CN105886829A - Graphene reinforced copper-based composite material and preparation method thereof - Google Patents
Graphene reinforced copper-based composite material and preparation method thereof Download PDFInfo
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- CN105886829A CN105886829A CN201610296765.3A CN201610296765A CN105886829A CN 105886829 A CN105886829 A CN 105886829A CN 201610296765 A CN201610296765 A CN 201610296765A CN 105886829 A CN105886829 A CN 105886829A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
Abstract
The invention discloses a graphene reinforced copper-based composite material. The graphene reinforced copper-based composite material comprises, by weight, 0.5-5% of graphene subjected to surface modification, 2-5% of graphite, 6-15% of Ti3SiC2, and the balance copper. The graphene subjected to surface modification is graphene subjected to gallic acid modification. According to the copper-based composite material, the dispersity of the graphene subjected to surface modification is good, the content of impurities is low, the complete surface appearance is kept, the graphene, the graphite powder, the Ti3SiC2 powder and the copper powder jointly play the enhancement function, the mechanical property and friction abrasion resistance of the copper-based composite material are remarkably improved, and meanwhile the excellent intensity and shock resistance are achieved. The invention further discloses a preparation method of the copper-based composite material. The method is simple in process, production is easy, and wide application prospects are achieved.
Description
Technical field
The invention belongs to the preparing technical field of composite, relate to a kind of Cu-base composites, particularly to a kind of stone
Ink alkene strengthens Cu-base composites and preparation method thereof.
Background technology
2004, Andre Geim and Konstantin Novoselov from University of Manchester utilized machinery first
Stripping method is successfully separated out stable Graphene, and Graphene is just with two-dimensional structure and unique electricity, optics, the mechanics of its uniqueness
Deeply paid close attention to by numerous scholars etc. performance.Graphene have high mechanical strength, the most elastic, low thermal coefficient of expansion,
The excellent characteristics such as size is little make it become most potential reinforcement material.
Graphene achieves development quickly in terms of strengthening polymer composite, but is strengthening metal-base composites
Aspect there is also many difficulties.Main difficulty among these is that Graphene has the biggest ratio table as other nano material
, there is the biggest Van der Waals force, easy aggregately stacked, be difficult in metallic matrix dispersed in area and specific surface energy.Another
Aspect, the surface activity of Graphene is relatively low, poor with the wettability of metallic matrix, which results in the interface between itself and metallic matrix
In conjunction with poor.These factors can have a strong impact on the performances such as the density of metal-base composites, and mechanics, electricity, fretting wear,
Especially friction and wear behavior.In metallic composite field, Cu-base composites is widely used as materials of electronic components, cunning
Dynamic material, contact material, heat exchange material etc..Therefore, Graphene is of greatest concern in terms of strengthening Cu-base composites.
For solving problem above, some researchs at present are devoted to first to be modified Graphene copper facing or nickel plating, then
Use powder metallurgic method to prepare Graphene again and strengthen Cu-base composites.But Graphene is modified copper facing or nickel plating, work
Skill is complicated, and energy consumption is big.Also some researchs are had to be devoted to use strong acid or nitration mixture that Graphene carries out pretreatment, but this place
Reason mode has certain destruction to Graphene, Graphene can be cut into minimum Graphene, destroy its specific surface, and
Often need higher temperature and long period, when processing, easily produce the gas of contaminative simultaneously.
Chinese invention patent application CN104711443A discloses a kind of graphene/copper composite material and preparation method thereof,
By corronil powder and the common mechanical ball milling of crystalline flake graphite, mechanical ball milling adds ethanol as wet grinding media, by mechanical force from
Graphite separates Graphene, tentatively obtains Graphene/copper composite powder, then obtained by powder metallurgy, hot extrusion, rolling technique
The composite of Graphene/copper.The method cannot ensure that crystalline flake graphite is completely exfoliated into graphene film, can there is graphite and reunite
Problem.
Chinese invention patent application CN103736993A discloses a kind of graphenic surface modification and process for dispersing, described side
Method comprises the steps: step one: weigh copper sulfate pentahydrate, nickel sulfate, citric acid, boric acid are configured to mixed solution A, stir
Mix；Step 2: mixed solution A is positioned in magnetic agitation water-bath heating, adds graphene oxide solution, stirring, system
Become mixed solution B；Step 3: add ortho phosphorous acid sodium solution, stirring in solution B, be accelerated reaction, at ultrasonic disperse
Reason, can obtain homodisperse graphene/copper composite material solution；Step 5: solution is carried out repeatedly with micropore filtering film
Sucking filtration, repeatedly washing to pH is neutrality, is vacuum dried, reduction.The method step is numerous and diverse, and can exist reduction the most thoroughly remain oxygen
The possibility of functionalized graphene；Processing procedure uses plurality of reagents simultaneously, the effect toxic to human body of its mesoboric acid.
Summary of the invention
It is an object of the invention to overcome the Graphene in the presence of prior art and metal composite difficulty or composite effect
The best deficiency, it is provided that a kind of Graphene strengthens Cu-base composites.This Cu-base composites by surface-modified Graphene,
Powdered graphite, Ti3SiC2Powder and copper powders composition, the most surface-modified Graphene is the Graphene that gallic acid is modified.
This modified graphene is Graphene to add gallic acid aqueous solution modification make, and has good dispersion, the spy that impurity content is low
Point, and maintain complete specific surface.In this Cu-base composites, the performance of each component produces the effect strengthened altogether, significantly improves
The wear resistance of Cu-base composites and intensity and impact resistance, reduce the density of Cu-base composites.
In order to realize foregoing invention purpose, the invention provides techniques below scheme:
A kind of Graphene strengthens Cu-base composites, including the following component of percentage by weight: surface-modified Graphene
0.5～5%, graphite 2～5%, Ti3SiC26～15%, surplus be copper；
Described surface-modified Graphene is the Graphene that gallic acid is modified.Specifically, it is that Graphene is added
The Graphene that gallic acid aqueous solution modification obtains.
Gallic acid, also known as gallic acid, gallic acid, its chemical entitled Gallic Acid, chemical formula is C6H2
(OH)3COOH, chemical structural formula as shown in formula I, belongs to polyphenols, also belongs to organic acid.
Gallic acid is combined with graphenic surface defect sites by self phenolic hydroxyl group, thus Graphene is carried out table
Face is modified, and improves its dispersive property, simultaneously because the existence of the functional group such as carboxyl and hydroxyl, also can be more multifunctional at surface grafting
Group and biological function macromole.On the other hand, gallic acid can also be adsorbed in graphenic surface by non-chemically effect, passes through
In gallic acid, the π key on phenyl ring and the π key on Graphene are implemented in combination with absorption.The two common effect is more conducive to improve graphite
The dispersibility of alkene, and Graphene generation shear action will not be caused mechanical damage or chemical damage.Otherwise, directly will not locate
Graphene and the copper powders of reason make Cu-base composites, there will be the hole formed because Graphene is reunited, cause in matrix
The combination property of material reduces, and does not reaches good reinforced effects.
Applicant finds through many experiments, when the weight percent content of component each in Cu-base composites is for change through surface
The Graphene 0.5 of property～5%, powdered graphite 2～5%, Ti3SiC2Powder 6～15%, surplus is when being copper powders, the property of each component
Can produce the effect of common enhancing, and between Graphene and Copper substrate, form preferable interface cohesion, and then it is compound to strengthen cuprio
The wear resistance of material and intensity and resistance to impact.Graphite has protection Copper substrate, the effect of anti-melting welding, although stone
Ink is nonwetting with Copper substrate, but the membership that adds of graphite changes the Wear Mechanism of copper, the adhesive wear of fine copper transfer to multiple
The abrasive wear of condensation material, and graphite linings laminated structure, have self lubricity, can form carbon film, thus rise between friction pair
Effect to anti-attrition.Ti3SiC2Good with Copper substrate wettability, lamellar structure is on the friction and wear behavior improving composite
Play the biggest effect.Graphene has extraordinary mechanical property, forms preferable interface knot between Graphene and Copper substrate
Closing, during extraneous loading force, stress can be transferred to Graphene by interface, thus reach the effect of enhancing body.
Following percentage by weight raw material can be used accordingly to prepare above-mentioned Graphene and to strengthen Cu-base composites: through surface
Modified Graphene 0.5～5%, powdered graphite 2～5%, Ti3SiC2Powder 6～15%, surplus be copper powders.Prepare raw material to exist
In forming process, basic holding is lossless, or acceptable loss in production technology, and it is corresponding that final processing prepares
Composite.
Preferably, Cu-base composites includes following component by weight percentage: surface-modified Graphene 0.5～
2%, powdered graphite 2～4%, Ti3SiC2Powder 8～12%, surplus be copper powders.The most preferably, Cu-base composites is by weight
Amount percentage ratio includes following component: surface-modified Graphene 0.5%, powdered graphite 3%, Ti3SiC2Powder 10%, surplus
For copper powders.
It is further preferred that described surface-modified Graphene is made through following methods: Graphene is joined and does not eats
In sub-aqueous acid, it is uniformly dispersed, stands, filter, take filtering residue and be vacuum dried, obtain the Graphene of surface modification.
Preferably, described gallic acid aqueous solution is prepared by deionized water, and in gallic acid aqueous solution, gallic acid is dense
Degree is 3～18mg/mL.Gallic acid, is on the one hand combined with graphenic surface defect sites by self phenolic hydroxyl group, grafting
Functional group thus Graphene is carried out surface modification；On the other hand, it is to utilize its big pi-conjugated structure, with Graphene, π-π heap occurs
Long-pending effect, thus Graphene is modified, improve the dispersibility of Graphene.Applicant finds through test of many times, works as Galla Turcica (Galla Helepensis)
When the concentration of aqueous acid is less than 3mg/mL, graphenic surface due to functional group more in non-grafting, thus can affect its point
Dissipate the raising of property.Along with the increase of gallic acid concentration of aqueous solution, the amount of the gallic acid of graphenic surface absorption can increase, when
When the concentration of gallic acid aqueous solution is more than 18mg/mL, the amount of the gallic acid of graphenic surface absorption exceedes it in water
Maxima solubility (11.49mg/mL), produces the most disadvantageous to the π-π adsorption between gallic acid and Graphene on the contrary
Impact, makes the gallic acid of graphenic surface be desorbed, the phenomenon that modification amount reduces occurs, it is impossible to plays raising Graphene and divides
Dissipate the effect of property.Preferably, the concentration of described gallic acid aqueous solution is 5～11.49mg/mL, the most preferably, and described no food
The concentration of sub-aqueous acid is 10mg/mL.
Preferably, the ratio of the weight of described Graphene and the volume of gallic acid aqueous solution be 0.05～0.5g:20～
60mL；More preferably 0.05～0.2g:30～50mL；Optimal preferably 0.1g:40mL.
Preferably, described Graphene is single-layer graphene or multi-layer graphene.Graphene is used to strengthen Cu-base composites
When, owing to composite combines, the when of using the Graphene of monolayer, reinforced effects highlights, but Graphene exists
Content in Copper substrate improves space and is limited by spatial distribution, and reinforced effects is difficult to reach optimum level.Use multilamellar stone
The when of ink alkene, although Graphene itself has the structure of multilamellar, but Graphene can preferably reach to strengthen composite
Saturated level so that the performance boost effect of composite is more significantly.
Preferably, the time of described standing is 12～30h.For gallic acid stronger acids, character is the gentleest, and it is modified
The grafting bonding that the process of Graphene is the gentleest strengthens, and the adsorption of Van der Waals force.It is less than between upon standing
12h, the response time is too short, is unfavorable for the abundant combination of gallic acid and Graphene；Being longer than 30h between upon standing, it modifies work
With not being further added by, and precipitate the gallic acid partial exfoliation that also can make to have combined with Graphene for a long time in the solution,
Reduce reinforced effects.Preferably, time of repose is 20～25h；When stand time be 20-25 little time when, gallic acid
Reaching maximum with the binding capacity of Graphene, and bond strength is good, the modified reinforced effects for Graphene is optimal.The most excellent
Select time of repose 24 hours.
Preferably, described vacuum drying temperature is 60 DEG C～80 DEG C；When vacuum drying temperature is less than 60 DEG C, it is dried effect
Rate is low；When baking temperature is higher than 80 DEG C, can cause between damage and gallic acid and the Graphene of grafted functional group non-chemically
Weakening of effect, in some instances it may even be possible to can destroy the binding site of modification, reduces the dispersive property of modified graphene.The most excellent
Choosing vacuum drying temperature is 60～70 DEG C, optimal preferably 60 DEG C.
Preferably, the described vacuum drying time is 1～3h.When vacuum is less than 1h drying time, and Graphene cannot not be dried completely
Entirely, affect the performance of Graphene and it is characterized；It is longer than 3h between when drying, the damage of grafted functional group can be caused and do not eat
Non-chemically act between son acid and Graphene weakens.More preferably 1～2h, the most preferably 2h.
By above to gallic acid concentration of aqueous solution, the ratio of weight and the volume of gallic acid aqueous solution of Graphene,
Quiescent time, vacuum drying temperature and time preferred, the dispersibility of surface-modified Graphene can be improved further, with
Time reduce the impurity content of Graphene, and then significantly improve the wear resistance of Cu-base composites and intensity and resistance to punching
Hitting property, reduces its density.
Another object of the present invention is to provide the preparation method of described Cu-base composites.
The preparation method of a kind of Cu-base composites, comprises the steps:
(1) Graphene is joined in gallic acid aqueous solution, is uniformly dispersed, stand, filter, take filtering residue carry out vacuum do
Dry, obtain the Graphene of surface modification.
(2) by the Graphene of surface modification and copper powders, powdered graphite, Ti3SiC2Powder carries out ball milling and mixes powder, must answer
Close powder.
(3) composite powder is carried out hot pressed sintering, cool down, then hip treatment obtains Graphene and strengthens cuprio composite wood
Material.
Preferably, in described step (2), ball milling uses agate ball and Achates spherical tank, and rotational speed of ball-mill is 150～300 turns/
Min, Ball-milling Time is 40～60min.Spheroidal graphite rotating speed is less than 150 turns/min, and Ball-milling Time is less than 40min, can cause composite powder
, there is " segregation " phenomenon during making follow-up hot pressed sintering in end mixing inequality；Spheroidal graphite rotating speed is higher than 300 turns/min, ball
Time consuming, higher than 60min, has obvious shear action to Graphene.It is further preferred that rotational speed of ball-mill is 200 turns/min,
Ball-milling Time is 50min.Controlling the rotating speed of ball milling, time parameter well both can ensure that the mixing uniformity of raw material, again can be more
The good character controlling the product that material obtains during follow-up sinter molding.
Preferably, in described step (2), ball milling uses medium to be the tert-butyl alcohol, and its powder drying mode is lyophilization.
Preferably, the temperature of described step (3) hot pressed sintering is 900～1000 DEG C；When sintering temperature can be led less than 900 DEG C
Cause sintering imperfect, the sintering neck being firmly combined with between copper granule, can not be formed, do not reach the purpose of densification；Sintering temperature is higher than
1000 DEG C, have Ti3SiC2Thermal decomposition phenomenon, has crisp phase TiC and generates.More preferably 950 DEG C.
Preferably, in described step (3), the pressure of hot pressed sintering is 25～40MPa；Sintering pressure is less than 25Mpa, compound
In material compaction process, the adhesion between copper granule is weak, and defect easily occurs in material；Sintering pressure is higher than 40Mpa, in material
Stress is big, is easily caused material cracks.It is further preferred that the pressure of hot pressed sintering is 25～30MPa, most preferably it is preferably
28MPa。
Preferably, in described step (3), the time of hot pressed sintering is 1～4h；Sintering time is shorter than 1h, can cause sintering not
Completely, good combination can not be formed between each phase, not have the effect of enhancing；Sintering time is longer than 4h, can there is copper granule
The phenomenon of abnormal growth, Copper substrate, in large stretch of block, strengthen the faying face mutually and between Copper substrate and reduces, and reinforced effects is paid no attention to
Think.More preferably 1～3h；Optimal preferably 2h.
Compared with prior art, beneficial effects of the present invention:
(1) in Cu-base composites of the present invention, the Graphene of surface modification is used, and without gallic acid
The Graphene processed is compared, and the graphene dispersion of this surface modification is good, and impurity content is low.Corresponding graphene dispersion
Good, big with Copper substrate bonded area, reinforced effects is good；Less impurity can effectively avoid some impurity element to cause matrix
The phenomenon of abnormal grain growth.
(2) Graphene modified through surface of present invention application, maintains the integrity of Graphene, overcomes tradition strong
After acid treatment, the surface of Graphene is destroyed serious, and the big specific surface area that Graphene is high is the key that its bridging effect is formed,
Especially when material is by extraneous stress, big interface bonding energy plays Stress Transfer effect, drops stress concentration, reduces defect
Appearance.
(3) Cu-base composites of the present invention is by the Graphene of surface modification, powdered graphite, Ti3SiC2Powder and copper powders
Composition；Control the weight percent content of each component simultaneously, make the performance of each component produce the effect strengthened altogether, significantly improve
The wear resistance of Cu-base composites and intensity and resistance to impact, reduce its density.
(4) modified graphene of application in the enhancing Cu-base composites of the present invention, preparation method is simple and reliable, easily
Produce, and the method does not produce the pollutant such as waste water, spent acid during preparing modified graphene.
Accompanying drawing illustrates:
Fig. 1 is the Graphene Fourier transform infrared spectroscopy figure after variable concentrations gallic acid aqueous solution processes.
Fig. 2 is SEM figure after the composite batch mixing that embodiment 5～7 Graphene content after ball mill mixing is different.
Fig. 3 is embodiment 6 composite powder EDS figure after ball mill mixing.
Detailed description of the invention
Below in conjunction with test example and detailed description of the invention, the present invention is described in further detail.But this should not understood
Scope for the above-mentioned theme of the present invention is only limitted to below example, and all technology realized based on present invention belong to this
The scope of invention.
The single-layer graphene related in the embodiment of the present invention and few layer graphene are purchased from Chinese Academy of Sciences's Chengdu organic chemistry
Company limited.
Embodiment 1
Few layer graphene is joined in the gallic acid aqueous solution of 10mg/mL, be uniformly dispersed, wherein the weight of Graphene
It is 0.1g:40mL with the ratio of the volume of gallic acid aqueous solution；Stand 24h, filter, take filtering residue at 60 DEG C, be vacuum dried 2h,
Obtain the Graphene of surface modification.
The Graphene 0.1g of the surface modification prepared by the present embodiment 1 is dispersed in 100mL deionized water, stands
After 5 days, precipitate under gravity and gradually increase, but between Graphene, remain in that dispersity, do not reunite；Simultaneously
Contrast with the most modified Graphene, precipitation i.e. occurs after standing 1 day, and agglomeration occurs between Graphene, show reality
The Graphene of the surface modification executing example 1 preparation has the dispersibility of excellence.
Described few layer graphene specific surface is 400～700m2/ g, thickness, 0.55～3.74nm, has high specific surface
Feature.
Embodiment 2
Few layer graphene is joined in the gallic acid aqueous solution of 3mg/mL, be uniformly dispersed, wherein the weight of Graphene
It is 0.5g:60mL with the ratio of the volume of gallic acid aqueous solution；Stand 12h, filter, take filtering residue at 70 DEG C, be vacuum dried 1h,
Obtain the Graphene of surface modification.
The Graphene 0.1g of the surface modification prepared by the present embodiment is dispersed in 100mL deionized water, stands 3
After it, precipitate under gravity and gradually increase, but between Graphene, remain in that dispersity, do not reunite.Show
The Graphene of the surface modification of embodiment 2 preparation has the dispersibility of excellence.
Embodiment 3
Few layer graphene is joined in the gallic acid aqueous solution (supersaturated solution) of 18mg/mL, be uniformly dispersed, wherein
The weight of Graphene is 0.05g:20mL with the ratio of the volume of gallic acid aqueous solution；Stand 30h, filter, take filtering residue at 80 DEG C
Lower vacuum drying 3h, obtains the Graphene of surface modification.
The Graphene 0.1g of the surface modification prepared by the present embodiment is dispersed in 100mL deionized water, stands 2
After it, precipitate under gravity and gradually increase, but between Graphene, remain in that dispersity, do not reunite.Show
The Graphene of the surface modification of embodiment 2 preparation has the dispersibility of excellence.
Comparative example 1～3 understands, the Graphene of the surface modification of embodiment 1 preparation stand 5 days after just at gravity
Increasingly generate under effect and between precipitation, and Graphene, the most well keep dispersity, do not reunite, and embodiment 2
After 2～3 days, precipitation, therefore embodiment 1 institute is generated the most under gravity with the Graphene of the surface modification of 3 preparations
The method stated is substantially better than the method described in embodiment 2 and 3.
Embodiment 4
The concentration of the discussion gallic acid aqueous solution impact on graphene dispersion on the basis of embodiment 1.
The concentration changing gallic acid aqueous solution is 5mg/mL, 20mg/mL (supersaturated solution), and remaining is all with embodiment 1,
Respectively obtain the Graphene of surface modification.
Graphene (5mg/mL) 0.1g of the surface modification prepared by the present embodiment is dispersed in 100mL deionized water
In, after standing 3 days, precipitate under gravity and gradually increase, but between Graphene, remain in that dispersity, do not roll into a ball
Poly-.
Graphene (20mg/mL) 0.1g of the surface modification prepared by the present embodiment is dispersed in 100mL deionization
In water, after standing 1 day, precipitating under gravity and gradually increase, gradually there is slight agglomeration in Graphene.Show when not
When the concentration of gallate-based aqueous solution is 20mg/mL, the modification of Graphene is substantially reduced by it.
Fig. 1 is the Graphene FTIR spectrum figure after variable concentrations gallic acid aqueous solution processes.Meanwhile, use
The Graphene (pure CNFs) processed without gallic acid aqueous solution contrasts.Wherein, the Graphene that 10mg/mL gallic acid processes
Sample is the modified graphene sample that embodiment 1 prepares.The sample that 5mg/mL, 20mg/mL gallic acid processes is this reality
Execute the sample that example 4 prepares according to the technique of the scenario of embodiment 1.
As seen from Figure 1, the Fourier transform infrared spectroscopy figure peak of the Graphene processed without gallic acid aqueous solution
Shape is wider and peak value is more weak；And the Graphene after gallic acid aqueous solution (5mg/mL, 10mg/mL) processes is at 3430cm-1
And 1640cm-1Neighbouring there is stronger absworption peak, is belonging respectively to stretching vibration absworption peak and the bending vibration absworption peak of-O-H, its
The peak value of middle 10mg/mL is the strongest.The more functional group of graphenic surface grafting or gallic acid are by non-as can be seen here
Chemical action is adsorbed in graphenic surface, thus improves the dispersibility of Graphene.And continue to increase gallic acid aqueous solution
Concentration is to 20mg/mL, 3430cm-1And 1640cm-1Neighbouring absworption peak is substantially with the stone processed without gallic acid aqueous solution
Ink alkene, this is owing to the amount of the gallic acid of graphenic surface absorption exceedes its maxima solubility in water, thus to no food
π-π adsorption between son acid and Graphene produces very adverse influence, makes the gallic acid of graphenic surface occur de-
Attached, the phenomenon that modification amount reduces occurs, and then affects the dispersibility of Graphene.
According to embodiment 4, through the Graphene that 10mg/mL gallic acid aqueous solution processes, just at weight after standing five days
Increasingly generate under the effect of power and between precipitation, and Graphene, remain in that good dispersity, do not reunite, and warp
Graphene after 5mg/mL gallic acid aqueous solution processes generates precipitation, the most under gravity through 20mg/mL
After Graphene after the process of gallic acid aqueous solution stands 1 day, precipitating under gravity and gradually increase, Graphene gradually occurs
Slight agglomeration.Stone simultaneously according to FTIR spectrum figure, after 10mg/mL gallic acid aqueous solution processes
Ink alkene surface has more functional group, thus further increases the dispersibility of Graphene.To sum up, 20mg/mL and 5mg/mL
Comparing with 10mg/mL, obvious difference, achieve unforeseeable effect, therefore 10mg/mL is gallic acid aqueous solution of the present invention
Optium concentration.
Embodiment 5
The Graphene of the surface modification that Example 1 prepares；(2) by weight, agate ball and Achates spherical tank are used
By 0.5 part of Graphene, 3 parts of powdered graphites, 10 parts of Ti3SiC2Powder, 86.5 parts of copper powders carry out ball milling and mix powder, and rotating speed is 200
Turning/min, Ball-milling Time is 50min, makes powder mix homogeneously, obtains composite powder；(3) composite powder is carried out hot pressed sintering 2h,
The temperature of hot pressed sintering is 950 DEG C, pressure is 28MPa, furnace cooling, obtains cuprio composite block material；(4) block that will obtain
Body material carries out high temperature insostatic pressing (HIP) 2h, and HIP sintering temperature is 900 DEG C, pressure is 100MPa, rapid cooling, obtains Graphene and strengthens copper
Based composites.
Embodiment 6
The Graphene of the surface modification that Example 2 prepares；(2) by weight, agate ball and Achates spherical tank are used
By 1 part of Graphene, 5 parts of powdered graphites, 15 parts of Ti3SiC2Powder, 79 parts of copper powders carry out ball milling and mix powder, and rotating speed is 150 turns/
Min, Ball-milling Time is 60min, makes powder mix homogeneously, obtains composite powder；(3) composite powder is carried out hot pressed sintering 3h, heat
The temperature of pressure sintering is 900 DEG C, pressure is 40MPa, furnace cooling, obtains cuprio composite block material；(4) block that will obtain
Material carries out high temperature insostatic pressing (HIP) 2h, and HIP sintering temperature is 900 DEG C, pressure is 100MPa, rapid cooling, obtains Graphene and strengthens cuprio
Composite.
Embodiment 7
The Graphene of the surface modification that Example 1 prepares；(2) by weight, agate ball and Achates spherical tank are used
By 1.5 parts of Graphenes, 2 parts of powdered graphites, 6 parts of Ti3SiC2Powder, 90.5 parts of copper powders carry out ball milling and mix powder, and rotating speed is 200 turns/
Min, Ball-milling Time is 50min, makes powder mix homogeneously, obtains composite powder；(3) composite powder is carried out hot pressed sintering 2h, heat
The temperature of pressure sintering is 950 DEG C, pressure is 28MPa, furnace cooling, obtains cuprio composite block material；(4) block that will obtain
Material carries out high temperature insostatic pressing (HIP) 2h, and HIP sintering temperature is 900 DEG C, pressure is 100MPa, rapid cooling, obtains Graphene and strengthens cuprio
Composite.
Using scanning electron microscope (SEM) to characterize the Graphene enhancing Cu-base composites that embodiment 5-7 prepares, result is such as
Shown in Fig. 2.
3000 times of SEM figures of composite powder after ball mill mixing during (a) is embodiment 5 in Fig. 2, its left side is owing to ball milling is high
The mechanism generation cold weldings such as pressure and the copper particle cluster of diffusion, be attached on copper particle cluster receives for flake graphite alkene
Rice sheet.
During in Fig. 2, (b) is embodiment 6, after ball mill mixing, 10000 times of SEM of composite powder scheme, the stratiform of central, clear shape
Material is graphene nanometer sheet, embeds in copper particulate polymers.
The SEM figure of 10000 times of composite powder after ball mill mixing during (c) is embodiment 6 in Fig. 2, transparent sheet-like thing is
Graphene nanometer sheet, during graphene nanometer sheet embeds Copper substrate as can be seen from FIG., illustrates that mechanical milling process can promote matrix and increasing
Interface cohesion between strong phase.
10000 times of SEM figure of composite powder after ball mill mixing during (d) is embodiment 7 in Fig. 2, it can be seen that strengthen mutually some
Broken, it may be possible to the mechanism of ball milling causes, this reduces the size strengthening phase to a certain extent, is conducive to strengthening phase
Dispersed.Ball milling can change the shape of powder particle, and copper granule is the most mellow and the fullest, illustrates that ball milling cold welding effect is the poorest, in embodiment 5
～in 7, cold welding phenomenon is obvious between copper granule, it can be seen that few layer graphene is attached on copper granule, illustrate that compounding effect is overall
Well, the architectural feature of integral material is not impacted by the interpolation of graphene nanometer sheet simultaneously.
Fig. 3 is the EDS figure of (b) in Fig. 2.The unit detected have C, Cu, Ti, Si.White granular as seen from Figure 3
Ti3SiC2It is distributed in graphenic surface, illustrates that the ball milling method that embodiment 5～7 is used well disperses to make to strengthening to have mutually
With.
Use Archimedes method measures above-described embodiment and prepared by comparative example the density of Cu-base composites, consistency,
And measure its Brinell hardness, tensile strength and comprcssive strength, its result is as shown in table 1.
The experimental result of table 1 embodiment 5～7
As seen from the results in Table 1, the Cu-base composites that the Cu-base composites of embodiment 5 preparation is prepared with embodiment 6 and 7
Comparing, its micro-vickers hardness has been respectively increased 5.33HV, 7.6HV；Tensile strength be respectively increased 36.54MPa,
76.25MPa；Comprcssive strength has been respectively increased 21.94MPa, 32.71MPa.Therefore, the Cu-base composites phase of embodiment 5 preparation
The Cu-base composites prepared for embodiment 6 and embodiment 7, has more excellent hardness and resistance to impact, and embodiment 5 is
The preferred forms of Cu-base composites of the present invention.It follows that only when the composition percentage by weight of Cu-base composites
Than being calculated as Graphene 1～9%, powdered graphite 2～5%, Ti3SiC2Powder 6～15%, surplus is when being copper powders, can be only achieved this
Effect described in invention.
Test example
The fine copper (comparative example) that the Cu-base composites of testing example 5～7 preparation and same sintering process prepare,
Rub resistance under different Graphene content (%wt), different loads (F), rotating speed (r/min) three factor (I), polishing machine, its
Result is as shown in table 2.
The rub resistance of Cu-base composites prepared by table 2 embodiment 5-7, polishing machine
As shown in Table 2, the Cu-base composites of embodiment 5 preparation is in load 400N, the condition of velocity of rotation 150r/min
Under, wear extent is only 0.0263g, rubs and examines coefficient and be only 0.296；Under conditions of load 500, sliding speed 50r/min, abrasion
Amount also only has 0.0358g, rubs and examines coefficient and be only 0.329.It follows that Cu-base composites of the present invention not only has very
Good intensity and resistance to impact, have the rub resistance of excellence, polishing machine simultaneously.
Claims (10)
1. Graphene strengthens a Cu-base composites, including the following component of percentage by weight: surface-modified Graphene
0.5 ~ 5%, graphite 2 ~ 5%, Ti3SiC26 ~ 15%, surplus is copper；
Described surface-modified Graphene is the Graphene that gallic acid is modified.
Graphene the most according to claim 1 strengthens Cu-base composites, it is characterised in that: Cu-base composites is by weight
Percentage ratio includes following component: surface-modified Graphene 0.5 ~ 2%, powdered graphite 2 ~ 4%, Ti3SiC2Powder 8 ~ 12%, surplus
For copper powders.
Graphene the most according to claim 1 strengthens Cu-base composites, it is characterised in that described surface-modified stone
Ink alkene is made through following methods: is joined by Graphene in gallic acid aqueous solution, is uniformly dispersed, and stands, and filters, takes filtering residue and enter
Row vacuum drying, obtains the Graphene of surface modification.
Graphene the most according to claim 3 strengthens Cu-base composites, it is characterised in that: described gallic acid aqueous solution
Being prepared by deionized water, in gallic acid aqueous solution, the concentration of gallic acid is 3 ~ 18 mg/mL.
Graphene the most according to claim 3 strengthen Cu-base composites, it is characterised in that: the weight of described Graphene with
The ratio of the volume of gallic acid aqueous solution is 0.05 ~ 0.5g:20 ~ 60mL.
6. a preparation method for Cu-base composites, comprises the steps:
(1) Graphene is joined in gallic acid aqueous solution, is uniformly dispersed, stand, filter, take filtering residue and be vacuum dried,
Obtain the Graphene of surface modification；
(2) by the Graphene of surface modification and copper powders, powdered graphite, Ti3SiC2Powder carries out ball milling and mixes powder, obtains composite powder
End；
(3) composite powder is carried out hot pressed sintering, cool down, then hip treatment obtains Graphene and strengthens Cu-base composites.
The preparation method of Cu-base composites the most according to claim 6, it is characterised in that: ball milling in described step (2)
Using agate ball and Achates spherical tank, rotational speed of ball-mill is 150 ~ 300 turns/min, and Ball-milling Time is 40 ~ 60min.
The preparation method of Cu-base composites the most according to claim 6, it is characterised in that: ball milling in described step (2)
Employing medium is the tert-butyl alcohol.
The preparation method of Cu-base composites the most according to claim 6, it is characterised in that: described step (3) hot pressing is burnt
The temperature of knot is 900 ~ 1000 DEG C.
The preparation method of Cu-base composites the most according to claim 6, it is characterised in that: hot pressing in described step (3)
The pressure of sintering is 25 ~ 40MPa.
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| CN109112328A (en) * | 2017-06-26 | 2019-01-01 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene/copper alloy and its preparation and application |
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