CN109277560A - A kind of preparation method of high-strength and high ductility graphene/metallic composite - Google Patents

A kind of preparation method of high-strength and high ductility graphene/metallic composite Download PDF

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Publication number
CN109277560A
CN109277560A CN201810437448.8A CN201810437448A CN109277560A CN 109277560 A CN109277560 A CN 109277560A CN 201810437448 A CN201810437448 A CN 201810437448A CN 109277560 A CN109277560 A CN 109277560A
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graphene
strength
metallic composite
composite preparation
composite
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褚克
王钒
魏小平
耿中荣
黄大建
李渊博
康皓
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Lanzhou Jiaotong University
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Lanzhou Jiaotong University
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    • B22F1/0003
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06Metallic powder characterised by the shape of the particles
    • B22F1/068Flake-like particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/105Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention relates to a kind of preparation methods of graphene/metallic composite, belong to metal-base composites technical field.Include the following steps: to configure certain density graphene oxide solution, be quickly poured into liquid nitrogen after heating water bath.Solid after freezing is melted, is placed in liquid nitrogen and is rapidly frozen again after ethanol/water solution high speed shear-mixed is uniform with metal powder later, then freeze-drying obtains graphene oxide/composite metal powder.Graphene/metallic composite of high-compactness is obtained through discharge plasma sintering after composite powder thermal reduction.Neural network structure is presented in graphene in graphene/metallic composite prepared by the present invention, and metallic matrix good toughness can be kept while improving the intensity of composite material, and the performance of composite material is substantially better than similar composite material.Process simple possible of the invention, step is easily operated, high safety and reliability, low in cost, is suitable for large-scale production.

Description

A kind of preparation method of high-strength and high ductility graphene/metallic composite
Technical field
The invention belongs to metal-base composites technical field, specially a kind of neural network structure graphene enhances metal The preparation method of based composites.
Background technique
The rapid development of modern industry, to the mechanical property of metal-base composites, more stringent requirements are proposed, traditional fiber And the addition of reinforced particulate such as oxide, the introducing of carbide nanometer particle, while improving metal-base composites intensity Make metal toughness decline obvious instead.So the metal-base composites for researching and developing high-intensity and high-tenacity becomes current Metal Substrate The hot spot of composite material research.
Graphene is a kind of carbon atom with sp2Only one carbon atom of the planar honeycomb shape structure of hybridized orbit composition is thick The two-dimensional material of degree, specific surface area (2630 m with super large2/ g), elasticity modulus is up to 1 TPa, and tensile strength can reach 1060 GPa are to be currently known the highest material of intensity (up to 130 GPa), also harder than diamond.Increasing of the graphene as metal When strong body, the stress of matrix is significantly increased by the effects of crystal grain refinement, dislocation strengthening and stress transfer, so blocky stone Black alkene metal-base composites has good mechanical property.The advantage for giving full play to graphene prepares high performance metal Base graphene composite material can bring quantum jump to the development of metal and composite material.Such as: Yue et al. (Journal of 691 (2017) 755-762 of Alloys and Compounds) selection copper particle be matrix, graphene nanometer sheet as enhancing Body has successfully prepared graphene/copper composite material using the technique that ball milling and vacuum heating-press sintering combine, as the result is shown stone When black alkene nanometer sheet content is 0.5 wt%, the tensile strength for the graphene/copper composite material prepared is 230 MPa or so, About 25% is improved than fine copper, while the Vickers hardness of graphene/copper composite material reaches 52 HV or so, improves 13% than fine copper Left and right.But as the agglomeration of graphene can occur for the increase of graphene nanometer sheet amount, graphene nanometer sheet gradually with copper Matrix is gradually disengaged so that composite property declines, and composite material tension failure result is also changed into brittleness by ductile rupture and breaks It splits.Muhammad Rashad et al. (Materials International 24(2014) 101-108) pass through semi-finished product powder Metallurgy method and hot extrusion method successfully prepare graphene nanometer sheet-aluminium composite material, and result of study shows relative to pure aluminum substrate Material, the yield strength that the graphene reinforced aluminum matrix composites of 0.3 wt% are added improve 14.7%, and tensile strength improves 11%, respectively reach 195 MPa and 280 MPa.At the same time, toughness 9% has dropped 5% or so compared to pure aluminum substrate.
Most of researchs at present are to pass through graphene nanometer sheet or redox graphene and metal powder mechanical mixed Conjunction or chemically combined mode, in the base using graphene as Dispersion of Reinforcement.But graphene/the metal prepared is multiple The performance of condensation material is unsatisfactory.Its reason is mainly that the interfacial wettability between graphene and metallic element is poor, and binding force is weak, Poor dispersion is easy to happen reunion.Especially the too high levels of graphene when, the porosity of composite material rises, graphene More easy to reunite, this greatly weakens graphene to the strengthening effect of composite materials property, and the intensity of composite material is significantly Plasticity and toughness are substantially reduced instead while raising.
Summary of the invention
The present invention combines bad for graphene and metal interface, and graphene dispersion is uneven after mixing, the group of being easy to appear The problems such as poly-, using the graphene that can not only prepare neural network structure, but also it is mixed with copper to avoid graphene Lamination problem ensure that composite powder uniformly mixes.Obtained composite material strength maintains Metal Substrate while raising again The good toughness of body.
To achieve the above object, the invention adopts the following technical scheme:
A kind of preparation method of high-strength and high ductility graphene/metallic composite, specific steps include:
1) certain density graphene oxide solution is configured, is quickly poured into liquid nitrogen after heating water bath to certain temperature.
2) it is put again after alcohol/water solution high speed shear-mixed is uniform after melting the solid of freezing with metal powder It is placed in liquid nitrogen and is rapidly frozen, then freeze-drying obtains graphene oxide/metal mixed powder.
3) discharge plasma sintering obtains graphene/metallic composite of high-compactness after heat-treating composite powder.
Preferably, graphene oxide is laminated structure in step 1), and diameter is 10 ~ 50 μm, with a thickness of 2 ~ 10 Nm, single layer rate be about 99%, purity 99.8%.
Preferably, the concentration of graphene oxide solution is 0.5 ~ 3 mg/mL in step 1).
Preferably, in step 1) the control of ultrasonic disperse device frequency in 10000 ~ 20000 Hz, ultrasonic time 0.5 ~ 2.0 h, ultrasonic temperature are controlled at 20 ~ 45 DEG C.
Preferably, the temperature of heating water bath is 60 ~ 90 DEG C in step 1), and heating time is 10 ~ 30 min.
Preferably, metal powder is one to multiple kind in aluminium, copper, nickel, iron and its alloy powder in step 2.
Preferably, the volume fraction of graphene oxide is 0.5 ~ 3 vol% in step 2.
Preferably, the ratio of water and ethyl alcohol is its 1:9 ~ 3:7 v/v in solution in step 2.
Preferably, the revolving speed of step 2 high speed shearing is 5000 ~ 20000 rpm, and incorporation time is 1 ~ 3 h;
Preferably, the time being freeze-dried in step 2 is 24 ~ 72 h, 10 Pa of relative degree of vacuum.
Preferably, the parameter heat-treated in step 3) are as follows: reduction temperature is 300 ~ 500 DEG C, and the recovery time is 1 ~ 3 H, reducing atmosphere are hydrogen, and protective atmosphere is argon gas, and its ratio be 1:9 ~ 3:7 v/v.
Preferably, discharge plasma sintering parameter in step 3) are as follows: sintering temperature is 500 ~ 800 DEG C, sintering pressure For 30 ~ 50 MPa, sintering time is 5 ~ 10 min.
In graphene/metallic composite prepared by the present invention, graphene showed after liquid nitrogen frozen it is similar The structure (attached drawing 2) of neural network, the graphene of neural network structure is closely arranged in by high speed shear mixed metal powder Interlayer and surface, be evenly distributed.When material stress cracks, " dendron " of neural network structure graphene can be played The effect of bridging causes crack deflection or crack branching, to delay/hinder the extension of crackle.
Therefore composite material interface prepared by the present invention is well combined, even tissue, compact structure, while intensity improves Maintain the good toughness of metallic matrix.Rationally, simple process is efficient, high safety and reliability, at low cost for instant component proportion It is honest and clean, it can satisfy industrial application.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Fig. 2 is the scanning electron microscope diagram of the neural network structure graphene of one embodiment of the present of invention.
Specific embodiment
In order to keep advantages and objects of the present invention more clear, with the following Examples, to specific implementation of the invention Mode makes more detailed description, in the following description, elaborates many concrete details in order to adequately understand this Invention.The present invention is not limited by the specific implementation of following discloses.
Embodiment one
In aqueous solution by graphene oxide (piece diameter is 20 μm, with a thickness of 2 nm) dispersion, 1 h of ultrasonic disperse is configured to concentration For the graphene oxide solution of 2 mg/mL.Then it is quickly poured into liquid nitrogen after heating 20 min under 80 DEG C of bath temperatures.It will Graphene oxide after freezing melts, and the flake copper powder (graphene oxide volume fraction is 1%) with 10 μm is in water/alcoholic solution (v:v=1:9) high speed shear-mixed, revolving speed is 10000 rpm when mixing, and incorporation time is 1 h, obtains graphene-copper mixing Dispersion liquid.Mixed dispersion liquid is placed in rapidly to freezing in liquid nitrogen to be freeze-dried after forming solid, drying time is 48 h, is obtained Graphene/copper composite powder.Graphene/copper powders are transferred in tube furnace, under argon gas/hydrogen (9:1 v/v) atmosphere, 60 min are restored at a temperature of 300 DEG C.Composite powder after thermal reduction carries out discharge plasma sintering, and sintering temperature is 700 DEG C, Sintering pressure is 50 MPa, and sintering time is 8 min, obtains block graphene/copper composite material.The composite material of preparation is through drawing Measuring is stretched, tensile strength can reach 385 MPa, elongation percentage 29%.
Embodiment two
In aqueous solution by graphene oxide (piece diameter is 20 μm, with a thickness of 2 nm) dispersion, 1 h of ultrasonic disperse is configured to concentration The graphene oxide solution of 1 mg/mL.Then it is quickly poured into liquid nitrogen after heating 20 min at a temperature of 80 DEG C of waters.It will be cold Graphene oxide after jelly melts, with 5 μm of spherical copper powder (graphene oxide volume fraction is 1%) water/alcoholic solution (v: V=1:9) high speed shear-mixed, revolving speed is 10000 rpm when mixing, and incorporation time is 2 h, obtains graphene-copper mixing point Dispersion liquid.Mixed dispersion liquid is poured into rapidly after liquid nitrogen frozen forms solid and be freeze-dried, drying time is 48 h, obtains graphite Alkene/copper composite powder.Graphene-copper powders are transferred in tube furnace, under argon gas/hydrogen (9:1 v/v) atmosphere, 400 DEG C At a temperature of restore 60 min.Composite powder after thermal reduction is subjected to discharge plasma sintering, sintering temperature is 700 DEG C, sintering Pressure is 50 MPa, and sintering time is 8 min, obtains block graphene/copper composite material.The composite material finally obtained is through drawing Measuring is stretched, tensile strength can reach 397 MPa, elongation percentage 32%.
Embodiment three
In aqueous solution by graphene oxide (piece diameter is 10 μm, with a thickness of 2 nm) dispersion, 1 h of ultrasonic disperse is configured to concentration The graphene oxide solution of 1 mg/mL.Then it is quickly poured into liquid nitrogen after heating 20 min under 60 DEG C of bath temperatures.It will be cold Graphene oxide after jelly melts, with 2 μm of aluminium powder (graphene oxide volume fraction is 1%) water/alcoholic solution (v:v=1: 9) high speed shear-mixed, revolving speed is 10000 rpm when mixing, and incorporation time is 1 h, obtains graphene-aluminium mixed dispersion liquid. Mixed dispersion liquid is placed in rapidly in liquid nitrogen after freezing forms solid and is freeze-dried, drying time is 48 h, obtain graphene/ Aluminium composite powder.Graphene-aluminium composite powder is transferred in tube furnace, under argon gas/hydrogen (9:1 v/v) atmosphere, 300 60 min are restored at a temperature of DEG C.Composite powder after thermal reduction is subjected to discharge plasma sintering, sintering temperature is 550 DEG C, is burnt Knot pressure power is 50 MPa, and sintering time is 8 min, obtains block graphene/aluminum composite material.The composite material warp finally obtained Stretching experiment measurement, tensile strength can reach 255 MPa, elongation percentage 28%.
Example IV
In aqueous solution by graphene oxide (piece diameter is 10 μm, with a thickness of 2 nm) dispersion, 60 min of ultrasonic disperse is configured to The graphene oxide solution of 1 mg/mL of concentration.Then it is quickly poured into liquid nitrogen after heating 20 min at a temperature of 80 DEG C of waters. Graphene oxide after freezing is melted, with 1 μm of nickel powder (graphene oxide volume fraction is 1%) alcohol/water solution (v: V=1:9) high speed shear-mixed, revolving speed is 10000 rpm when mixing, and incorporation time is 60 min, obtains graphene-nickel mixing Dispersion liquid.Mixed dispersion liquid is poured into rapidly after liquid nitrogen frozen forms solid and be freeze-dried, drying time is 48 h, obtains graphite Alkene/nickel composite powder.Graphene-nickel powder is transferred in tube furnace, under argon gas/hydrogen (7:3 v/v) atmosphere, 400 DEG C At a temperature of restore 60 min.Composite powder after thermal reduction is subjected to discharge plasma sintering, sintering temperature is 800 DEG C, sintering Pressure is 50 MPa, and sintering time is 10 min, obtains block graphene/nickel composite material.The composite material warp finally obtained Stretching experiment measurement, intensity can reach 850 MPa, elongation percentage 30%.
Above example will be helpful to those skilled in the art and further understand the present invention, but not limit this in any form Invention.It should be pointed out that those skilled in the art, without departing from the inventive concept of the premise, may be used also To make several modifications and improvements.These are all within the scope of protection of the present invention.

Claims (12)

1. a kind of high-strength and high ductility graphene/metallic composite, it is characterized in that method includes the following steps:
(1) certain density graphene oxide solution is configured, is quickly poured into liquid nitrogen after heating water bath to certain temperature;
(2) are placed again after ethanol/water solution high speed shear-mixed is uniform with metal powder after the solid of freezing is melted It is rapidly frozen in liquid nitrogen, then freeze-drying obtains graphene oxide/composite metal powder;
(3) discharge plasma sintering obtains graphene/metallic composite of high-compactness after heat-treating composite powder.
2. such as claim 1 high-strength and high ductility graphene/metallic composite preparation method, it is characterized in that the step 1) In, graphene oxide is laminated structure, diameter is 10 ~ 50 μm, with a thickness of 2 ~ 10 nm, single layer rate be about 99%, purity is 99.8%。
3. such as claim 1 high-strength and high ductility graphene/metallic composite preparation method, it is characterized in that the step 1) In, the concentration of graphene oxide solution is 0.5 ~ 3 mg/mL.
4. such as claim 1 high-strength and high ductility graphene/metallic composite preparation method, it is characterized in that the step 1) In, the control of ultrasonic disperse device frequency exists in 10000 ~ 20000 Hz, 0.5 ~ 2.0 h of ultrasonic time, ultrasonic temperature control 20 ~ 45 ℃。
5. such as claim 1 high-strength and high ductility graphene/metallic composite preparation method, it is characterized in that the step 1) In, the temperature of heating water bath is 60 ~ 90 DEG C, and heating time is 10 ~ 30 min.
6. such as claim 1 high-strength and high ductility graphene/metallic composite preparation method, it is characterized in that the step 2) In, metal powder is one to multiple kind in aluminium, copper, nickel, iron and its alloy powder.
7. such as claim 1 high-strength and high ductility graphene/metallic composite preparation method, it is characterized in that the step 2) In, the volume fraction of graphene oxide is 0.5 ~ 3 vol%.
8. such as claim 1 high-strength and high ductility graphene/metallic composite preparation method, it is characterized in that the step 2) In, the ratio of water and ethyl alcohol is its 1:9 ~ 3:7 v/v in solution.
9. such as claim 1 high-strength and high ductility graphene/metallic composite preparation method, it is characterized in that the step 2) In, the revolving speed of high speed shear is 5000 ~ 20000 rpm, and incorporation time is 1 ~ 3 h.
10. such as claim 1 high-strength and high ductility graphene/metallic composite preparation method, it is characterized in that the step 2) In, the time of freeze-drying is 24 ~ 72 h, 10 Pa of relative degree of vacuum.
11. such as claim 1 high-strength and high ductility graphene/metallic composite preparation method, it is characterized in that the step 3) In, the parameter of thermal reduction are as follows: reduction temperature is 300 ~ 500 DEG C, and the recovery time is 1 ~ 3 h, and reducing atmosphere is hydrogen, is protected Shield atmosphere is argon gas, and its ratio be 1:9 ~ 3:7 v/v.
12. such as claim 1 high-strength and high ductility graphene/metallic composite preparation method, it is characterized in that being put in step 3) Electric plasma agglomeration parameter are as follows: sintering temperature is 500 ~ 800 DEG C, and sintering pressure is 30 ~ 50 MPa, sintering time 5 ~10 min。
CN201810437448.8A 2018-05-09 2018-05-09 A kind of preparation method of high-strength and high ductility graphene/metallic composite Pending CN109277560A (en)

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Cited By (6)

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CN109825734A (en) * 2019-04-01 2019-05-31 江西理工大学 Collaboration enhancing Cu-base composites and preparation method thereof
CN111549246A (en) * 2020-04-24 2020-08-18 郑州大学 Preparation method of high-toughness graphene/ZK 61 magnesium alloy composite material
CN111686714A (en) * 2020-07-27 2020-09-22 兰州交通大学 Preparation method of oxygen-enriched vacancy cerium-molybdenum-based nanosphere electrochemical nitrogen fixation catalyst
CN111701598A (en) * 2020-06-29 2020-09-25 兰州交通大学 Efficient iron-molybdenum-based nitrogen reduction electrocatalyst and preparation method thereof
CN113333773A (en) * 2021-06-24 2021-09-03 中国矿业大学 Method for preparing metal particle-loaded coal-based graphene through high-temperature thermal shock
CN113894293A (en) * 2021-10-08 2022-01-07 江苏省特种设备安全监督检验研究院 Method for preparing graphene composite 18Ni-300 antifriction metal material based on SLM technology

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CN105821227A (en) * 2016-06-01 2016-08-03 哈尔滨理工大学 Method for preparing graphene reinforced copper base composite material
CN105838913A (en) * 2016-04-08 2016-08-10 上海和伍复合材料有限公司 Graphene/nickel composite material and preparation method thereof
CN106226365A (en) * 2016-08-11 2016-12-14 安徽省宁国天成电工有限公司 A kind of graphene/copper composite material and its preparation method and application
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Publication number Priority date Publication date Assignee Title
CN109825734A (en) * 2019-04-01 2019-05-31 江西理工大学 Collaboration enhancing Cu-base composites and preparation method thereof
CN111549246A (en) * 2020-04-24 2020-08-18 郑州大学 Preparation method of high-toughness graphene/ZK 61 magnesium alloy composite material
CN111701598A (en) * 2020-06-29 2020-09-25 兰州交通大学 Efficient iron-molybdenum-based nitrogen reduction electrocatalyst and preparation method thereof
CN111686714A (en) * 2020-07-27 2020-09-22 兰州交通大学 Preparation method of oxygen-enriched vacancy cerium-molybdenum-based nanosphere electrochemical nitrogen fixation catalyst
CN113333773A (en) * 2021-06-24 2021-09-03 中国矿业大学 Method for preparing metal particle-loaded coal-based graphene through high-temperature thermal shock
CN113894293A (en) * 2021-10-08 2022-01-07 江苏省特种设备安全监督检验研究院 Method for preparing graphene composite 18Ni-300 antifriction metal material based on SLM technology

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