CN105525124A - Preparation method for in-situ synthesis of three-dimensional graphene-reinforced copper-based composite material - Google Patents
Preparation method for in-situ synthesis of three-dimensional graphene-reinforced copper-based composite material Download PDFInfo
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Abstract
The invention relates to a preparation method for in-situ synthesis of a three-dimensional graphene-reinforced copper-based composite material. The preparation method comprises the following steps: taking copper nitrate trihydrate as a copper source, mixing the copper source with a solid carbon source (glucose or citric acid) and a water-soluble salt template (sodium chloride), then adding the mixture into water to dissolve the mixture, performing stirring uniformly to obtain a precursor solution; performing freeze-drying dehydration to obtain a mixed powder precursor; performing heating to 600-800 DEG C, performing heat preservation for 1-3 h, and then perform cooling quickly to obtain self-assembly powder; washing off sodium chloride by suction filtration, and performing vacuum drying; pouring the product into an ethanol solution of copper nitrate; performing water-bath evaporation drying and vacuum drying; under atmosphere protection, performing heating to 600-800 DEG C, performing heat preservation for 1-3 h, and obtaining three-dimensional graphene-copper particle composite powder by furnace cooling; and molding according to a vacuum hot-pressing sintering technology. The blocky material prepared according to the method has the characteristic that the graphene has good dispersity and is closely combined with a copper base; and meanwhile, the blocky material has excellent toughness and mechanical properties.
Description
Technical field
The present invention relates to a kind of fabricated in situ three-dimensional grapheme and strengthen Cu-base composites preparation method, belong to nano material preparation technology.
Background technology
Graphene, owing to having special monoatomic layer structure, has excellent tensile strength and Young's modulus, and be it is believed that it is the desirable nanometer activeness and quietness material of a class, the surface of its fold contributes to improving the bonding force between itself and basal body interface and contact area; The two-dirnentional structure of its uniqueness effectively can hinder the migration of dislocation and significantly reduce the expansion of matrix material fine cracks, thus has important using value in the composite.Cu-base composites is owing to having excellent mechanical property, and the functional performance such as high conductivity, thermal conductivity is widely used in electronic material, structured material field.Existing research report confirms, joined by Graphene in Copper substrate, effectively can play highly malleablized to improve the effect of mechanical property while not reducing high conductivity, thermal conductivity, development prospect is bright.
In the preparation method of block composite material, what current investigator mainly adopted is as the methods such as powder metallurgy mechanically mixing, stirring casting join Graphene in metallic matrix.Korea S S.H.Hong teach problem group proposes " molecular level mixing " and has prepared graphene/copper composite material in conjunction with the method for discharge plasma sintering.When the content of redox Graphene is 2.5vol.%, the yield strength of this matrix material reaches 335MPa, improves 80% than fine copper; The Cu-base composites that reed teach problem group has utilized the three-dimensional porous copper of China fir template synthesis-oxide impregnation Graphene-hydrogen reducing technology to prepare containing 1.2vol.% redox graphene reinforcement is opened by Shanghai Communications University, its yield strength reaches 233MPa, improve 120% than fine copper, tension set also exceedes fine copper matrix simultaneously; Existing research shows, Graphene improves hardness, intensity, the thermostability of metallic matrix, effectively reduces the hot expansibility etc. of body material.Theoretical according to mesomechanics, as Graphene effectively carries, the tensile strength of graphene/copper composite material should at more than 1000MPa, and Young's modulus should at more than 200GPa.But the maximum enhancing that the method for current existing report realizes is than only having 120%, visible, in existing powder compounding technology, the potentiality that Graphene strengthens not yet give full play to, Graphene strengthens the mechanical property of Cu-base composites far below theory expectation, major cause is: the Graphene adopted when (1) prepares matrix material is generally prepared by graphite oxide reduction method, the textural defect of this kind of redox Graphene is many, mechanical property and electrical and thermal conductivity poor, easily there is surface reaction in itself and Copper substrate compound tense, thus greatly have impact on mechanics and the physicals of matrix material, (2) there is very strong Van der Waals force between (comprising redox Graphene) in Graphene, very easily reunite and form graphite flake, thus be difficult to realize in Copper substrate dispersed, and the Graphene after serious agglomeration is by the same with common graphite flake, can lose the excellent properties such as the special mechanical property of Graphene, electroconductibility, structural stability.The dispersion of Graphene can be promoted to a certain extent by traditional high-energy mechanical ball milling method, but vigorous reactive force havoc in the mechanical milling process Structure and Properties of Graphene, cause strengthening effect to decline to a great extent.In sum, existing powder compounding technology can not meet three primary conditions that Graphene gives full play to strengthening effect simultaneously, namely structure intact, be uniformly dispersed, be combined well with basal body interface, become the bottleneck that restriction Graphene strengthens the development of copper based structures matrix material.Therefore, seeking new technology of preparing to overcome now methodical deficiency, is the key of development High-performance graphene copper metallic based structures matrix material.
Summary of the invention
The present invention aims to provide a kind of fabricated in situ three-dimensional grapheme and strengthens Cu-base composites preparation method, and the method process is simple, block materials obtained in this approach have graphene dispersion good, with the compact feature of Copper substrate; There is the tough excellent mechanical performance had both simultaneously.
The present invention is realized by following technical proposals,
A kind of fabricated in situ three-dimensional grapheme strengthens Cu-base composites preparation method, it is characterized in that comprising following process:
1. being copper source with Gerhardite, is 3:1 ~ 4:1 and solid carbon source glucose C by C and Cu elemental mole ratios
6h
12o
6or citric acid C
6h
8o
7, mix with water-soluble salt template sodium chloride nacl according to the elemental mole ratios 100:1 ~ 200:1 of Na and Cu, be that 1:3 ~ 1:5 adds in deionized water and dissolves according to the mass ratio of NaCl and water afterwards, magnetic agitation is even, obtains the precursor solution of transparent and homogeneous.
2. by step 1. in precursor solution freeze-drying and dehydrating after the drying solid powder that obtains, grinding obtains mixed powder presoma after sieving;
3. the composite powder presoma 2. step obtained, under atmosphere protection, temperature rise rate is that 2 ~ 10 DEG C/min is warming up to 600 ~ 800 DEG C, insulation 1 ~ 3h, fast cooling cooling afterwards, obtains the self-assembly powder of three-dimensional sodium-chlor-graphene-supported copper nano particles;
4. self-assembly powder step 3. obtained uses deionized water suction filtration to wash away sodium-chlor, obtains three-dimensional grapheme supported copper nano-particles reinforcement powdered material after vacuum-drying;
5. pour in the ethanolic soln of cupric nitrate by the powdered material that 4. step obtains, in cupric nitrate, in copper and powdered material, carbon mass ratio is 30:1 ~ 100:1, and magnetic agitation is even, more than supersound process half an hour; Be placed in 70 DEG C of water-baths and stir evaporate to dryness, and 80 DEG C of dryings obtain the coated three-dimensional grapheme composite powder material of basic copper nitrate in vacuum drying oven;
6. the powder that 5. step obtains is placed in Noah's ark, under atmosphere protection, under atmosphere protection, temperature rise rate is that 2 ~ 10 DEG C/min is warming up to 600 ~ 800 DEG C, insulation 1 ~ 3h, with stove cooling, obtains three-dimensional grapheme-copper Particles dispersed powder;
7. be placed in graphite jig by the step powdered material obtained 6., adopt vacuum hot pressing sintering technique shaping, sintering temperature is 600 ~ 1000 DEG C, sintered heat insulating time 0.2 ~ 1h, obtains three-dimensional grapheme and strengthens Cu-based bulk composite material.
The present invention has the following advantages: first the present invention uses solid carbon source chemical Vapor deposition process fabricated in situ three-dimensional grapheme supported copper nano particle, and the copper nano particles of graphenic surface to be conducive in follow-up dipping-calcining process as the forming core site of cupric nitrate and to be conducive to the interface cohesion of Graphene and Copper substrate; Three-dimensional grapheme structure is that stacking can not occur in copper recombination process reunites, and is conducive to the dispersed of Graphene; Meanwhile, the Graphene utilizing present method to obtain strengthens Cu-base composites and have excellent toughening effect while improving intensity.
Accompanying drawing explanation
The SEM photo of the three-dimensional grapheme supported copper powder of nanometric particles of Fig. 1 obtained by the embodiment of the present invention 1.
The SEM photo of the coated three-dimensional grapheme powder of the basic copper nitrate of Fig. 2 obtained by the embodiment of the present invention 1.
The SEM photo of the three-dimensional grapheme-copper composite powder of Fig. 3 obtained by the embodiment of the present invention 1.
The three-dimensional grapheme of Fig. 4 obtained by the embodiment of the present invention 1 strengthens copper block materials TEM photo.
Fig. 5 is three-dimensional grapheme Raman spectrogram in the material obtained in the embodiment of the present invention 1 different step.
The Graphene of Fig. 6 obtained by the embodiment of the present invention 1 strengthens the tensile property curve of copper block materials and fine copper;
The Graphene of Fig. 7 obtained by the embodiment of the present invention 2 strengthens the tensile property curve of copper block materials and fine copper;
Embodiment
First operational path of the present invention is described below, then further illustrates the present invention in conjunction with the embodiments.
Fabricated in situ three-dimensional grapheme strengthens Cu-base composites preparation method, it is characterized in that comprising following process:
1. be the Powdered Gerhardite (Cu (NO) of 1.0 ~ 5.0g with quality
33H
2o) being copper source, is 3:1 ~ 4:1 and solid carbon source glucose (C by C and Cu elemental mole ratios
6h
12o
6) or citric acid (C
6h
8o
7), mix with water-soluble salt template sodium-chlor (NaCl) according to the elemental mole ratios 100:1 ~ 200:1 of Na and Cu, be that 1:3 ~ 1:5 adds in deionized water and dissolves according to the mass ratio of NaCl and water afterwards, magnetic agitation is even, obtains the precursor solution of transparent and homogeneous.
2. by step 1. in mixing solutions be placed in freezing 12 ~ 24h under refrigerator-20 DEG C of conditions, obtain solid state biased sample, to be placed in freeze drier lyophilize 24 ~ 36h under-50 ~-10 DEG C of conditions, dehydration obtains drying solid powder, and grinding obtains mixed powder presoma after sieving;
3. the composite powder that 2. step obtains is placed in Noah's ark, under atmosphere protection, atmosphere is the one in hydrogen, nitrogen, argon gas or hydrogen+nitrogen, hydrogen+argon gas, gas flow rate is 50 ~ 200mL/min, temperature rise rate is that 2 ~ 10 DEG C/min is warming up to 600 ~ 800 DEG C, insulation 1 ~ 3h, fast cooling cooling (cooling rate average out to 50 ~ 100 DEG C/min), obtains the self-assembly powder of three-dimensional sodium-chlor-graphene-supported copper nano particles afterwards;
4. composite powder step 3. obtained uses deionized water suction filtration to wash away sodium-chlor, obtains three-dimensional grapheme supported copper nano-particles reinforcement powdered material after 80 DEG C of vacuum drying oven dryings;
5. pour in the ethanolic soln of cupric nitrate by the powdered material that 4. step obtains, in cupric nitrate, in copper and powdered material, carbon mass ratio is 30:1 ~ 100:1, and magnetic agitation is even, supersound process 30min; Be placed in 70 DEG C of water-baths and stir evaporate to dryness, and 80 DEG C of dryings obtain the coated three-dimensional grapheme composite powder material of basic copper nitrate in vacuum drying oven;
6. the powder that 5. step obtains is placed in Noah's ark, under atmosphere protection, atmosphere is the one in hydrogen, argon gas or hydrogen+nitrogen, hydrogen+argon gas, gas flow rate is 50 ~ 200mL/min, temperature rise rate is that 2 ~ 10 DEG C/min is warming up to 600 ~ 800 DEG C, insulation 1 ~ 3h, with stove cooling, obtains three-dimensional grapheme-copper Particles dispersed powder;
7. be placed in graphite jig by the step powdered material obtained 6., adopt vacuum hot pressing sintering technique shaping, sintering temperature is 600 ~ 1000 DEG C, vacuum tightness <10
-4pa, sintered heat insulating time 0.2 ~ 1h, obtain three-dimensional grapheme and strengthen Cu-based bulk composite material.
Embodiment 1
Take sodium-chlor 36.590g, glucose 0.938g, Gerhardite 2.265g is placed in beaker, weighs 121mL deionized water dissolving, magnetic agitation evenly (>6h) obtains settled solution, to be put in culture dish freezing 24h under freezer compartment of refrigerator-20 DEG C of conditions; Sample after freezing is put in freeze-drying in freeze drier, and lyophilisation condition is :-20 DEG C, freeze-drying time 24h.Sample grinding after freeze-drying is obtained presoma composite powder (powder diameter ~ 100 order); (temperature rise rate 10 DEG C/min under precursor powder being placed in tube furnace hydrogen atmosphere, holding temperature 750 DEG C, soaking time 2h, gas flow 100mL/min) calcining, room temperature (dropping to 100 DEG C in 5min) is quickly cooled to after insulation terminates, the composite powder that obtains is adopted suction filtration washing removing sodium-chlor template, and in vacuum drying oven, under 80 DEG C of conditions, be incubated 2h drying obtain three-dimensional grapheme supported copper powder of nanometric particles powder.Preparation Gerhardite (quality 36.405g) ethanolic soln 250mL, adds three-dimensional grapheme supported copper powder of nanometric particles 0.357g after magnetic agitation is even, and ultrasonic 30min, make it mix; In water-bath, 70 DEG C of condition decline ethanol stir evaporate to dryness afterwards, and 80 DEG C of dryings in vacuum drying oven, obtain three-dimensional grapheme/basic copper nitrate mixed powder after grinding; Afterwards by 30g three-dimensional grapheme/basic copper nitrate composite powder calcining reduction under 400 DEG C of hydrogen atmospheres in tube furnace, obtain three-dimensional grapheme/copper composite powder (Graphene content is 4.0vol.%); The three-dimensional grapheme of about 40g is placed in
in graphite jig, vacuum heating-press sintering parameter is temperature rise rate 10 DEG C/min, 800 DEG C of insulations 1h, vacuum tightness <10
-4mPa, obtains Graphene/copper billet composite material.Stretched performance test, the yield strength that the three-dimensional grapheme that the present embodiment obtains strengthens Cu-base composites is 197MPa, and comparatively fine copper improves 70%; Tensile strength 264MPa, comparatively fine copper improves 20%; Young's modulus 96GPa, comparatively fine copper improves 74%; The fine copper sample that tension set is also prepared compared with same procedure is high.
Embodiment 2
Take sodium-chlor 36.590g, glucose 0.938g, Gerhardite 2.265g is placed in beaker, weighs 121mL deionized water dissolving, magnetic agitation evenly (>6h) obtains settled solution, to be put in culture dish freezing 24h under freezer compartment of refrigerator-20 DEG C of conditions; Sample after freezing is put in freeze-drying in freeze drier, and lyophilisation condition is :-20 DEG C, freeze-drying time 24h.Sample grinding after freeze-drying is obtained presoma composite powder (powder diameter ~ 100 order); (temperature rise rate 10 DEG C/min under precursor powder being placed in tube furnace hydrogen atmosphere, holding temperature 750 DEG C, soaking time 2h, gas flow 100mL/min) calcining, room temperature (dropping to 100 DEG C in 5min) is quickly cooled to after insulation terminates, the composite powder that obtains is adopted suction filtration washing removing sodium-chlor template, and in vacuum drying oven, under 80 DEG C of conditions, be incubated 2h drying obtain three-dimensional grapheme supported copper powder of nanometric particles powder.Preparation Gerhardite (quality 37.088g) ethanolic soln 250mL, adds three-dimensional grapheme supported copper powder of nanometric particles 0.176g after magnetic agitation is even, and ultrasonic 30min, make it mix; In water-bath, 70 DEG C of condition decline ethanol stir evaporate to dryness afterwards, and 80 DEG C of dryings in vacuum drying oven, obtain three-dimensional grapheme/basic copper nitrate mixed powder after grinding; Afterwards by 30g three-dimensional grapheme/basic copper nitrate composite powder calcining reduction under 400 DEG C of hydrogen atmospheres in tube furnace, obtain three-dimensional grapheme/copper composite powder (Graphene content is 2.0vol.%); Three-dimensional grapheme/the copper composite powder of about 40g is placed in
in graphite jig, vacuum heating-press sintering parameter is temperature rise rate 10 DEG C/min, 800 DEG C of insulations 1h, vacuum tightness <10-
4mPa, obtains Graphene/copper billet composite material.The yield strength that the three-dimensional grapheme that the present embodiment obtains strengthens Cu-base composites is 285MPa, and comparatively fine copper improves 145%; Tensile strength 298MPa, comparatively fine copper improves 36%; Young's modulus 97GPa, comparatively fine copper improves 76%.
Embodiment 3
Take sodium-chlor 36.590g, glucose 0.938g, Gerhardite 2.265g is placed in beaker, weighs 121mL deionized water dissolving, magnetic agitation evenly (>6h) obtains settled solution, to be put in culture dish freezing 24h under freezer compartment of refrigerator-20 DEG C of conditions; Sample after freezing is put in freeze-drying in freeze drier, and lyophilisation condition is :-20 DEG C, freeze-drying time 24h.Sample grinding after freeze-drying is obtained presoma composite powder (powder diameter ~ 100 order); (temperature rise rate 10 DEG C/min under precursor powder being placed in tube furnace hydrogen atmosphere, holding temperature 750 DEG C, soaking time 2h, gas flow 100mL/min) calcining, room temperature (dropping to 100 DEG C in 5min) is quickly cooled to after insulation terminates, the composite powder that obtains is adopted suction filtration washing removing sodium-chlor template, and in vacuum drying oven, under 80 DEG C of conditions, be incubated 2h drying obtain three-dimensional grapheme supported copper powder of nanometric particles powder.Preparation Gerhardite (quality 37.422g) ethanolic soln 250mL, adds three-dimensional grapheme supported copper powder of nanometric particles 0.088g after magnetic agitation is even, and ultrasonic 30min, make it mix; In water-bath, 70 DEG C of condition decline ethanol stir evaporate to dryness afterwards, and 80 DEG C of dryings in vacuum drying oven, obtain three-dimensional grapheme/basic copper nitrate mixed powder after grinding; Afterwards by 30g three-dimensional grapheme/basic copper nitrate composite powder calcining reduction under 400 DEG C of hydrogen atmospheres in tube furnace, obtain three-dimensional grapheme/copper composite powder (Graphene content is 1.0vol.%); Three-dimensional grapheme/the copper composite powder of about 40g is placed in
in graphite jig, vacuum heating-press sintering parameter is temperature rise rate 10 DEG C/min, 800 DEG C of insulations 1h, vacuum tightness <10
-4mPa, obtains Graphene/copper billet composite material.The yield strength that the three-dimensional grapheme that the present embodiment obtains strengthens Cu-base composites is 243MPa, and comparatively fine copper improves 110%; Tensile strength 219MPa, comparatively fine copper improves 26%; Young's modulus 112GPa, comparatively fine copper improves 104%.
Embodiment 4
Take sodium-chlor 36.590g, glucose 0.938g, Gerhardite 2.265g is placed in beaker, weighs 121mL deionized water dissolving, magnetic agitation evenly (>6h) obtains settled solution, to be put in culture dish freezing 24h under freezer compartment of refrigerator-20 DEG C of conditions; Sample after freezing is put in freeze-drying in freeze drier, and lyophilisation condition is :-20 DEG C, freeze-drying time 24h.Sample grinding after freeze-drying is obtained presoma composite powder (powder diameter ~ 100 order); (temperature rise rate 10 DEG C/min under precursor powder being placed in tube furnace hydrogen atmosphere, holding temperature 750 DEG C, soaking time 2h, gas flow 100mL/min) calcining, room temperature (dropping to 100 DEG C in 5min) is quickly cooled to after insulation terminates, the composite powder that obtains is adopted suction filtration washing removing sodium-chlor template, and in vacuum drying oven, under 80 DEG C of conditions, be incubated 2h drying obtain three-dimensional grapheme supported copper powder of nanometric particles powder.Preparation Gerhardite (quality 36.405g) ethanolic soln 250mL, adds three-dimensional grapheme supported copper powder of nanometric particles 0.357g after magnetic agitation is even, and ultrasonic 30min, make it mix; In water-bath, 70 DEG C of condition decline ethanol stir evaporate to dryness afterwards, and 80 DEG C of dryings in vacuum drying oven, obtain three-dimensional grapheme/basic copper nitrate mixed powder after grinding; Afterwards by 30g three-dimensional grapheme/basic copper nitrate composite powder calcining reduction under 400 DEG C of hydrogen atmospheres in tube furnace, obtain three-dimensional grapheme/copper composite powder (Graphene content is 4.0vol.%); Three-dimensional grapheme/the copper composite powder of about 40g is placed in
in graphite jig, vacuum heating-press sintering parameter is temperature rise rate 10 DEG C/min, 600 DEG C of insulations 1h, vacuum tightness <10
-4mPa, obtains Graphene/copper billet composite material.
Embodiment 5
Take sodium-chlor 36.590g, glucose 0.938g, Gerhardite 2.265g is placed in beaker, weighs 121mL deionized water dissolving, magnetic agitation evenly (>6h) obtains settled solution, to be put in culture dish freezing 24h under freezer compartment of refrigerator-20 DEG C of conditions; Sample after freezing is put in freeze-drying in freeze drier, and lyophilisation condition is :-20 DEG C, freeze-drying time 24h.Sample grinding after freeze-drying is obtained presoma composite powder (powder diameter ~ 100 order); (temperature rise rate 10 DEG C/min under precursor powder being placed in tube furnace hydrogen atmosphere, holding temperature 750 DEG C, soaking time 2h, gas flow 100mL/min) calcining, room temperature (dropping to 100 DEG C in 5min) is quickly cooled to after insulation terminates, the composite powder that obtains is adopted suction filtration washing removing sodium-chlor template, and in vacuum drying oven, under 80 DEG C of conditions, be incubated 2h drying obtain three-dimensional grapheme supported copper powder of nanometric particles powder.Preparation Gerhardite (quality 36.405g) ethanolic soln 250mL, adds three-dimensional grapheme supported copper powder of nanometric particles 0.357g after magnetic agitation is even, and ultrasonic 30min, make it mix; In water-bath, 70 DEG C of condition decline ethanol stir evaporate to dryness afterwards, and 80 DEG C of dryings in vacuum drying oven, obtain three-dimensional grapheme/basic copper nitrate mixed powder after grinding; Afterwards by 30g three-dimensional grapheme/basic copper nitrate composite powder calcining reduction under 400 DEG C of hydrogen atmospheres in tube furnace, obtain three-dimensional grapheme/copper composite powder (Graphene content is 4.0vol.%); Three-dimensional grapheme/the copper composite powder of about 40g is placed in
in graphite jig, vacuum heating-press sintering parameter is temperature rise rate 10 DEG C/min, 700 DEG C of insulations 1h, vacuum tightness <10
-4mPa, obtains Graphene/copper billet composite material.
Embodiment 6
Take sodium-chlor 36.590g, citric acid 1.000g, Gerhardite 2.265g is placed in beaker, weighs 121mL deionized water dissolving, magnetic agitation evenly (>6h) obtains settled solution, to be put in culture dish freezing 24h under freezer compartment of refrigerator-20 DEG C of conditions; Sample after freezing is put in freeze-drying in freeze drier, and lyophilisation condition is-20 DEG C, freeze-drying time 24h.Sample grinding after freeze-drying is obtained presoma composite powder (powder diameter ~ 100 order); (temperature rise rate 10 DEG C/min under precursor powder being placed in tube furnace hydrogen atmosphere, holding temperature 750 DEG C, soaking time 2h, gas flow 100mL/min) calcining, room temperature (dropping to 100 DEG C in 5min) is quickly cooled to after insulation terminates, the composite powder that obtains is adopted suction filtration washing removing sodium-chlor template, and in vacuum drying oven, under 80 DEG C of conditions, be incubated 2h drying obtain three-dimensional grapheme supported copper powder of nanometric particles powder.Preparation Gerhardite (quality 36.405g) ethanolic soln 250mL, adds three-dimensional grapheme supported copper powder of nanometric particles 0.357g after magnetic agitation is even, and ultrasonic 30min, make it mix; In water-bath, 70 DEG C of condition decline ethanol stir evaporate to dryness afterwards, and 80 DEG C of dryings in vacuum drying oven, obtain three-dimensional grapheme/basic copper nitrate mixed powder after grinding; Afterwards by 30g three-dimensional grapheme/basic copper nitrate composite powder calcining reduction under 300 DEG C of hydrogen atmospheres in tube furnace, obtain three-dimensional grapheme/copper composite powder (Graphene content is 4.0vol.%); Three-dimensional grapheme/the copper composite powder of about 40g is placed in
in graphite jig, vacuum heating-press sintering parameter is temperature rise rate 10 DEG C/min, 800 DEG C of insulations 1h, vacuum tightness <10
-4mPa, obtains Graphene/copper billet composite material.
Claims (2)
1. fabricated in situ three-dimensional grapheme strengthens a Cu-base composites preparation method, it is characterized in that comprising following process:
1. being copper source with Gerhardite, is 3:1 ~ 4:1 and solid carbon source glucose C by C and Cu elemental mole ratios
6h
12o
6or citric acid C
6h
8o
7, mix with water-soluble salt template sodium chloride nacl according to the elemental mole ratios 100:1 ~ 200:1 of Na and Cu, be that 1:3 ~ 1:5 adds in deionized water and dissolves according to the mass ratio of NaCl and water afterwards, magnetic agitation is even, obtains the precursor solution of transparent and homogeneous.
2. by step 1. in precursor solution freeze-drying and dehydrating after the drying solid powder that obtains, grinding obtains mixed powder presoma after sieving;
3. the composite powder presoma 2. step obtained, under atmosphere protection, temperature rise rate is that 2 ~ 10 DEG C/min is warming up to 600 ~ 800 DEG C, insulation 1 ~ 3h, fast cooling cooling afterwards, obtains the self-assembly powder of three-dimensional sodium-chlor-graphene-supported copper nano particles;
4. self-assembly powder step 3. obtained uses deionized water suction filtration to wash away sodium-chlor, obtains three-dimensional grapheme supported copper nano-particles reinforcement powdered material after vacuum-drying;
5. pour in the ethanolic soln of cupric nitrate by the powdered material that 4. step obtains, in cupric nitrate, in copper and powdered material, carbon mass ratio is 30:1 ~ 100:1, and magnetic agitation is even, more than supersound process half an hour; Be placed in 70 DEG C of water-baths and stir evaporate to dryness, and 80 DEG C of dryings obtain the coated three-dimensional grapheme composite powder material of basic copper nitrate in vacuum drying oven;
6. the powder that 5. step obtains is placed in Noah's ark, under atmosphere protection, temperature rise rate is that 2 ~ 10 DEG C/min is warming up to 600 ~ 800 DEG C, insulation 1 ~ 3h, with stove cooling, obtains three-dimensional grapheme-copper Particles dispersed powder;
7. be placed in graphite jig by the step powdered material obtained 6., adopt vacuum hot pressing sintering technique shaping, sintering temperature is 600 ~ 1000 DEG C, sintered heat insulating time 0.2 ~ 1h, obtains three-dimensional grapheme and strengthens Cu-based bulk composite material.
2. preparation method according to claim 1, is characterized in that, step 3. with the one that step atmosphere is 4. in hydrogen, nitrogen, argon gas or hydrogen+nitrogen, hydrogen+argon gas, gas flow rate is 50 ~ 200mL/min.
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