CN111270171A - Nano-carbon reinforced Mo-Cu-Zr composite material and preparation method thereof - Google Patents
Nano-carbon reinforced Mo-Cu-Zr composite material and preparation method thereof Download PDFInfo
- Publication number
- CN111270171A CN111270171A CN202010159303.3A CN202010159303A CN111270171A CN 111270171 A CN111270171 A CN 111270171A CN 202010159303 A CN202010159303 A CN 202010159303A CN 111270171 A CN111270171 A CN 111270171A
- Authority
- CN
- China
- Prior art keywords
- powder
- composite
- composite material
- graphene
- aqueous solution
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 197
- 229910017985 Cu—Zr Inorganic materials 0.000 title claims abstract description 79
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 151
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000843 powder Substances 0.000 claims abstract description 52
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 51
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 49
- 229940074391 gallic acid Drugs 0.000 claims abstract description 35
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 33
- JMGZEFIQIZZSBH-UHFFFAOYSA-N Bioquercetin Natural products CC1OC(OCC(O)C2OC(OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5)C(O)C2O)C(O)C(O)C1O JMGZEFIQIZZSBH-UHFFFAOYSA-N 0.000 claims abstract description 25
- IVTMALDHFAHOGL-UHFFFAOYSA-N eriodictyol 7-O-rutinoside Natural products OC1C(O)C(O)C(C)OC1OCC1C(O)C(O)C(O)C(OC=2C=C3C(C(C(O)=C(O3)C=3C=C(O)C(O)=CC=3)=O)=C(O)C=2)O1 IVTMALDHFAHOGL-UHFFFAOYSA-N 0.000 claims abstract description 25
- FDRQPMVGJOQVTL-UHFFFAOYSA-N quercetin rutinoside Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 FDRQPMVGJOQVTL-UHFFFAOYSA-N 0.000 claims abstract description 25
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000005493 rutin Nutrition 0.000 claims abstract description 25
- 229960004555 rutoside Drugs 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 22
- IKGXIBQEEMLURG-BKUODXTLSA-N rutin Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@@H]1OC[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-BKUODXTLSA-N 0.000 claims abstract 6
- 238000000498 ball milling Methods 0.000 claims description 60
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 31
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 31
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 31
- 238000009694 cold isostatic pressing Methods 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 26
- 238000009768 microwave sintering Methods 0.000 claims description 20
- 238000000465 moulding Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000000280 densification Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 abstract description 13
- 230000003014 reinforcing effect Effects 0.000 abstract description 9
- 230000001976 improved effect Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- PRVKLYVQRIDKIC-UHFFFAOYSA-N [Mo].[Cu].[Zr] Chemical compound [Mo].[Cu].[Zr] PRVKLYVQRIDKIC-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical group CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 36
- 239000002002 slurry Substances 0.000 description 36
- 238000003825 pressing Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 238000007710 freezing Methods 0.000 description 24
- 230000008014 freezing Effects 0.000 description 24
- IKGXIBQEEMLURG-NVPNHPEKSA-N rutin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-NVPNHPEKSA-N 0.000 description 21
- 238000005245 sintering Methods 0.000 description 19
- 238000001035 drying Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
- 239000010949 copper Substances 0.000 description 14
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 12
- 229910017315 Mo—Cu Inorganic materials 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 10
- 229910052750 molybdenum Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 239000002048 multi walled nanotube Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 208000010392 Bone Fractures Diseases 0.000 description 3
- 206010017076 Fracture Diseases 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003305 rutin Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000011156 metal matrix composite Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 206010010214 Compression fracture Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- HVQAJTFOCKOKIN-UHFFFAOYSA-N flavonol Natural products O1C2=CC=CC=C2C(=O)C(O)=C1C1=CC=CC=C1 HVQAJTFOCKOKIN-UHFFFAOYSA-N 0.000 description 1
- 150000002216 flavonol derivatives Chemical class 0.000 description 1
- 235000011957 flavonols Nutrition 0.000 description 1
- 235000007983 food acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
-
- 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
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- 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
-
- 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
-
- 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
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
- C22C49/10—Refractory metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Fluid Mechanics (AREA)
- Optics & Photonics (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a nano-carbon reinforced Mo-Cu-Zr composite material and a preparation method thereof, wherein the nano-carbon reinforced Mo-Cu-Zr composite material comprises 0-1.5% of carbon nano-tubes subjected to surface modification, 0-1.5% of graphene subjected to surface modification and the balance of molybdenum-copper-zirconium powder; the surface-modified carbon nanotube is obtained by modifying the carbon nanotube with a gallic acid aqueous solution, and the surface-modified graphene is obtained by modifying graphene with a rutin aqueous solution; the Mo-Cu-Zr composite material disclosed by the invention is low in impurity content, the structural integrity of the added reinforcing phase component is kept, the reinforcing effect can be exerted, and the strength and hardness performance of the Mo-Cu-Zr composite material are obviously improved; in addition, the invention also discloses a preparation method of the nano-carbon reinforced Mo-Cu-Zr composite material, and the method has the advantages of simple process, easiness in production and wide application prospect.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a nanocarbon reinforced Mo-Cu-Zr composite material and a preparation method thereof.
Background
Molybdenum (Mo) and copper (Cu) are neither reactive nor soluble, and generally only pseudo-alloys can be formed. The pseudo alloy has the characteristics of two metal materials of Mo and Cu at the same time, makes up for the deficiencies of the Mo and the Cu, has complementary advantages and has good comprehensive performance. Mainly has excellent electric and heat conducting performance,
Low and adjustable thermal expansion coefficient, high hardness and high strength. Since scientists began to research Mo-Cu composite materials, Mo-Cu composite materials have been widely used in electrodes, electrical contact materials, electronic packaging materials, high temperature structural materials, and the like. China has abundant molybdenum ore resources, which provides a favorable environment for the vigorous development of metal Mo and alloy products thereof in China. However, because Mo and Cu have large melting points and are not mutually soluble, Mo and Cu are difficult to mutually dissolve even in a molten state, a completely compact Mo-Cu composite material is difficult to obtain by powder metallurgy liquid phase sintering or infiltration by adopting a traditional smelting method, and the prepared material has the problems of uneven microstructure and the like, so that the potential of the Mo-Cu composite material cannot be fully exerted, and the application of the Mo-Cu composite material is limited. Therefore, the exploration of a new process and a new technology for preparing the Mo-Cu composite material not only has positive practical significance, but also has good development prospect.
At present, the research on Mo-Cu composite materials mainly focuses on the preparation of ultrafine powder, and certain achievements are obtained on the preparation process of the powder, and an oxide co-reduction method, a mechanical alloying method, a mechanical thermochemical method and the like are designed. However, these methods still have some disadvantages that the oxide co-reduction method is slightly inferior in uniformity of raw material mixing, and the mechanical alloying method and the mechanical thermochemical method often introduce impurities into the powder during the mechanical mixing process, thereby lowering the practical application value of the Mo — Cu composite. In recent years, the addition of a transition metal activator into Mo-Cu composite powder greatly reduces sintering temperature and energy consumption in the preparation process, receives attention from people, and is widely applied to the synthesis and preparation of various Mo-Cu composite materials. The scholars at home and abroad generally think that in the process of strengthening sintering, a small amount of activating agent precipitates on the surface of matrix particles to form a second phase which is easy to diffuse matrix atoms, so that the sintering process is accelerated, the Mo phase sintering process can be promoted, and the density of the material can be improved. Zr element can form solid solution and intermetallic compound with Mo and Cu at the same time, and is added into the Mo-Cu composite material as an activating agent, so that the interface combination condition between Mo and Cu can be theoretically improved, a tighter combination interface can be formed, the compactness of the material is hopefully improved, and the Mo-Cu composite material with better performance can be obtained.
On the other hand, since the carbon nanotube and the graphene are respectively found, the research of broad scholars is facilitated, and the carbon nanotube has excellent optical, thermal, electrical and mechanical properties due to the unique structure, extremely high mechanical strength and ideal elasticity, low thermal expansion coefficient, small size and other excellent characteristics; graphene has high strength, large specific surface area and good elongation. Carbon nanotubes and graphene are ideal materials as the reinforcing phase of the composite material. Carbon nanotubes and graphene are widely used as reinforcing phases for composites, and rapid development has been made in polymer-based composites. The nano-carbon materials such as Graphene (Graphene) and Carbon Nanotubes (CNTs) have excellent electric and thermal conductivity and high strength, and are widely used in research and application of composite materials.
However, carbon nanotubes and graphene also present many difficulties in their application in reinforcing metal matrix composites. On one hand, since the carbon nanotubes and the graphene are all nano materials, the carbon nanotubes and the graphene have extremely large specific surface area and specific surface energy, and have large van der waals force, are easy to agglomerate and entangle, and are difficult to uniformly disperse in a metal matrix. On the other hand, the surface activity of the carbon nanotubes and graphene is low, and the wettability with the metal matrix is poor, so that the interface bonding strength between the carbon nanotubes and graphene and the metal matrix is poor. These factors seriously affect the mechanical, electrical, frictional and wear properties of the metal matrix composite.
In order to solve the above problems, a great deal of research has been carried out on chemical plating and molecular level mixing methods, but these methods have complex processes and high energy consumption, and the structures of carbon nanotubes and graphene are damaged to some extent during the pretreatment process, which will weaken the enhancement effect.
Disclosure of Invention
One of the purposes of the invention is to overcome the problem that the carbon nano tube and the graphene in the prior art are difficult to be fully matched with a matrix material to fully exert the reinforcing effect when applied to the composite material, and provide a nano-carbon reinforced Mo-Cu-Zr composite material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a nano-carbon reinforced Mo-Cu-Zr composite material comprises molybdenum powder, copper powder and zirconium powder, wherein the weight ratio of the molybdenum powder to the zirconium powder is (50-60): (10-20), the material also comprises surface-modified carbon nanotubes and/or surface-modified graphene, wherein the mass of the surface-modified carbon nanotubes accounts for 0-1.5% of the total mass of the molybdenum powder, the copper powder and the zirconium powder, and the mass of the surface-modified graphene accounts for 0-1.5% of the total mass of the molybdenum powder, the copper powder and the zirconium powder.
The Mo-Cu-Zr composite material provided by the invention combines two carbon nano materials as a nano reinforcing phase to design and obtain a brand new Mo-Cu-Zr alloy and nano carbon material composite reinforcing material. Through modification optimization, the carbon nano tube and graphene have good dispersibility, and can well play a role in reinforcing when being added and applied to the composite material, and then the overall raw material component matching proportion relation design of the composite reinforced material is greatly optimized and adjusted, so that the comprehensive performance of the material is optimal.
Through extensive experimental research of the inventor, the performance of each component can generate synergistic enhancement effect when the weight percentage of each component in the Mo-Cu-Zr composite material is the proportion. On one hand, the carbon nano tube, the graphene and the copper matrix form better interface combination, and the enhancement effect is obviously improved; on the other hand, the carbon film can be formed between the friction pairs by adjusting and controlling the dosage ratio of the carbon nano tubes and the graphene, so that the anti-friction effect is achieved, the addition ratio of the zirconium powder is optimized, on one hand, the zirconium powder can form a solid solution with the molybdenum-copper matrix to achieve the solid solution strengthening effect, on the other hand, the crystal grain size of the molybdenum-copper matrix can be adjusted and reduced, the fine crystal strengthening effect is achieved, and the mechanical strength of the Mo-Cu-Zr composite material is optimized.
Further, the carbon nano tube subjected to surface modification is a carbon nano tube modified by a gallic acid solution, the mass ratio of the carbon nano tube to the gallic acid is 1:0.5-8, and the gallic acid is calculated by the mass of the gallic acid dissolved in the gallic acid solution. Preferably, the mass ratio of the carbon nanotubes to the gallic acid is 1:2-6, and the proper mass ratio of the gallic acid ensures that the total amount of the gallic acid adsorbed on the carbon nanotubes is proper in the modification process, so that the dispersion effect and the performance reduction influence are balanced mutually.
Gallic acid, also called gallic acid, has chemical formula C6H2(OH)3COOH, belonging to the polyphenols. Hydroxyl groups connected to benzene rings in the gallic acid have extremely strong activity, are combined with the surfaces of the carbon nanotubes, and modify the surfaces of the carbon nanotubes; non-woven fabricThe food acid can also be adsorbed on the surface of the carbon nano tube by non-chemical action. The interaction of the two components not only helps to improve the dispersibility of the carbon nano tube, but also does not produce shearing action on the carbon nano tube to cause chemical damage.
Preferably, the gallic acid solution is a 1% to 100% saturated gallic acid solution.
Preferably, the gallic acid solution is an aqueous solution of gallic acid.
The gallic acid is dissolved in the solution in advance, and then the gallic acid and the carbon nano tube are mutually attracted to carry out uniform adsorption modification, so that the carbon nano tube is more fully modified, and the dispersion effect is better. The 1% -100% is calculated by taking the saturated solution of the gallic acid solution as 100% concentration, and the concentration of 1% is diluted by 100 times relative to the saturated solution of the gallic acid solution.
Preferably, the gallic acid solution is a 20% to 100% concentration gallic acid solution. The gallic acid solution with proper concentration is selected, and the higher solution concentration is favorable for the interaction of the gallic acid in the solution and the carbon nano tube to realize modification.
Preferably, the ratio of the mass of the carbon nanotubes to the volume of the aqueous solution of gallic acid is 0.1g:40 mL. The concentration of the gallic acid aqueous solution is 0.3-1.15g/100 mL.
Further, the graphene subjected to surface modification is graphene modified by a rutin solution, and the mass ratio of the graphene to the rutin is 1: 0.5-8. Rutin is calculated by the mass of rutin dissolved in the solution. The proper amount of rutin forms proper modification strength on the graphene.
Rutin, also known as rutin, vitamin P, is a typical representative of flavonols. Due to the existence of the aromatic structure, rutin can generate pi-pi conjugated interaction with the surface of graphene, and is adsorbed on the surface of the graphene, and active groups are grafted on the surface of the graphene, so that the dispersion performance is improved; on the other hand, phenolic hydroxyl groups of rutin can interact with defect sites on the surface of graphene so as to modify the surface of the graphene, and meanwhile, more active groups and biological functional macromolecules can be grafted on the surface due to the existence of active groups such as hydroxyl groups. The combined action of the two aspects is more beneficial to improving the dispersion performance of the graphene, and the complete structure of the graphene is not damaged.
Preferably, the rutin solution is a rutin aqueous solution.
Preferably, the rutin solution is 1% -100% saturated rutin solution. The concentration of the rutin solution is relative to the 100% saturated rutin solution. Preferably, the rutin solution is 20% -100% saturated rutin solution.
Further, the volume ratio of the mass of the graphene to the volume of the rutin aqueous solution is 0.1g to 40 mL.
The carbon nano tube subjected to surface modification has the characteristics of good dispersity and low impurity content of the carbon nano tube and the graphene subjected to surface modification, and the complete structure is maintained.
Further, the carbon nanotube subjected to surface modification is a carbon nanotube modified by a gallic acid solution, and the graphene subjected to surface modification is graphene modified by a rutin solution.
The modification process is as follows: and putting the carbon nano tube into a gallic acid solution, performing ultrasonic dispersion, standing, filtering and drying to obtain the modified carbon nano tube.
And putting the graphene into a rutin solution, performing ultrasonic dispersion, standing, filtering and drying to obtain the modified graphene.
Preferably, the ultrasonic dispersion time is 30min, the standing time is 24h, the vacuum drying temperature is 60 ℃, and the vacuum drying time is 2 h. In the modification method of the carbon nano tube and the graphene, a brand-new modification method integrating physical adsorption and chemical adsorption is adopted, so that the method is efficient and reliable, does not generate pollutants such as wastewater, waste acid and the like, and is simple in process, easy to produce and stable and reliable in modification effect.
Further, the nano-carbon reinforced Mo-Cu-Zr composite material comprises the following components in percentage by weight: 0-1.5% of carbon nano-tube subjected to surface modification, 60% of molybdenum powder, 30% of copper powder and 10% of zirconium powder.
Further, the nano-carbon reinforced Mo-Cu-Zr composite material comprises the following components in percentage by weight: 0-1.5% of graphene subjected to surface modification, 55% of molybdenum powder, 30% of copper powder and 15% of zirconium powder.
Further, the nano-carbon reinforced Mo-Cu-Zr composite material comprises the following components in percentage by weight: 0.9% of carbon nano tube subjected to surface modification, 0.1% of graphene subjected to surface modification, 50% of molybdenum powder, 30% of copper powder and 20% of zirconium powder. By adopting the proportion, the performance of the prepared composite material reaches the best, the density can reach 99.79 percent, the hardness is 385.36HV, and the compression strength reaches 966.93 MPa.
The invention also aims to provide a method for preparing the reinforced Mo-Cu-Zr composite material, which ensures that the performance of the Mo-Cu-Zr composite material obtained by matching various raw material components is better by optimally designing the preparation method of the Mo-Cu-Zr composite material.
A preparation method of a Mo-Cu-Zr composite material comprises the following steps:
(1) adding carbon nanotubes into a gallic acid aqueous solution, performing ultrasonic dispersion, standing, filtering, and vacuum drying filter residues to obtain surface-modified carbon nanotubes;
(2) adding graphene into a rutin aqueous solution, performing ultrasonic dispersion, standing, filtering, and vacuum-drying filter residues to obtain surface-modified graphene;
(3) mixing the surface-modified carbon nano tube, the surface-modified graphene, molybdenum powder, copper powder and zirconium powder, and performing ball milling to obtain composite powder;
(4) performing cold press molding on the composite powder, placing the composite powder in a steel mold, performing pre-pressing molding at the pressure of 10MPa to obtain a composite material pressed blank, and then performing cold isostatic pressing; specifically, for example, a 5g sample of the composite powder is placed in a mold with the diameter of 16mm, the composite powder is molded under 10MPa, the pressure is maintained for 1min, and then the composite powder is subjected to cold isostatic pressing densification, and the pressure is maintained for 1 min;
(5) and (3) performing microwave sintering on the composite material pressed compact, and cooling to obtain the nano-carbon reinforced Mo-Cu-Zr composite material.
According to the method for preparing the Mo-Cu-Zr composite material, the carbon nano tube and the graphene are subjected to corresponding modification treatment to be converted into the carbon nano material with good dispersibility, then the carbon nano material and other raw materials are mixed and ball-milled to enable various raw material components to fully act to form a mixed material, and finally the composite powder is subjected to cold press molding and microwave sintering to obtain the nano-carbon reinforced Mo-Cu-Zr composite material. The whole preparation method is simple and easy to implement, strong in pertinence, high in pretreatment conversion efficiency of the nano carbon material, fully and uniformly dispersed in the ball milling of the mixed material, the enhancement effect of the carbon nano material is embodied and exerted to the maximum extent, the overall property performance of the composite material finally reaches the design expectation, the mechanical strength is higher, and the comprehensive wear resistance is more excellent.
Further, the ball milling in the step (3) adopts agate balls and agate ball tanks, the ball-material ratio is 10:1, the ball milling rotating speed is 350 r/min, and the ball milling time is 120 min.
Further, the pressure of the cold isostatic pressing in the step (4) is 150 MPa.
Further, the temperature of the microwave sintering in the step (5) is 1170 ℃, the temperature rising time is 30min, and then the temperature is preserved for 120 min.
Compared with the prior art, the invention has the advantages that:
1. the components of the raw material of the nano-carbon reinforced Mo-Cu-Zr composite material are subjected to long-term research and iteration by the inventor, and a brand-new optimized component application and matching proportion relation are provided, so that the properties of the Mo-Cu-Zr composite material in various aspects such as hardness, strength and the like are comprehensively optimized;
2. the preparation raw material components of the Mo-Cu-Zr composite material are subjected to brand-new optimal design and adjustment of mutual correlation of the content ratios of the components, so that the raw material components of the Mo-Cu-Zr composite material can generate a synergistic coordination and co-enhancement effect, the metallographic phase of a metal material matrix in the Mo-Cu-Zr composite material is changed, a brand-new alloy base phase is formed, and the compactness and the strength of the Mo-Cu-Zr composite material are remarkably improved by matching with the enhancement effect of nano carbon;
3. the nano-carbon reinforced Mo-Cu-Zr composite material has better dispersibility and lower impurity content, keeps the structural integrity of the carbon nano-tube and the graphene, has good reinforcing effect when being applied to the composite material, and fully exerts the performance advantage characteristics of the nano-material;
4. the invention provides a preparation method of a Mo-Cu-Zr composite material, which is characterized in that the preparation method is matched with a formula composition and a matching proportion of a brand-new optimized design, a microwave sintering process is adopted for sintering and forming, the enhancement effect of the raw material component formula on the performance of the Mo-Cu-Zr composite material is fully exerted, the sintering process is controlled to obtain the Mo-Cu-Zr composite material with a uniform and compact structure, and the comprehensive performance advantage of a new material is effectively exerted.
Drawings
FIG. 1 is an SEM image (magnification: 5000) of a composite powder after ball milling in example 4 of the present invention;
FIG. 2 is a gold phase diagram (500 times) of a nanocarbon-reinforced Mo-Cu-Zr composite material prepared in example 11 of the present invention;
FIG. 3 is an SEM image (magnification of 5000) of a compression fracture of a Mo-Cu-Zr composite material prepared in inventive example 8.
Detailed Description
The invention will be further explained with reference to the drawings.
The "parts" in the following examples mean parts by weight unless otherwise specified.
The modified carbon nanotubes described in the following examples are prepared by the following method: adding carbon nanotubes into a gallic acid aqueous solution with the concentration of 10 mu g/mL, wherein the volume ratio of the mass of the carbon nanotubes to the gallic acid aqueous solution is 0.1g:40mL, then ultrasonically dispersing for 30min, standing for 24h, filtering, and vacuum drying filter residue at the drying temperature of 60 ℃ for 2h to obtain the product;
the modified graphene described in the following examples is prepared by the following method: adding graphene into a rutin aqueous solution with the concentration of 0.02 mu g/mL, wherein the volume ratio of the mass of the graphene to the rutin aqueous solution is 0.1g:40mL, then ultrasonically dispersing for 30min, standing for 24h, filtering, and vacuum drying filter residue at the drying temperature of 60 ℃ for 2h to obtain the product.
Example 1
Mo-Cu-Zr composite material
(1) According to the weight parts, 60 parts of molybdenum powder, 30 parts of copper powder and 10 parts of zirconium powder are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the Mo-Cu-Zr composite material.
Example 2
Mo-Cu-Zr composite material
(1) According to the weight parts, 60 parts of molybdenum powder, 30 parts of copper powder, 10 parts of zirconium powder and 0.5 part of modified carbon nano tube are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling rotating speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the nano-carbon reinforced Mo-Cu-Zr composite material.
Example 3
Mo-Cu-Zr composite material
(1) According to the weight parts, 60 parts of molybdenum powder, 30 parts of copper powder, 10 parts of zirconium powder and 1.0 part of modified carbon nano tube are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling rotating speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the nano-carbon reinforced Mo-Cu-Zr composite material.
Example 4
Mo-Cu-Zr composite material
(1) According to the weight parts, 60 parts of molybdenum powder, 30 parts of copper powder, 10 parts of zirconium powder and 1.5 parts of modified carbon nano tubes are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling rotating speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the nano-carbon reinforced Mo-Cu-Zr composite material.
Example 5
Mo-Cu-Zr composite material
(1) According to the weight parts, 55 parts of molybdenum powder, 30 parts of copper powder and 15 parts of zirconium powder are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the Mo-Cu-Zr composite material.
Example 6
Mo-Cu-Zr composite material
(1) According to the weight parts, 55 parts of molybdenum powder, 30 parts of copper powder, 15 parts of zirconium powder and 0.5 part of modified graphene are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball-material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling rotating speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the nano-carbon reinforced Mo-Cu-Zr composite material.
Example 7
Mo-Cu-Zr composite material
(1) According to the weight parts, 55 parts of molybdenum powder, 30 parts of copper powder, 15 parts of zirconium powder and 1.0 part of modified graphene are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball-material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling rotating speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the nano-carbon reinforced Mo-Cu-Zr composite material.
Example 8
Mo-Cu-Zr composite material
(1) According to the weight parts, 55 parts of molybdenum powder, 30 parts of copper powder, 15 parts of zirconium powder and 1.5 parts of modified graphene are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball-material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling rotating speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the nano-carbon reinforced Mo-Cu-Zr composite material.
Example 9
Mo-Cu-Zr composite material
(1) According to the weight parts, 50 parts of molybdenum powder, 30 parts of copper powder and 20 parts of zirconium powder are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the Mo-Cu-Zr composite material.
Example 10
Mo-Cu-Zr composite material
(1) According to parts by weight, 50 parts of molybdenum powder, 30 parts of copper powder, 20 parts of zirconium powder, 0.7 part of modified carbon nano tube and 0.3 part of modified graphene are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball-material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling rotating speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the nano-carbon reinforced Mo-Cu-Zr composite material.
Example 11
Mo-Cu-Zr composite material
(1) According to parts by weight, 50 parts of molybdenum powder, 30 parts of copper powder, 20 parts of zirconium powder, 0.8 part of modified carbon nano tube and 0.2 part of modified graphene are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball-material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling rotating speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the nano-carbon reinforced Mo-Cu-Zr composite material.
Example 12
Mo-Cu-Zr composite material
(1) According to parts by weight, 50 parts of molybdenum powder, 30 parts of copper powder, 20 parts of zirconium powder, 0.9 part of modified carbon nano tube and 0.1 part of modified graphene are subjected to ball milling and powder mixing by adopting agate balls and an agate ball tank, the ball-material ratio is 10:1, the ball milling medium is tert-butyl alcohol, the ball milling rotating speed is 350 r/min, and the ball milling time is 2 hours; (2) placing the ball-milled composite slurry into a freezing device for freezing treatment, and after the composite slurry is frozen, placing the composite slurry into a vacuum freeze dryer for drying; (3) placing the prepared composite powder in a steel die, pre-pressing and forming the composite powder at the pressure of 10MPa, and then carrying out cold isostatic pressing densification treatment on a pressed blank, wherein the pressing pressure is 150 MPa; (4) and (3) carrying out microwave sintering molding on the blank subjected to cold isostatic pressing, sintering for 2h at 1170 ℃ under the protection of argon, and then cooling along with a furnace to obtain the nano-carbon reinforced Mo-Cu-Zr composite material.
Test 1
The Mo-Cu-Zr composite materials prepared in the above examples are tested by an electron microscope and other instruments, and the test results of some examples are as follows:
fig. 1 is an SEM picture of the composite powder after ball milling in example 4, in which the surface-modified carbon nanotubes are uniformly dispersed among the particles of molybdenum, copper and zirconium, and a series of changes such as particle deformation, breakage and cold welding occur due to the mechanical action during the ball milling process, thereby forming copper particle aggregates.
FIG. 2 is a metallographic picture of a nanocarbon-reinforced Mo-Cu-Zr composite material obtained in example 11. Figure 2 shows that the molybdenum, copper and zirconium are uniformly distributed throughout.
FIG. 3 is an SEM picture of a compressed fracture of the Mo-Cu-Zr composite material prepared in example 8, and it can be observed that graphene embedded in a matrix exists on the fracture, and also broken carbon nanotubes and broken graphene are observed on the fracture of the Mo-Cu-Zr composite materials prepared in other examples, and the broken carbon nanotubes and broken graphene play a role in bridging and load transfer in the Mo-Cu-Zr composite material.
Test 2
The density of the Mo-Cu-Zr composite materials obtained in examples 1 to 12 was measured by the Archimedes method, i.e., after drying a wafer sample in an oven at 70 ℃ for 24 hours, the dry weight (W1) of the sample at room temperature was weighed on an analytical balance to an accuracy of 0.001 g. The test piece was then boiled in boiling water for 2 hours, and after cooling to room temperature, the saturated test piece was weighed to float in water (W2). Then, the specimen was taken out of the water, excess moisture on the surface of the specimen was gently wiped off with a water-saturated multi-layer gauze, the wet weight of the saturated specimen in the air was quickly weighed (W3), and the experiment was repeated 3 times to take an average value. The actual density (D) and the relative density (D) of the sintered body were calculated, D being (W1 × WDT)/(W3-W2), D being D/D0 × 100%. WDT is the density of water at room temperature, 0.9982g/cm3(20 ℃ C.). d0Is the theoretical density;
the results are shown in Table 1.
TABLE 1 compactness of Mo-Cu-Zr composite materials
In the table, the units of the test results are as follows: density (%).
As can be seen from the results in Table 1, the Mo-Cu-Zr composite materials prepared as described above have a density which varies depending on the composition. The density of the 70Mo30Cu composite material prepared by cold isostatic pressing and then microwave sintering is 86.85%, while when the Cu content is unchanged and 10 wt.% of Zr is added and 10 wt.% of Mo is reduced, the density of the composite material is reduced to 83.38%, while the Mo content is correspondingly reduced along with the increase of the Zr content, the density of the composite material is increased, the densities of the composite materials of 15 wt.% of Zr and 20 wt.% of Zr are 95.36% and 97.63 respectively, and the complete density of the composite material is basically realized.
The results in table 1 show that when MWCNTs (i.e., modified carbon nanotubes) are added to the composite material, the density of the composite material is low as a whole, and is below 85%. And with increasing MWCNTs content there is a downward trend, when the MWCNTs content is increased to 1.5 wt.%, the density is more reduced to 70.27%; the addition of GNPs (namely modified graphene) also has a similar trend, but the addition of a proper amount of the GNPs and the modified graphene can coordinate and enhance the effect, so that the compactness reaches more than 99%.
Test 3
The hardness of the Mo-Cu-Zr composite material obtained in the above example was measured by using an HV-50 Vickers hardness tester to measure the Vickers hardness, the load was 10kg, the dwell time was 15s, 5 points were measured for each sample, and the average was calculated; the compressive strength is tested and represented by a WDW-3100 microcomputer controlled electronic universal material testing machine. The results are shown in Table 2.
TABLE 2 hardness and compressive Strength of Mo-Cu-Zr composites
Sample (I) | Composition (I) | MWCNTs | GNPs | hardness/HV | Compressive strength/MPa |
Example 1 | 60Mo30Cu10Zr | 0 | 0 | 107.10 | 400.37 |
Example 2 | 60Mo30Cu10Zr | 0.5 | 0 | 112.44 | 493.92 |
Example 3 | 60Mo30Cu10Zr | 1.0 | 0 | 97.44 | 445.70 |
Example 4 | 60Mo30Cu10Zr | 1.5 | 0 | 66.20 | 245.49 |
Example 5 | 55Mo30Cu15Zr | 0 | 0 | 291.72 | 786.98 |
Example 6 | 55Mo30Cu15Zr | 0 | 0.5 | 186.29 | 508.00 |
Example 7 | 55Mo30Cu15Zr | 0 | 1.0 | 104.39 | 372.66 |
Example 8 | 55Mo30Cu15Zr | 0 | 1.5 | 92.86 | 310.17 |
Example 9 | 50Mo30Cu20Zr | 0 | 0 | 314.38 | 805.93 |
Example 10 | 50Mo30Cu20Zr | 0.7 | 0.3 | 217.38 | 530.35 |
Example 11 | 50Mo30Cu20Zr | 0.8 | 0.2 | 323.64 | 953.54 |
Example 12 | 50Mo30Cu20Zr | 0.9 | 0.1 | 385.36 | 966.93 |
As can be seen from the test results in Table 2, the hardness of the composite material increased with increasing Zr content in the composite material. With the increase of the content of MWCNTs in the composite material, the hardness of the composite material is reduced, which is mainly due to the fact that the agglomeration of the MWCNTs is increased, and the compactness of the composite material is reduced. The hardness of the composite material is closely related to the density thereof. As the content of GNPs in the composite increases, the hardness of the composite decreases, mainly due to the increased agglomeration of GNPs, resulting in a decrease in compactness. The hardness of the composite material is closely related to the density thereof. With the increase of the content of GNPs in the composite material, the hardness of the composite material is reduced, and the strength of the composite material is closely related to the compactness thereof.
According to the analysis of the performance test results of the examples, when the composition of the Mo-Cu-Zr composite material is, by weight, 0.8% of the surface-modified carbon nanotube, 0.2% of the surface-modified graphene, 50% of the molybdenum powder, 30% of the copper powder, and 20% of the zirconium powder, or 0.9% of the surface-modified carbon nanotube, 0.1% of the surface-modified graphene, 50% of the molybdenum powder, 30% of the copper powder, and 20% of the zirconium powder, better hardness and compressive strength can be achieved.
In addition, the influence of the isostatic pressure on the performance of the composite material is also considered, and on the basis of example 12, the pressing pressure is respectively changed into 130MPa and 160MPa, and the rest is unchanged, so that the compactness is respectively 96.35 percent and 98.53 percent, the hardness is respectively 367.16 and 373.57, and the compressive strength is respectively 950.66MPa and 958.29MPa, and the influence of the isostatic pressure on the composite material is proved to be very obvious.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A nano-carbon reinforced Mo-Cu-Zr composite material is characterized in that: comprises molybdenum powder, copper powder and zirconium powder, wherein the weight ratio of the molybdenum powder to the copper powder to the zirconium powder is (50-60) and 30: (10-20), the material also comprises surface-modified carbon nanotubes and/or surface-modified graphene, wherein the mass of the surface-modified carbon nanotubes accounts for 0-1.5% of the total mass of the molybdenum powder, the copper powder and the zirconium powder, and the mass of the surface-modified graphene accounts for 0-1.5% of the total mass of the molybdenum powder, the copper powder and the zirconium powder.
2. The nanocarbon reinforced Mo-Cu-Zr composite material of claim 1, wherein:
the surface-modified carbon nanotube is obtained by modifying the carbon nanotube with a gallic acid aqueous solution, and the surface-modified graphene is obtained by modifying graphene with a rutin aqueous solution.
3. The nanocarbon reinforced Mo-Cu-Zr composite of claim 2, wherein:
the carbon nano tube subjected to surface modification is prepared by the following method: adding carbon nanotubes into a gallic acid aqueous solution, performing ultrasonic dispersion, standing, filtering, and vacuum drying filter residues to obtain surface-modified carbon nanotubes;
the surface-modified graphene is prepared by the following method: adding graphene into a rutin aqueous solution, performing ultrasonic dispersion, standing, filtering, and vacuum-drying filter residues to obtain surface-modified graphene.
4. The nanocarbon reinforced Mo-Cu-Zr composite of claim 3, wherein: the concentration of the gallic acid aqueous solution is 3-11.5 mug/mL; the concentration of the rutin aqueous solution is 0.02 mu g/mL.
5. The nanocarbon reinforced Mo-Cu-Zr composite of claim 3, wherein: the volume ratio of the mass of the carbon nano tube to the gallic acid aqueous solution is 0.1g:40 mL; the volume ratio of the mass of the graphene to the volume of the rutin aqueous solution is 0.1g:40 mL.
6. The nanocarbon reinforced Mo-Cu-Zr composite of claim 3: the ultrasonic dispersion time is 30 min; the standing time is 24 hours; the temperature of the vacuum drying is 60 ℃, and the time of the vacuum drying is 2 h.
7. The method for preparing a nanocarbon reinforced Mo-Cu-Zr composite material according to any one of claims 1 to 6, characterized by comprising the following steps:
(1) adding carbon nanotubes into a gallic acid aqueous solution, performing ultrasonic dispersion, standing, filtering, and vacuum drying filter residues to obtain surface-modified carbon nanotubes;
(2) adding graphene into a rutin aqueous solution, performing ultrasonic dispersion, standing, filtering, and vacuum-drying filter residues to obtain surface-modified graphene;
(3) performing ball milling on the surface-modified carbon nano tube and the surface-modified graphene with molybdenum powder, copper powder and zirconium powder to obtain composite powder;
(4) placing the composite powder into a mold, molding, maintaining pressure, and then performing cold isostatic pressing densification and pressure maintaining;
(5) and (3) performing microwave sintering on the composite material pressed compact, and cooling to obtain the nano-carbon reinforced Mo-Cu-Zr composite material.
8. The method of claim 7, wherein: and (3) performing ball milling by using agate balls and agate ball tanks, wherein the ball milling rotation speed is 350 r/min, and the ball milling time is 120 min.
9. The method of claim 7, wherein: and (4) the pressure of the cold isostatic pressing in the step (4) is 150 MPa.
10. The method of claim 7, wherein: the temperature of the microwave sintering in the step (5) is room temperature-1170 ℃, the time of the microwave sintering is temperature rise for 30min, and the temperature is preserved for 120 min.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010159303.3A CN111270171B (en) | 2020-03-09 | 2020-03-09 | Nano-carbon reinforced Mo-Cu-Zr composite material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010159303.3A CN111270171B (en) | 2020-03-09 | 2020-03-09 | Nano-carbon reinforced Mo-Cu-Zr composite material and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111270171A true CN111270171A (en) | 2020-06-12 |
CN111270171B CN111270171B (en) | 2021-07-30 |
Family
ID=70995529
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010159303.3A Active CN111270171B (en) | 2020-03-09 | 2020-03-09 | Nano-carbon reinforced Mo-Cu-Zr composite material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111270171B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114855054A (en) * | 2022-05-13 | 2022-08-05 | 赵克中 | Molybdenum-zirconium-based alloy material and preparation method thereof |
CN115821137A (en) * | 2022-11-24 | 2023-03-21 | 广州市华司特合金制品有限公司 | Tungsten alloy for ski counterweight and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108517435A (en) * | 2018-05-21 | 2018-09-11 | 西南交通大学 | A kind of magnetic-levitation train nano-sized carbon enhancing Cu-base composites and preparation method thereof |
CN109207762A (en) * | 2018-10-29 | 2019-01-15 | 四川大学 | A method of tungsten molybdenum copper composite material is prepared with microwave sintering |
-
2020
- 2020-03-09 CN CN202010159303.3A patent/CN111270171B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108517435A (en) * | 2018-05-21 | 2018-09-11 | 西南交通大学 | A kind of magnetic-levitation train nano-sized carbon enhancing Cu-base composites and preparation method thereof |
CN109207762A (en) * | 2018-10-29 | 2019-01-15 | 四川大学 | A method of tungsten molybdenum copper composite material is prepared with microwave sintering |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114855054A (en) * | 2022-05-13 | 2022-08-05 | 赵克中 | Molybdenum-zirconium-based alloy material and preparation method thereof |
CN115821137A (en) * | 2022-11-24 | 2023-03-21 | 广州市华司特合金制品有限公司 | Tungsten alloy for ski counterweight and preparation method thereof |
CN115821137B (en) * | 2022-11-24 | 2024-01-05 | 广州市华司特合金制品有限公司 | Tungsten alloy for snowboard weight and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN111270171B (en) | 2021-07-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108517435B (en) | Nano-carbon reinforced copper-based composite material for maglev train and preparation method thereof | |
Duan et al. | Effect of CNTs content on the microstructures and properties of CNTs/Cu composite by microwave sintering | |
CN106513694B (en) | A kind of preparation method of graphene/metal composite powder | |
CN106399766B (en) | A kind of carbon nanotube and graphene collaboration reinforced aluminum matrix composites and preparation method | |
CN104084578B (en) | A kind of carbon nanotube reinforced copper-base composite material and preparation method thereof | |
CN108145169B (en) | High-strength high-conductivity graphene reinforced copper-based composite material, and preparation method and application thereof | |
CN111270171B (en) | Nano-carbon reinforced Mo-Cu-Zr composite material and preparation method thereof | |
CN105081310A (en) | Method for preparing grapheme reinforced aluminum matrix composite material | |
CN110157931B (en) | Nano carbon reinforced metal matrix composite material with three-dimensional network structure and preparation method thereof | |
CN114293051B (en) | Preparation method of high-temperature softening resistant high-strength high-conductivity copper-based composite material formed part | |
CN107385269A (en) | A kind of method that carbon nanotube reinforced copper-base composite material is prepared using microwave | |
CN104862513A (en) | Method for preparing multiwalled carbon nanotube reinforced metal matrix composite by discharge plasma (SPS) sintering | |
CN108559866A (en) | A kind of high-strength high-conductivity Cu-Ti alloys and preparation method thereof | |
CN107267792A (en) | A kind of preparation method of graphene enhancing copper or copper alloy bar | |
CN110257662A (en) | A kind of copper-graphite alkene composite material and preparation method | |
CN107570698A (en) | A kind of graphene coated titanium composite powder material and preparation method thereof | |
Huang et al. | Improving effect of carbonized quantum dots (CQDs) in pure copper matrix composites | |
CN109439964A (en) | Carbon nanotube-graphene collaboration reinforced aluminum matrix composites mechanical property preparation method | |
CN109811177A (en) | A kind of preparation method of highly conductive high-intensitive silver-graphene composite material | |
CN108251671B (en) | A kind of preparation method of doping graphene oxide enhancing ODS copper | |
CN105861872A (en) | Carbon nanotube reinforced copper-based composite material and preparation method thereof | |
CN114086013A (en) | High-strength high-conductivity ultrafine-grained tungsten-copper composite material and preparation method thereof | |
CN110551909B (en) | Method for improving heat conductivity of magnesium-based composite material by using nano diamond and magnesium-based composite material | |
CN103480837A (en) | Method for preparing high-thermal-conductivity CNT-Cu composite used at high temperature | |
US11773027B1 (en) | Preparation method and product of metal-matrix composite reinforced by nanoscale carbon materials |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |