Fe, Cr and the like on the surface of the graphene are eutectoid elements in titanium alloy, and all have certain solid solubility in a titanium matrix to form intermetallic compounds TixMyAnd (4) phase(s). Formed TixMyOn one hand, the titanium alloy matrix is enhanced like a framework, on the other hand, the interface wettability between graphene and the titanium alloy matrix is improved, and the interface bonding strength is improved. So that the titanium-graphene composite material keeps good strong plasticity matching effect.
The invention has the beneficial effects that:
compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, eutectoid metal elements (Cu, Ag, Fe, Cr and the like) in the titanium alloy are skillfully selected to modify graphene with large specific surface area, so as to form metal nano-layer particles. The adsorption property and the wettability between the graphene and the surface of the titanium alloy powder are improved, so that the graphene is uniformly dispersed on the surface of the titanium alloy powder. The serious damage of the traditional high-energy ball milling dispersion to the structure of the graphene and the formation of titanium carbide in the powder mixing process are avoided.
2. In-situ reaction is utilized to form intermetallic compound Ti with controllable content between graphene and titanium alloy matrix interface or in titanium alloy matrixxMy. On one hand, the growth of the graphene into the matrix like a skeleton is enhanced, the titanium alloy matrix is enhanced, on the other hand, the interface wettability between the graphene and the titanium alloy matrix is improved, and the interface bonding strength is improved. Furthermore metal particles on the surface of graphene and formed in situTixMyThe contact between titanium atoms of the titanium alloy powder and carbon atoms in the graphene can be isolated, the titanium-carbon interface reaction energy is reduced, and the excessive formation of titanium carbide is prevented, so that the structural integrity of the graphene and the titanium matrix is damaged, the reinforcing effect of the graphene is enhanced, the plasticity of the titanium-graphene composite material is improved, and the titanium-graphene composite material with good matching of strong plasticity is obtained.
3. The invention has simple operation process, high repeatability and high purity. The prepared titanium-graphene composite material has good strong plasticity matching and can be processed into plates, bars, wires and the like. Has wide application prospect.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a field emission scanning electron microscope image of composite powder prepared in example 2 and comparative example 2 of the present invention; wherein a is a field emission scanning electron microscope image of the composite powder Ti-rGO prepared in the comparative example 2 under 200 times, b is a field emission scanning electron microscope image of the composite powder Ti-Ag @ rGO prepared in the example 2 under 50 times, and c is a image of the surface of titanium powder in b magnified 20000 times;
FIG. 2 is a transmission photo at 500000 times of Ti-Ag @ rGO of a titanium-graphene sheet prepared in example 2 of the present invention; wherein a is the element distribution condition at the interface of Ag @ rGO and the titanium matrix, and b is a corresponding surface scanning distribution diagram of a;
FIG. 3 is a graph showing the relationship between tensile mechanical properties at room temperature of the composite materials prepared in examples 1 to 2 of the present invention and those prepared in comparative examples 1 to 2.
Detailed Description
Example 1:
preparation of eutectoid metal element Cu modified graphene nano powder (Cu @ rGO)
1) Dispersing 0.5g of graphene oxide in a mixed solvent of 300mL of deionized water and 200mL of alcohol, and ultrasonically stirring and dispersing for 3 hours to form a uniform graphene oxide dispersion liquid;
2) dispersing 10g of copper chloride salt in 100mL of deionized water, and stirring and dispersing until the solution has no suspended matters to form a metal Cu ion salt solution;
3) dropwise adding the graphene oxide dispersion liquid obtained in the step 1) into the metal ion salt solution obtained in the step 2), ultrasonically stirring, stirring for 2 hours, and simultaneously dropwise adding 1mL of glacial acetic acid to improve the dispersibility; after stirring, adding 0.2mol/L sodium hydroxide solution into the mixed solution to adjust the pH value to be more than 10, then adding 30mL ascorbic acid with the concentration of 0.56mol/L and stirring until the solution is uniform;
4) putting the mixed solution obtained in the step 3) into a water bath kettle at 90 ℃, heating for reaction for 3 hours, and then centrifugally washing for more than 5 times by using deionized water until the pH value of the solution is neutral; the rotational speed of the centrifugal washing is 9000 r/min.
5) Putting the centrifuged mud mixture obtained in the step 4) into a culture dish, and freeze-drying to obtain Cu-modified graphene nano powder Cu @ rGO;
(II) preparing titanium-graphene composite powder
6) Ultrasonically dispersing the Cu @ rGO obtained in the step 5) in a mixed solvent of alcohol and deionized water, and mixing the alcohol and the deionized water according to the volume ratio of 4: 1; forming Cu @ rGO dispersion liquid after ultrasonic dispersion for 30 min;
7) adding pure titanium powder with the particle size of 75 mu m into the Cu @ rGO dispersion liquid obtained in the step 6); stirring in a water bath at 80 ℃, simultaneously adding 1mL of glacial acetic acid to realize uniform dispersion of Cu @ rGO on the surface of titanium powder, and uniformly dispersing to obtain Ti-Cu @ rGO slurry; after stirring and dispersing, further improving the dispersibility by low-energy ball milling, wherein the rotating speed of the low-energy ball milling is 150r/min, and the ball-material ratio is 3: 1, ball milling for 30min to obtain uniformly dispersed Ti-Cu @ rGO composite powder.
(III) preparing the titanium-graphene composite material with matched obdurability
8) Putting the Ti-Cu @ rGO composite powder obtained in the step 7) into a molybdenum alloy high-pressure die, and performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a titanium-graphene composite material blank; the pressure of the pressure sintering is 60MPa, the heating rate is 100 ℃/min, the temperature is 900 ℃, and the time is 5 min.
9) And (3) rolling or extruding the blank obtained in the step 8) at a high temperature to obtain a titanium-graphene plate or bar.
The temperature of high-temperature rolling or extrusion is 1000 ℃, the heat preservation time is 5min, the single-pass deformation is 1mm, and the total deformation can reach 83%.
Example 2:
preparation of eutectoid metal element Ag modified graphene nanopowder (Ag @ rGO)
1) Dispersing 1g of graphene oxide in a mixed solvent of 300mL of deionized water and 200mL of alcohol, and ultrasonically stirring and dispersing for 3.5 hours to form a uniform graphene oxide dispersion liquid;
2) dispersing 10g of silver nitrate salt into 100mL of deionized water, and stirring and dispersing until the solution has no suspended matters to form a metal Ag ion salt solution;
3) dropwise adding the graphene oxide dispersion liquid obtained in the step 1) into the metal ion salt solution obtained in the step 2), ultrasonically stirring, stirring for 2 hours, and simultaneously dropwise adding 3mL of glacial acetic acid to improve the dispersibility; after stirring, adding 0.2mol/L sodium hydroxide solution into the mixed solution to adjust the pH value to be more than 10, then adding 30mL ascorbic acid with the concentration of 0.56mol/L and stirring until the solution is uniform;
4) putting the mixed solution obtained in the step 3) into a water bath kettle at 90 ℃, heating for reaction for 3 hours, and then centrifugally washing for more than 5 times by using deionized water until the pH value of the solution is neutral; the rotational speed of the centrifugal washing is 9000 r/min.
5) Putting the centrifuged mud mixture obtained in the step 4) into a culture dish, and freeze-drying to obtain Ag modified graphene nano powder Ag @ rGO;
(II) preparing titanium-graphene composite powder
6) Ultrasonically dispersing the Ag @ rGO obtained in the step 5) in a mixed solvent of alcohol and deionized water, and mixing the alcohol and the deionized water according to the volume ratio of 4: 1; performing ultrasonic dispersion for 60min to form an Ag @ rGO dispersion liquid;
7) adding pure titanium powder with the particle size of 150 mu m into the Ag @ rGO dispersion liquid obtained in the step 6); stirring in a water bath at 80 ℃, simultaneously adding 5mL of glacial acetic acid to realize uniform dispersion of Ag @ rGO on the surface of titanium powder, and uniformly dispersing to obtain Ti-Ag @ rGO slurry; after stirring and dispersing, further improving the dispersibility by low-energy ball milling, wherein the rotating speed of the low-energy ball milling is 200r/min, and the ball-material ratio is 3: 1, ball milling for 15min to obtain uniformly dispersed Ti-Ag @ rGO composite powder.
(III) preparing the titanium-graphene composite material with matched obdurability
8) Putting the Ti-Ag @ rGO composite powder obtained in the step 7) into a molybdenum alloy high-pressure die, and performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a titanium-graphene composite material blank; the pressure of the pressure sintering is 45MPa, the heating rate is 100 ℃/min, the temperature is 800 ℃, and the time is 5 min.
9) And (3) rolling or extruding the blank obtained in the step 8) at a high temperature to obtain a titanium-graphene plate or bar.
The temperature of high-temperature rolling or extrusion is 800 ℃, the heat preservation time is 10min, the single-pass deformation is 1mm, and the total deformation can reach 83%.
Example 3:
preparation of eutectoid metal element Fe modified graphene nano powder (Fe @ rGO)
1) Dispersing 0.1g of graphene oxide in a mixed solvent of 300mL of deionized water and 200mL of alcohol, and ultrasonically stirring and dispersing for 5 hours to form a uniform graphene oxide dispersion liquid;
2) dispersing 30g of ferrous chloride salt in 100mL of deionized water, and stirring and dispersing until the solution has no suspended matters to form a metal Fe ion salt solution;
3) dropwise adding the graphene oxide dispersion liquid obtained in the step 1) into the metal ion salt solution obtained in the step 2), ultrasonically stirring, stirring for 2 hours, and simultaneously dropwise adding 5mL of glacial acetic acid to improve the dispersibility; after stirring, adding 0.2mol/L sodium hydroxide solution into the mixed solution to adjust the pH value to be more than 10, then adding 30mL ascorbic acid with the concentration of 0.56mol/L and stirring until the solution is uniform;
4) putting the mixed solution obtained in the step 3) into a water bath kettle at 90 ℃, heating for reaction for 3 hours, and then centrifugally washing for more than 5 times by using deionized water until the pH value of the solution is neutral; the rotational speed of the centrifugal washing is 9000 r/min.
5) Putting the centrifuged mud mixture obtained in the step 4) into a culture dish, and freeze-drying to obtain Fe-modified graphene nano powder Fe @ rGO;
(II) preparing titanium-graphene composite powder
6) Ultrasonically dispersing the Fe @ rGO obtained in the step 5) in a mixed solvent of alcohol and deionized water, and mixing the alcohol and the deionized water according to the volume ratio of 4: 1; performing ultrasonic dispersion for 45min to form Fe @ rGO dispersion liquid;
7) adding Ti-6Al-4V (TC4) alloy powder with the particle size of 100 mu m into the Fe @ rGO dispersion liquid obtained in the step 6); stirring in a water bath at 80 ℃, simultaneously adding 10mL of glacial acetic acid to realize uniform dispersion of Fe @ rGO on the surface of TC4 alloy powder, and uniformly dispersing to obtain TC4-Fe @ rGO slurry; after stirring and dispersing, further improving the dispersibility by low-energy ball milling, wherein the rotating speed of the low-energy ball milling is 100r/min, and the ball-material ratio is 3: 1, ball-milling for 45min to obtain uniformly dispersed TC4-Fe @ rGO composite powder.
(III) preparing the titanium-graphene composite material with matched obdurability
8) Putting the TC4-Fe @ rGO composite powder obtained in the step 7) into a molybdenum alloy die, and performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a titanium-graphene composite material blank; the pressure of the pressure sintering is 100MPa, the heating rate is 100 ℃/min, the temperature is 1000 ℃, and the time is 5 min.
9) And (3) rolling or extruding the blank obtained in the step 8) at a high temperature to obtain a titanium-graphene plate or bar.
The temperature of high-temperature rolling or extrusion is 900 ℃, the heat preservation time is 8min, the single-pass deformation is 1mm, and the total deformation can reach 83%.
Example 4:
preparation of eutectoid metal element Cr modified graphene nanopowder (Cr @ rGO)
1) Dispersing 1g of graphene oxide in a mixed solvent of 300mL of deionized water and 200mL of alcohol, and ultrasonically stirring and dispersing for 4 hours to form a uniform graphene oxide dispersion liquid;
2) dispersing 5g of chromic anhydride salt into 100mL of deionized water, and stirring and dispersing until the solution has no suspended matters to form a metal Cr ion salt solution;
3) dropwise adding the graphene oxide dispersion liquid obtained in the step 1) into the metal ion salt solution obtained in the step 2), ultrasonically stirring, stirring for 2 hours, and simultaneously dropwise adding 3mL of glacial acetic acid to improve the dispersibility; after stirring, adding 0.2mol/L sodium hydroxide solution into the mixed solution to adjust the pH value to be more than 10, then adding 30mL ascorbic acid with the concentration of 0.56mol/L and stirring until the solution is uniform;
4) putting the mixed solution obtained in the step 3) into a water bath kettle at 90 ℃, heating for reaction for 3 hours, and then centrifugally washing for more than 5 times by using deionized water until the pH value of the solution is neutral; the rotational speed of the centrifugal washing is 9000 r/min.
5) Putting the centrifuged muddy mixture obtained in the step 4) into a culture dish, and freeze-drying to obtain Cr-modified graphene nano powder Cr @ rGO;
(II) preparing titanium-graphene composite powder
6) Ultrasonically dispersing the Cr @ rGO obtained in the step 5) in a mixed solvent of alcohol and deionized water, and mixing the alcohol and the deionized water according to the volume ratio of 4: 1; carrying out ultrasonic dispersion for 60min to form Cr @ rGO dispersion liquid;
7) adding Ti600 alloy powder with the particle size of 100 mu m into the Cr @ rGO dispersion liquid obtained in the step 6); stirring in a water bath at 80 ℃, simultaneously adding 6mL of glacial acetic acid to realize uniform dispersion of Cr @ rGO on the surface of Ti600 alloy powder, and uniformly dispersing to obtain Ti600-Cr @ rGO slurry; after stirring and dispersing, further improving the dispersibility by low-energy ball milling, wherein the rotating speed of the low-energy ball milling is 100r/min, and the ball-material ratio is 3: 1, ball-milling for 45min to obtain uniformly dispersed Ti600-Cr @ rGO composite powder.
(III) preparing the titanium-graphene composite material with matched obdurability
8) Putting the Ti600-Cr @ rGO composite powder obtained in the step 7) into a molybdenum alloy die, and performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a titanium-graphene composite material blank; the pressure of the pressure sintering is 100MPa, the heating rate is 100 ℃/min, the temperature is 1000 ℃, and the time is 5 min.
9) And (3) rolling or extruding the blank obtained in the step 8) at a high temperature to obtain a titanium-graphene plate or bar.
The temperature of high-temperature rolling or extrusion is 900 ℃, the heat preservation time is 8min, the single-pass deformation is 1mm, and the total deformation can reach 83%.
Comparative example 1:
the difference from example 1 is that:
and (3) replacing the Ti-Cu @ rGO composite powder in the step 8) with the same amount of pure titanium powder, and performing the steps 8 and 9).
Comparative example 2:
the difference from example 1 is that:
directly repeating the steps 6) to 9) without using eutectoid metal element modified graphene nano powder to replace the Cu modified graphene nano powder Cu @ rGO in the embodiment 1).
The Ti-Cu @ rGO/Ti prepared in the example 1, the Ti-Ag @ rGO high-strength plastic composite material prepared in the example 2, the pure Ti material prepared in the comparative example 1 and the Ti-rGO composite material prepared in the comparative example 2 are subjected to composite powder morphology characterization observation and room temperature mechanical property test.
(1) Powder morphology characterization observation and microstructure characterization
The Ti-rGO prepared in the comparative example 2 and the Ti-Ag @ rGO prepared in the example 2 with the same content are taken to observe the dispersion situation of the rGO and the Ag @ rGO in the titanium powder under a field emission scanning electron microscope, and the result is shown in figure 1. As can be seen from fig. 1a, the rGO in comparative example 2 has a significant agglomeration phenomenon on the surface of the titanium powder, while the Ag @ rGO nano powder obtained by example 2 in fig. 1b is uniformly distributed on the surface of the titanium powder without significant agglomeration. Especially, 20000 times observation in fig. 1c shows that the Ag @ rGO nano powder is tightly wrapped on the surface of the titanium powder, and the Ag nano particles are uniformly distributed on the surface of the graphene powder without other phases. As can be seen from comparison of fig. 1, the presence of the eutectoid metal element improves the adsorbability and wettability between graphene and the surface of the titanium alloy powder, and realizes uniform dispersion of graphene on the surface of the titanium alloy powder. The serious damage of the traditional high-energy ball milling dispersion to the structure of the graphene and the formation of titanium carbide in the powder mixing process are avoided, and the effects of protecting the structural integrity and uniform dispersion of the graphene are well achieved.
The transmission photo and the element distribution condition at the interface of the titanium-graphene sheet material Ti-Ag @ rGO prepared in the embodiment 2 of the invention are shown in fig. 2, wherein a in the figure shows that no obvious pore exists between the Ag @ rGO and the titanium matrix, and the interface combination is good. In the figure, b is a profile of a surface scan corresponding to a, and it is found from b that there are TiC particles and TixAgyAnd the formation improves the interface wettability between the graphene and the titanium alloy matrix and improves the interface bonding strength. Simultaneously isolating the contact between titanium atoms of the titanium alloy powder and carbon atoms in the grapheneThe method reduces the reaction energy of the titanium-carbon interface, prevents excessive formation of titanium carbide, thereby damaging the structural integrity of the graphene and the titanium matrix, enhancing the strengthening effect of the graphene, improving the plasticity of the titanium-graphene composite material, and obtaining the titanium-graphene composite material with good matching of strong plasticity.
(2) Mechanical property test of composite material
The composite materials prepared in example 1, example 2, comparative example 1 and comparative example 2 were subjected to room temperature tensile mechanical property tests according to the national standard GB/T228.1-2010. The test results are shown in fig. 3.
As can be seen from FIG. 3, comparative example 1 is pure titanium having a strength of 650MPa and an elongation of 6%. The strength of the titanium-graphene composite material prepared in the comparative example 2 is 680MPa, the elongation is 10%, and it can be found from the comparative examples 1 and 2 that the addition of graphene can improve the strength and plasticity of the composite material, but the improvement range is limited, which is caused by the agglomeration of graphene in the powder, as shown in fig. 1 a. The strength of the composite material is greatly improved in the embodiments 1 and 2, and the strong plasticity matching of 900 MPa-10% can be achieved. This shows that the method of the present invention can exert the dispersion effect and the strengthening effect of the graphene in the titanium composite material to the maximum extent. The dispersibility of graphene in the surface of titanium powder is improved by modifying eutectoid elements on the surface of graphene, and then an intermetallic compound Ti with controllable content is formed between the interface of graphene and a titanium alloy matrix or in the titanium alloy matrix by utilizing in-situ reactionxMy. On one hand, the reinforcing phase grows into the matrix like a skeleton to reinforce the titanium alloy matrix, on the other hand, the interface wettability between the graphene and the titanium alloy matrix is improved, and the interface bonding strength is improved. Furthermore, metal particles on the surface of graphene and in-situ formed TixMyThe contact between titanium atoms of the titanium alloy powder and carbon atoms in the graphene can be isolated, the titanium-carbon interface reaction energy is reduced, and the excessive formation of titanium carbide is prevented, so that the structural integrity of the graphene and the titanium matrix is damaged, the reinforcing effect of the graphene is enhanced, the plasticity of the titanium-graphene composite material is improved, and the titanium-graphene composite material with good matching of strong plasticity is obtained.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiment according to the present invention are within the scope of the present invention.
Claims (10)
1. A preparation method of a titanium-graphene composite material with strong plasticity matching is characterized by comprising the following steps:
preparation of eutectoid metal element modified graphene nano powder
1) Dispersing graphene oxide in a mixed solvent of deionized water and alcohol, wherein the deionized water and the alcohol are mixed according to the volume ratio of 3:2, and ultrasonically stirring and dispersing to form a uniform graphene oxide dispersion liquid, wherein the ratio of the graphene oxide to the mixed solvent is 0.2-2 g/L;
2) dispersing 5-30 g of eutectoid metal salt in 100ml of deionized water, and stirring and dispersing until the solution has no suspended matters to form a metal ion salt solution;
3) dropwise adding the graphene oxide dispersion liquid obtained in the step 1) into the metal ion salt solution obtained in the step 2), ultrasonically stirring, and dropwise adding 1-5 mL of glacial acetic acid while stirring to realize uniform dispersion; after stirring for at least 2 hours, adding 0.2mol/L sodium hydroxide solution into the mixed solution to adjust the pH value to be more than 10, then adding 30ml ascorbic acid with the concentration of 0.56mol/L and stirring until the solution is uniform;
4) putting the mixed solution obtained in the step 3) into a water bath kettle at 90 ℃ for heating reaction for at least 3h, and then centrifugally washing the mixed solution for more than 5 times by using deionized water until the pH value of the solution is neutral;
5) putting the centrifuged mud mixture obtained in the step 4) into a culture dish, and freeze-drying to obtain eutectoid metal element modified graphene nano powder M @ rGO;
(II) preparing titanium-graphene composite powder
6) Ultrasonically dispersing the eutectoid metal element modified graphene nano powder M @ rGO obtained in the step 5) in a mixed solvent of alcohol and deionized water, wherein the alcohol and the deionized water are mixed according to the volume ratio of 4: 1; forming M @ rGO dispersion liquid after ultrasonic dispersion;
7) adding titanium alloy powder into the M @ rGO dispersion liquid obtained in the step 6); stirring and dispersing uniformly in a water bath at 80 ℃ to obtain M @ rGO/Ti powder slurry, and dripping glacial acetic acid while stirring to realize uniform dispersion of M @ rGO on the surface of titanium powder;
(III) preparing the titanium-graphene composite material with strong plasticity matching
8) Putting the M @ rGO/Ti powder slurry obtained in the step 7) into a molybdenum alloy high-pressure die, and performing pressure sintering by adopting a rapid plasma discharge sintering method to obtain a titanium-graphene composite material blank;
9) and (3) rolling or extruding the blank obtained in the step 8) at a high temperature to obtain a titanium-graphene plate or bar.
2. The method for preparing a strongly plastic-matched titanium-graphene composite material according to claim 1, wherein the ultrasonic stirring time in the step 1) is at least 3 hours.
3. The method for preparing a titanium-graphene composite material with strong plastic matching according to claim 1, wherein the eutectoid metal salt in step 2) includes but is not limited to silver nitrate salt, copper chloride salt, chromic anhydride salt, and ferrous chloride salt.
4. The method for preparing a strongly plastic-matched titanium-graphene composite material according to claim 1, wherein the rotation speed of the centrifugal washing in the step 4) is 9000 r/min.
5. The preparation method of the titanium-graphene composite material with strong plastic matching according to claim 1, wherein the ultrasonic dispersion time in the step 6) is 30-60 min.
6. The method for preparing a strongly plastic-matched titanium-graphene composite material according to claim 1, wherein the titanium alloy powder in step 7) includes but is not limited to pure titanium powder, Ti-6Al-4V, Ti 600.
7. The preparation method of the titanium-graphene composite material with the strong plastic matching property according to claim 1, wherein the particle size of the titanium alloy powder in the step 7) is 75-150 μm, and the content of glacial acetic acid is 1-10 mL.
8. The preparation method of the titanium-graphene composite material with the strong plastic matching property according to claim 1, wherein the dispersibility is further improved by low-energy ball milling after the stirring and the dispersing in the step 7), the rotating speed of the low-energy ball milling is 100-200 r/min, and the ball-to-material ratio is 3: 1, ball milling for 15-45 min.
9. The preparation method of the titanium-graphene composite material with the strong plastic matching performance according to claim 1, wherein the pressure of the pressure sintering in the step 8) is 45-100 MPa, the temperature rise rate is 100 ℃/min, the temperature is 800-1000 ℃, and the time is 5 min.
10. The preparation method of the titanium-graphene composite material with the matched strong plasticity according to claim 1, wherein the temperature of the high-temperature rolling or extrusion in the step 9) is 800-1000 ℃, the holding time is 5-10 min, the single-pass deformation is 1mm, and the total deformation is 83%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110316328.4A CN113070471A (en) | 2021-03-24 | 2021-03-24 | Preparation method of titanium-graphene composite material with strong plasticity matching |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110316328.4A CN113070471A (en) | 2021-03-24 | 2021-03-24 | Preparation method of titanium-graphene composite material with strong plasticity matching |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113070471A true CN113070471A (en) | 2021-07-06 |
Family
ID=76610659
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110316328.4A Pending CN113070471A (en) | 2021-03-24 | 2021-03-24 | Preparation method of titanium-graphene composite material with strong plasticity matching |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113070471A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114523101A (en) * | 2021-12-31 | 2022-05-24 | 宁夏大学 | Core-shell material of high-entropy oxide or high-entropy oxide and graphene coated high-entropy alloy and method for preparing bimodal-structure composite material |
CN115074566A (en) * | 2022-07-07 | 2022-09-20 | 西北有色金属研究院 | Method for improving performance of titanium-based composite material through modified and dispersed oxygen-containing graphene |
CN115821101A (en) * | 2022-12-01 | 2023-03-21 | 天津理工大学 | Degradable zinc-based composite material with high strength and antibacterial property and preparation method thereof |
CN115992323A (en) * | 2022-12-09 | 2023-04-21 | 西北工业大学 | Preparation method for preparing high-strength high-plasticity graphene titanium composite material through interface modification |
CN117226086A (en) * | 2023-11-15 | 2023-12-15 | 西安稀有金属材料研究院有限公司 | High-strength plastic multiphase heterogeneous titanium-based composite material and preparation method thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20150116639A (en) * | 2014-04-08 | 2015-10-16 | 성균관대학교산학협력단 | Method of manufacturing multilayer graphene coated composite powders by wire explosion |
CN107557612A (en) * | 2017-07-27 | 2018-01-09 | 中国航发北京航空材料研究院 | A kind of graphene enhancing titanium-based nano composite and preparation method |
CN107598175A (en) * | 2017-07-27 | 2018-01-19 | 中国航发北京航空材料研究院 | A kind of graphene and titanium alloy composite powder ball-milling preparation method |
CN110434347A (en) * | 2019-08-30 | 2019-11-12 | 西安稀有金属材料研究院有限公司 | A kind of graphene-rare earth mixes the preparation method of micro-structure titanium composite material |
CN110512110A (en) * | 2019-09-20 | 2019-11-29 | 安泰科技股份有限公司 | A kind of high-strength titanium alloy-graphene composite material and preparation method thereof |
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 |
CN111451491A (en) * | 2020-04-29 | 2020-07-28 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene reinforced copper-based composite material |
CN112144046A (en) * | 2020-09-23 | 2020-12-29 | 西安稀有金属材料研究院有限公司 | Co @ graphene-titanium-based composite material and preparation method thereof |
CN112410601A (en) * | 2020-12-02 | 2021-02-26 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene-boron heterostructure titanium-based composite material |
-
2021
- 2021-03-24 CN CN202110316328.4A patent/CN113070471A/en active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20150116639A (en) * | 2014-04-08 | 2015-10-16 | 성균관대학교산학협력단 | Method of manufacturing multilayer graphene coated composite powders by wire explosion |
CN107557612A (en) * | 2017-07-27 | 2018-01-09 | 中国航发北京航空材料研究院 | A kind of graphene enhancing titanium-based nano composite and preparation method |
CN107598175A (en) * | 2017-07-27 | 2018-01-19 | 中国航发北京航空材料研究院 | A kind of graphene and titanium alloy composite powder ball-milling preparation method |
CN110434347A (en) * | 2019-08-30 | 2019-11-12 | 西安稀有金属材料研究院有限公司 | A kind of graphene-rare earth mixes the preparation method of micro-structure titanium composite material |
CN110512110A (en) * | 2019-09-20 | 2019-11-29 | 安泰科技股份有限公司 | A kind of high-strength titanium alloy-graphene composite material and preparation method thereof |
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 |
CN111451491A (en) * | 2020-04-29 | 2020-07-28 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene reinforced copper-based composite material |
CN112144046A (en) * | 2020-09-23 | 2020-12-29 | 西安稀有金属材料研究院有限公司 | Co @ graphene-titanium-based composite material and preparation method thereof |
CN112410601A (en) * | 2020-12-02 | 2021-02-26 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene-boron heterostructure titanium-based composite material |
Non-Patent Citations (1)
Title |
---|
YUANLIN XUE等: "Formation Mechanism and Cohesive Energy Analysis of Metal-Coated Graphene Nanocomposites Using In-Situ Co-Reduction Method", 《MATERIALS》 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114523101A (en) * | 2021-12-31 | 2022-05-24 | 宁夏大学 | Core-shell material of high-entropy oxide or high-entropy oxide and graphene coated high-entropy alloy and method for preparing bimodal-structure composite material |
CN114523101B (en) * | 2021-12-31 | 2023-12-12 | 宁夏大学 | High-entropy oxide or high-entropy oxide, graphene coated high-entropy alloy core-shell material and method for preparing bimodal tissue composite material |
CN115074566A (en) * | 2022-07-07 | 2022-09-20 | 西北有色金属研究院 | Method for improving performance of titanium-based composite material through modified and dispersed oxygen-containing graphene |
CN115821101A (en) * | 2022-12-01 | 2023-03-21 | 天津理工大学 | Degradable zinc-based composite material with high strength and antibacterial property and preparation method thereof |
CN115821101B (en) * | 2022-12-01 | 2023-12-22 | 天津理工大学 | Degradable zinc-based composite material with high strength and antibacterial property and preparation method thereof |
CN115992323A (en) * | 2022-12-09 | 2023-04-21 | 西北工业大学 | Preparation method for preparing high-strength high-plasticity graphene titanium composite material through interface modification |
CN117226086A (en) * | 2023-11-15 | 2023-12-15 | 西安稀有金属材料研究院有限公司 | High-strength plastic multiphase heterogeneous titanium-based composite material and preparation method thereof |
CN117226086B (en) * | 2023-11-15 | 2024-02-02 | 西安稀有金属材料研究院有限公司 | High-strength plastic multiphase heterogeneous titanium-based composite material and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113070471A (en) | Preparation method of titanium-graphene composite material with strong plasticity matching | |
CN104630532B (en) | A kind of preparation method of carbide and rare earth oxide complex intensifying carefully brilliant tungsten material | |
CN111500911A (en) | Preparation method of high-toughness nano reinforced metal matrix composite material | |
CN109554565B (en) | Interface optimization method of carbon nanotube reinforced aluminum matrix composite | |
CN111408714B (en) | Preparation method of graphene reinforced copper-based composite material with dual-scale structure and in-situ growth | |
CN110172603B (en) | Preparation method of modified carbon nanotube reinforced titanium-based composite material | |
CN110434347B (en) | Preparation method of graphene-rare earth mixed microstructure titanium-based composite material | |
CN108097962B (en) | Preparation method of Nb-toughened titanium-aluminum-based alloy composite material | |
CN110592412A (en) | Nano AlN particle reinforced mixed crystal heat-resistant aluminum-based composite material and preparation method thereof | |
CN118086800B (en) | High-strength high-toughness aluminum-based silicon carbide composite material and preparation process thereof | |
CN110343890A (en) | A kind of method of carbon nanotube and rare earth composite strengthening magnesium-based composite material | |
CN111549246B (en) | Preparation method of high-toughness graphene/ZK 61 magnesium alloy composite material | |
CN1161483C (en) | High-strength in-situ Al-base composition | |
CN112846198A (en) | Nanoparticle reinforced metal matrix composite material and preparation method thereof | |
CN115584412A (en) | Bimodal grain structure TiAl alloy and preparation method thereof | |
CN103938023B (en) | A kind of in-situ autogenic titanium aluminium carbon highly malleablized TiAl 3intermetallic compound and preparation method thereof | |
CN111041258A (en) | Enhanced light metal matrix composite based on tungsten nanoparticles and preparation method thereof | |
CN112410601B (en) | Preparation method of graphene-boron heterostructure titanium-based composite material | |
CN108031841B (en) | Forming method of metal-based nano composite material part | |
Feng et al. | Enhancing the mechanical and electrical properties of CNTs/Cu composites by synthesizing WC nanoparticles on the surface of CNTs | |
CN110066952B (en) | Preparation method of zirconium oxide reinforced molybdenum alloy bar | |
CN112250102A (en) | Y2Ti2O7Composite nano-particles and preparation method and application thereof | |
CN111889685A (en) | Powder metallurgy method for improving dispersibility and dispersion amount of reinforcement | |
CN115780798A (en) | Nano boron carbide/copper composite material and preparation method thereof | |
CN112342419B (en) | Method for preparing TiC reinforced titanium-based composite material based on cross-linked modified sintered titanium hydride |
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 |
Application publication date: 20210706 |
|
RJ01 | Rejection of invention patent application after publication |