CN105525124B - Fabricated in situ three-dimensional grapheme strengthens Cu-base composites preparation method - Google Patents
Fabricated in situ three-dimensional grapheme strengthens Cu-base composites preparation method Download PDFInfo
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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
- C22C1/10—Alloys containing non-metals
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F2003/145—Both compacting and sintering simultaneously by warm compacting, below debindering temperature
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Abstract
The present invention relates to a kind of fabricated in situ three-dimensional grapheme enhancing Cu-base composites preparation method, including：Mixed with water soluble salt template sodium chloride as copper source with solid carbon source glucose or citric acid with Gerhardite, dissolving in deionized water is added afterwards, stirred, obtain precursor solution；Freeze-drying and dehydrating obtains mixed-powder presoma；600~800 DEG C are warming up to, 1~3h is incubated, fast cooling cooling, obtains self-assembly powder afterwards；Suction filtration washes away sodium chloride, vacuum drying；Pour into the ethanol solution of copper nitrate；Water bath method, and in vacuum drying；Under atmosphere protection, 600~800 DEG C are warming up to, are incubated 1~3h, lowered the temperature with stove, obtain three-dimensional grapheme copper Particles dispersed powder；Vacuum hot pressing sintering technique is molded.The characteristics of block materials obtained by the present invention have graphene dispersion good and Copper substrate is tightly combined；There is the tough excellent mechanical performance having both simultaneously.
Description
Technical field
The present invention relates to a kind of fabricated in situ three-dimensional grapheme enhancing Cu-base composites preparation method, belong to nano material
Technology of preparing.
Background technology
Graphene due to special monoatomic layer structure, with excellent tensile strength and elastic modelling quantity, by people
It is considered the preferable nanometer activeness and quietness material of a class, the surface of its fold is favorably improved its adhesion between basal body interface
And contact area；Its unique two-dimensional structure can effectively hinder the migration of dislocation and substantially reduce the expansion of composite fine cracks
Exhibition, thus there is important application value in the composite.Cu-base composites are because with excellent mechanical property, height is led
Electrically, the functional characteristic such as thermal conductivity is widely used in electronic material, structural material field.Existing research report card
It is real, Graphene is added in Copper substrate, can be effectively acted as while high conductivity, thermal conductivity is not reduced Strengthening and Toughening with
The effect of mechanical property is improved, development prospect is bright.
In terms of the preparation method of block composite material, current researcher is mainly used as powder metallurgy machinery is mixed
The methods such as conjunction, stirring casting are added to Graphene in metallic matrix.South Korea S.H.Hong professors seminar proposes that " molecular level is mixed
Conjunction " is prepared for graphene/copper composite material with reference to the method for discharge plasma sintering.When the content of redox Graphene is
During 2.5vol.%, the yield strength of the composite has reached 335MPa, and 80% is improved than fine copper；Shanghai Communications University Zhang Di
Professor seminar using China fir template prepare three-dimensional porous copper-oxide impregnation Graphene-hydrogen reducing technology be prepared for containing
The Cu-base composites of 1.2vol.% redox graphene reinforcements, its yield strength has reached 233MPa, is improved than fine copper
120%, while fracture elongation is also above fine copper matrix；Existing research shows that Graphene improves the hard of metallic matrix
Degree, intensity, heat endurance, effectively reduce hot expansibility of matrix material etc..Theoretical according to mesomechanics, such as Graphene has
Effect is carried, and the tensile strength of graphene/copper composite material should be in more than 1000MPa, and elastic modelling quantity should be in more than 200GPa.But mesh
The maximum enhancing ratio only 120% that the method for preceding existing report is realized, it is seen then that in existing powder complex technique, stone
The enhanced potentiality of black alkene not yet give full play to, and the mechanical property of Graphene enhancing Cu-base composites is far below theory expectation, main
Wanting reason is：(1) prepare what the Graphene used during composite was prepared generally by graphite oxide reducing process, this kind of oxidation
The fault of construction of reduced graphene is more, and mechanical performance is poor with electrical and thermal conductivity, and it is anti-that it is susceptible to interface with Copper substrate compound tense
Should, so as to leverage the mechanics and physical property of composite；(2) deposited between Graphene (including redox Graphene)
In very strong Van der Waals force, graphite flake is easily agglomerated into, thus be difficult to be realized in Copper substrate dispersed, and serious agglomeration
Graphene afterwards as common graphite flake, will can lose the special mechanical performance of Graphene, electric conductivity, structural stability etc.
Excellent properties.The dispersion of Graphene can be promoted to a certain extent by traditional high-energy mechanical ball milling method, but in mechanical milling process
The vigorous active force heavy damage structure and performance of Graphene, causes reinforcing effect to decline to a great extent.In sum, it is existing
Powder complex technique can not meet simultaneously three primary conditions that Graphene gives full play to invigoration effect, i.e. structure it is intact, point
Dissipate uniform and basal body interface to be well combined, the bottleneck of copper-based structural composite material development is strengthened as restriction Graphene.Therefore,
Seek new technology of preparing to overcome the shortcomings of existing method, be development High-performance graphene copper metal based structures composite
It is crucial.
The content of the invention
The present invention is intended to provide a kind of fabricated in situ three-dimensional grapheme enhancing Cu-base composites preparation method, the method mistake
Journey is simple, and obtained block materials have graphene dispersion good and the characteristics of Copper substrate is tightly combined in this approach；Simultaneously
With the tough excellent mechanical performance having both.
The present invention is realized by the following technical scheme,
A kind of fabricated in situ three-dimensional grapheme strengthens Cu-base composites preparation method, it is characterised in that including following mistake
Journey：
1. it is copper source with Gerhardite, is 3 by C and Cu elemental mole ratios:1~4:1 with solid carbon source glucose
C6H12O6Or citric acid C6H8O7, according to the elemental mole ratios 100 of Na and Cu:1~200:1 with water soluble salt template sodium chloride
NaCl mixes, and is afterwards 1 according to the mass ratio of NaCl and water:3~1:5 add dissolving in deionized water, and magnetic agitation is uniform, obtains
To 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, after grinding sieving
To mixed-powder presoma；
3. the composite powder presoma for 2. step being obtained, under atmosphere protection, heating rate heats up for 2~10 DEG C/min
To 600~800 DEG C, 1~3h is incubated, fast cooling cooling, obtains three-dimensional sodium chloride-graphene-supported copper nano particles afterwards
Self-assembly powder；
4. the self-assembly powder for 3. step being obtained washes away sodium chloride using deionized water suction filtration, is obtained after vacuum drying
Three-dimensional grapheme supported copper nano-particles reinforcement dusty material；
5. the dusty material that 4. step obtains is poured into the ethanol solution of copper nitrate, copper and powder material in copper nitrate
Carbon mass ratio is 30 in material:1~100:1, magnetic agitation is uniform, more than ultrasonically treated half an hour；It is placed in 70 DEG C of water-baths
Interior stirring is evaporated, and in vacuum drying chamber 80 DEG C be dried to obtain basic copper nitrate cladding three-dimensional grapheme composite powder material；
6. the powder that 5. step obtains is placed in Noah's ark, under atmosphere protection, under atmosphere protection, heating rate is 2
~10 DEG C/min is warming up to 600~800 DEG C, is incubated 1~3h, lowers the temperature with stove, obtains three-dimensional grapheme-copper Particles dispersed powder；
7. the dusty material for obtaining by step 6. is placed in graphite jig, is molded using vacuum hot pressing sintering technique, is burnt
Junction temperature is 600~1000 DEG C, 0.2~1h of sintered heat insulating time, and obtaining three-dimensional grapheme strengthens copper-based block composite material.
The present invention has advantages below：The present invention is first by solid carbon source chemical vapour deposition technique fabricated in situ three-dimensional stone
Black alkene loads copper nano particles, and the copper nano particles of graphenic surface are conducive in follow-up dipping-calcine technology as nitric acid
The forming core site of copper is simultaneously conducive to the interface cohesion of Graphene and Copper substrate；Three-dimensional grapheme structure be in copper recombination process not
Stacking reunion can occur, be conducive to the dispersed of Graphene；Meanwhile, the Graphene enhancing obtained using this method is copper-based compound
Material has excellent toughening effect while intensity is improved.
Brief description of the drawings
Fig. 1 is the SEM photograph of the three-dimensional grapheme supported copper powder of nanometric particles obtained by the embodiment of the present invention 1.
Fig. 2 is the SEM photograph of the basic copper nitrate cladding three-dimensional grapheme powder obtained by the embodiment of the present invention 1.
Fig. 3 is the SEM photograph of the three-dimensional grapheme-copper composite powder obtained by the embodiment of the present invention 1.
Fig. 4 is the three-dimensional grapheme enhancing copper block materials TEM photos obtained by the embodiment of the present invention 1.
Fig. 5 is three-dimensional grapheme Raman spectrograms in the material that obtains in the different step of the embodiment of the present invention 1.
Fig. 6 is the tensile property curve of the Graphene enhancing copper block materials obtained by the embodiment of the present invention 1 and fine copper；
Fig. 7 is the tensile property curve of the Graphene enhancing copper block materials obtained by the embodiment of the present invention 2 and fine copper；
Specific embodiment
Process route of the invention is illustrated first below, and the present invention is further illustrated then in conjunction with embodiment.
Fabricated in situ three-dimensional grapheme strengthens Cu-base composites preparation method, it is characterised in that including procedure below：
1. with powdered Gerhardite (Cu (NO) that quality is 1.0~5.0g3·3H2O it is) copper source, by C and Cu units
Plain mol ratio is 3:1~4:1 and solid carbon source glucose (C6H12O6) or citric acid (C6H8O7), rubbed according to the element of Na and Cu
You compare 100:1~200:1 mixes with water soluble salt template sodium chloride (NaCl), is afterwards 1 according to the mass ratio of NaCl and water:3
~1:5 add dissolving in deionized water, and magnetic agitation is uniform, obtains the precursor solution of transparent and homogeneous.
2. by step 1. in mixed solution be placed in refrigerator under the conditions of -20 DEG C 12~24h of freezing, obtain solid-like mixing
Sample, be placed in afterwards -50 in freeze drier~-10 DEG C under the conditions of 24~36h of freeze-drying, dehydration obtains drying solid powder
End, mixed-powder presoma is obtained after grinding sieving；
3. the composite powder that 2. step obtains is placed in Noah's ark, under atmosphere protection, atmosphere is hydrogen, nitrogen, argon gas
Or the one kind in hydrogen+nitrogen, hydrogen+argon gas, gas flow rate is 50~200mL/min, and heating rate is 2~10 DEG C/min liters
Temperature is incubated 1~3h to 600~800 DEG C, and fast cooling cooling (50~100 DEG C/min of cooling rate average out to), obtains three afterwards
Tie up the self-assembly powder of sodium chloride-graphene-supported copper nano particles；
4. the composite powder for 3. step being obtained washes away sodium chloride using deionized water suction filtration, and 80 DEG C of vacuum drying chambers are dried
After obtain three-dimensional grapheme supported copper nano-particles reinforcement dusty material；
5. the dusty material that 4. step obtains is poured into the ethanol solution of copper nitrate, copper and powder material in copper nitrate
Carbon mass ratio is 30 in material:1~100:1, magnetic agitation is uniform, ultrasonically treated 30min；It is placed in stirring in 70 DEG C of water-baths
Be evaporated, and in vacuum drying chamber 80 DEG C be dried to obtain basic copper nitrate cladding three-dimensional grapheme composite powder material；
6. the powder that 5. step obtains is placed in Noah's ark, under atmosphere protection, atmosphere is hydrogen, argon gas or hydrogen+nitrogen
One kind in gas, hydrogen+argon gas, gas flow rate is 50~200mL/min, heating rate is warming up to 600 for 2~10 DEG C/min~
800 DEG C, 1~3h is incubated, lowered the temperature with stove, obtain three-dimensional grapheme-copper Particles dispersed powder；
7. the dusty material for obtaining by step 6. is placed in graphite jig, is molded using vacuum hot pressing sintering technique, is burnt
Junction temperature is 600~1000 DEG C, vacuum<10-4Pa, 0.2~1h of sintered heat insulating time, obtain three-dimensional grapheme enhancing Cu-based bulk
Composite material.
Embodiment 1
Sodium chloride 36.590g is weighed, glucose 0.938g, Gerhardite 2.265g is placed in beaker, weigh 121mL
Deionized water dissolving, magnetic agitation it is uniform (>Settled solution 6h) is obtained, is put in culture dish in -20 DEG C of conditions of freezer compartment of refrigerator
Lower freezing 24h；Sample after freezing is put in freeze drier and is freezed, lyophilisation condition is：- 20 DEG C, freeze-drying time 24h.Will
Sample grinding after lyophilized obtains presoma composite powder (powder diameter~100 mesh)；Precursor powder is placed in tube furnace
(10 DEG C/min of heating rate, 750 DEG C of holding temperature, soaking time 2h, gas flow 100mL/min) calcining under hydrogen atmosphere,
Insulation is quickly cooled to room temperature (100 DEG C are dropped in 5min) after terminating, the composite powder that will be obtained removes dechlorination using suction filtration washing
Change sodium template, and 2h is incubated under the conditions of 80 DEG C in vacuum drying chamber and be dried to obtain three-dimensional grapheme supported copper powder of nanometric particles
Powder.Gerhardite (quality 36.405g) ethanol solution 250mL is prepared, magnetic agitation uniformly adds three-dimensional grapheme afterwards
Supported copper powder of nanometric particles 0.357g, and ultrasound 30min, are well mixed it；Decline after 70 DEG C of conditions in water-bath
Ethanol stirring is evaporated, and 80 DEG C of dryings in vacuum drying chamber, and three-dimensional grapheme/basic copper nitrate mixed powder is obtained after grinding
End；Afterwards by 30g three-dimensional graphemes/basic copper nitrate composite powder in tube furnace calcining reduction under 400 DEG C of hydrogen atmospheres, obtain
To three-dimensional grapheme/copper composite powder (Graphene content is 4.0vol.%)；The three-dimensional grapheme of 40g or so is placed inStone
In black mould, vacuum heating-press sintering parameter is 10 DEG C/min of heating rate, 800 DEG C of insulation 1h, vacuum<10-4MPa, obtains stone
Black alkene/copper billet composite material.Stretched performance test, the three-dimensional grapheme enhancing Cu-base composites that the present embodiment is obtained
Yield strength be 197MPa, compared with fine copper improve 70%；Tensile strength 264MPa, 20% is improved compared with fine copper；Young's modulus
96GPa, 74% is improved compared with fine copper；Fracture elongation is also high compared with fine copper sample prepared by same procedure.
Embodiment 2
Sodium chloride 36.590g is weighed, glucose 0.938g, Gerhardite 2.265g is placed in beaker, weigh 121mL
Deionized water dissolving, magnetic agitation it is uniform (>Settled solution 6h) is obtained, is put in culture dish in -20 DEG C of conditions of freezer compartment of refrigerator
Lower freezing 24h；Sample after freezing is put in freeze drier and is freezed, lyophilisation condition is：- 20 DEG C, freeze-drying time 24h.Will
Sample grinding after lyophilized obtains presoma composite powder (powder diameter~100 mesh)；Precursor powder is placed in tube furnace
(10 DEG C/min of heating rate, 750 DEG C of holding temperature, soaking time 2h, gas flow 100mL/min) calcining under hydrogen atmosphere,
Insulation is quickly cooled to room temperature (100 DEG C are dropped in 5min) after terminating, the composite powder that will be obtained removes dechlorination using suction filtration washing
Change sodium template, and 2h is incubated under the conditions of 80 DEG C in vacuum drying chamber and be dried to obtain three-dimensional grapheme supported copper powder of nanometric particles
Powder.Gerhardite (quality 37.088g) ethanol solution 250mL is prepared, magnetic agitation uniformly adds three-dimensional grapheme afterwards
Supported copper powder of nanometric particles 0.176g, and ultrasound 30min, are well mixed it；Decline after 70 DEG C of conditions in water-bath
Ethanol stirring is evaporated, and 80 DEG C of dryings in vacuum drying chamber, and three-dimensional grapheme/basic copper nitrate mixed powder is obtained after grinding
End；Afterwards by 30g three-dimensional graphemes/basic copper nitrate composite powder in tube furnace calcining reduction under 400 DEG C of hydrogen atmospheres, obtain
To three-dimensional grapheme/copper composite powder (Graphene content is 2.0vol.%)；By the three-dimensional grapheme/copper composite powder of 40g or so
End is placed inIn graphite jig, vacuum heating-press sintering parameter is 10 DEG C/min of heating rate, 800 DEG C of insulation 1h, vacuum<10
-4MPa, obtains Graphene/copper billet composite material.The three-dimensional grapheme that the present embodiment is obtained strengthens bending for Cu-base composites
Intensity is taken for 285MPa, 145% is improved compared with fine copper；Tensile strength 298MPa, 36% is improved compared with fine copper；Young's modulus 97GPa, compared with
Fine copper improves 76%.
Embodiment 3
Sodium chloride 36.590g is weighed, glucose 0.938g, Gerhardite 2.265g is placed in beaker, weigh 121mL
Deionized water dissolving, magnetic agitation it is uniform (>Settled solution 6h) is obtained, is put in culture dish in -20 DEG C of conditions of freezer compartment of refrigerator
Lower freezing 24h；Sample after freezing is put in freeze drier and is freezed, lyophilisation condition is：- 20 DEG C, freeze-drying time 24h.Will
Sample grinding after lyophilized obtains presoma composite powder (powder diameter~100 mesh)；Precursor powder is placed in tube furnace
(10 DEG C/min of heating rate, 750 DEG C of holding temperature, soaking time 2h, gas flow 100mL/min) calcining under hydrogen atmosphere,
Insulation is quickly cooled to room temperature (100 DEG C are dropped in 5min) after terminating, the composite powder that will be obtained removes dechlorination using suction filtration washing
Change sodium template, and 2h is incubated under the conditions of 80 DEG C in vacuum drying chamber and be dried to obtain three-dimensional grapheme supported copper powder of nanometric particles
Powder.Gerhardite (quality 37.422g) ethanol solution 250mL is prepared, magnetic agitation uniformly adds three-dimensional grapheme afterwards
Supported copper powder of nanometric particles 0.088g, and ultrasound 30min, are well mixed it；Decline after 70 DEG C of conditions in water-bath
Ethanol stirring is evaporated, and 80 DEG C of dryings in vacuum drying chamber, and three-dimensional grapheme/basic copper nitrate mixed powder is obtained after grinding
End；Afterwards by 30g three-dimensional graphemes/basic copper nitrate composite powder in tube furnace calcining reduction under 400 DEG C of hydrogen atmospheres, obtain
To three-dimensional grapheme/copper composite powder (Graphene content is 1.0vol.%)；By the three-dimensional grapheme/copper composite powder of 40g or so
End is placed inIn graphite jig, vacuum heating-press sintering parameter is 10 DEG C/min of heating rate, 800 DEG C of insulation 1h, vacuum<10- 4MPa, obtains Graphene/copper billet composite material.The three-dimensional grapheme that the present embodiment is obtained strengthens the surrender of Cu-base composites
Intensity is 243MPa, and 110% is improved compared with fine copper；Tensile strength 219MPa, 26% is improved compared with fine copper；Young's modulus 112GPa, compared with
Fine copper improves 104%.
Embodiment 4
Sodium chloride 36.590g is weighed, glucose 0.938g, Gerhardite 2.265g is placed in beaker, weigh 121mL
Deionized water dissolving, magnetic agitation it is uniform (>Settled solution 6h) is obtained, is put in culture dish in -20 DEG C of conditions of freezer compartment of refrigerator
Lower freezing 24h；Sample after freezing is put in freeze drier and is freezed, lyophilisation condition is：- 20 DEG C, freeze-drying time 24h.Will
Sample grinding after lyophilized obtains presoma composite powder (powder diameter~100 mesh)；Precursor powder is placed in tube furnace
(10 DEG C/min of heating rate, 750 DEG C of holding temperature, soaking time 2h, gas flow 100mL/min) calcining under hydrogen atmosphere,
Insulation is quickly cooled to room temperature (100 DEG C are dropped in 5min) after terminating, the composite powder that will be obtained removes dechlorination using suction filtration washing
Change sodium template, and 2h is incubated under the conditions of 80 DEG C in vacuum drying chamber and be dried to obtain three-dimensional grapheme supported copper powder of nanometric particles
Powder.Gerhardite (quality 36.405g) ethanol solution 250mL is prepared, magnetic agitation uniformly adds three-dimensional grapheme afterwards
Supported copper powder of nanometric particles 0.357g, and ultrasound 30min, are well mixed it；Decline after 70 DEG C of conditions in water-bath
Ethanol stirring is evaporated, and 80 DEG C of dryings in vacuum drying chamber, and three-dimensional grapheme/basic copper nitrate mixed powder is obtained after grinding
End；Afterwards by 30g three-dimensional graphemes/basic copper nitrate composite powder in tube furnace calcining reduction under 400 DEG C of hydrogen atmospheres, obtain
To three-dimensional grapheme/copper composite powder (Graphene content is 4.0vol.%)；By the three-dimensional grapheme/copper composite powder of 40g or so
End is placed inIn graphite jig, vacuum heating-press sintering parameter is 10 DEG C/min of heating rate, 600 DEG C of insulation 1h, vacuum<10- 4MPa, obtains Graphene/copper billet composite material.
Embodiment 5
Sodium chloride 36.590g is weighed, glucose 0.938g, Gerhardite 2.265g is placed in beaker, weigh 121mL
Deionized water dissolving, magnetic agitation it is uniform (>Settled solution 6h) is obtained, is put in culture dish in -20 DEG C of conditions of freezer compartment of refrigerator
Lower freezing 24h；Sample after freezing is put in freeze drier and is freezed, lyophilisation condition is：- 20 DEG C, freeze-drying time 24h.Will
Sample grinding after lyophilized obtains presoma composite powder (powder diameter~100 mesh)；Precursor powder is placed in tube furnace
(10 DEG C/min of heating rate, 750 DEG C of holding temperature, soaking time 2h, gas flow 100mL/min) calcining under hydrogen atmosphere,
Insulation is quickly cooled to room temperature (100 DEG C are dropped in 5min) after terminating, the composite powder that will be obtained removes dechlorination using suction filtration washing
Change sodium template, and 2h is incubated under the conditions of 80 DEG C in vacuum drying chamber and be dried to obtain three-dimensional grapheme supported copper powder of nanometric particles
Powder.Gerhardite (quality 36.405g) ethanol solution 250mL is prepared, magnetic agitation uniformly adds three-dimensional grapheme afterwards
Supported copper powder of nanometric particles 0.357g, and ultrasound 30min, are well mixed it；Decline after 70 DEG C of conditions in water-bath
Ethanol stirring is evaporated, and 80 DEG C of dryings in vacuum drying chamber, and three-dimensional grapheme/basic copper nitrate mixed powder is obtained after grinding
End；Afterwards by 30g three-dimensional graphemes/basic copper nitrate composite powder in tube furnace calcining reduction under 400 DEG C of hydrogen atmospheres, obtain
To three-dimensional grapheme/copper composite powder (Graphene content is 4.0vol.%)；By the three-dimensional grapheme/copper composite powder of 40g or so
End is placed inIn graphite jig, vacuum heating-press sintering parameter is 10 DEG C/min of heating rate, 700 DEG C of insulation 1h, vacuum<10-4MPa, obtains Graphene/copper billet composite material.
Embodiment 6
Sodium chloride 36.590g is weighed, citric acid 1.000g, Gerhardite 2.265g is placed in beaker, weigh 121mL
Deionized water dissolving, magnetic agitation it is uniform (>Settled solution 6h) is obtained, is put in culture dish in -20 DEG C of conditions of freezer compartment of refrigerator
Lower freezing 24h；Sample after freezing is put in freeze drier and is freezed, lyophilisation condition is -20 DEG C, freeze-drying time 24h.To freeze
Sample grinding after dry obtains presoma composite powder (powder diameter~100 mesh)；Precursor powder is placed in hydrogen in tube furnace
(10 DEG C/min of heating rate, 750 DEG C of holding temperature, soaking time 2h, gas flow 100mL/min) calcining under gas atmosphere, protects
Temperature is quickly cooled to room temperature (100 DEG C are dropped in 5min) after terminating, the composite powder that will be obtained removes chlorination using suction filtration washing
Sodium template, and insulation 2h is dried to obtain three-dimensional grapheme supported copper powder of nanometric particles powder under the conditions of 80 DEG C in vacuum drying chamber
End.Gerhardite (quality 36.405g) ethanol solution 250mL is prepared, magnetic agitation uniformly adds three-dimensional grapheme to bear afterwards
Copper-loaded powder of nanometric particles 0.357g, and ultrasound 30min, are well mixed it；Decline second after 70 DEG C of conditions in water-bath
Alcohol stirring is evaporated, and 80 DEG C of dryings in vacuum drying chamber, and three-dimensional grapheme/basic copper nitrate mixed-powder is obtained after grinding；
Afterwards by 30g three-dimensional graphemes/basic copper nitrate composite powder in tube furnace calcining reduction under 300 DEG C of hydrogen atmospheres, obtain
Three-dimensional grapheme/copper composite powder (Graphene content is 4.0vol.%)；By the three-dimensional grapheme/copper composite powder of 40g or so
It is placed inIn graphite jig, vacuum heating-press sintering parameter is 10 DEG C/min of heating rate, 800 DEG C of insulation 1h, vacuum<10- 4MPa, obtains Graphene/copper billet composite material.
Claims (2)
1. a kind of fabricated in situ three-dimensional grapheme strengthens Cu-base composites preparation method, it is characterised in that including procedure below：
1. it is copper source with Gerhardite, is 3 by C and Cu elemental mole ratios:1~4:1 and solid carbon source glucose C6H12O6Or
Citric acid C6H8O7, according to the elemental mole ratios 100 of Na and Cu:1~200:1 mixes with water soluble salt template sodium chloride nacl, it
It is afterwards 1 according to the mass ratio of NaCl and water:3~1:5 add dissolving in deionized water, and magnetic agitation is uniform, obtains transparent and homogeneous
Precursor solution；
2. by step 1. in precursor solution freeze-drying and dehydrating after the drying solid powder that obtains, mixed after grinding sieving
Close powder precursor；
3. the composite powder presoma for 2. step being obtained, under atmosphere protection, heating rate is warming up to for 2~10 DEG C/min
600~800 DEG C, 1~3h is incubated, afterwards fast cooling cooling, obtains three-dimensional sodium chloride-graphene-supported copper nano particles oneself
Assembly powder；
4. the self-assembly powder for 3. step being obtained washes away sodium chloride using deionized water suction filtration, and three-dimensional is obtained after vacuum drying
Graphene-supported copper nano particles composite powder material；
5. the dusty material that 4. step obtains is poured into the ethanol solution of copper nitrate, in copper nitrate in copper and dusty material
Carbon mass ratio is 30:1~100:1, magnetic agitation is uniform, more than ultrasonically treated half an hour；It is placed in 70 DEG C of water-baths and stirs
Mix and be evaporated, and in vacuum drying chamber 80 DEG C be dried to obtain basic copper nitrate cladding three-dimensional grapheme composite powder material；
6. the powder that 5. step obtains is placed in Noah's ark, under atmosphere protection, heating rate is warming up to for 2~10 DEG C/min
600~800 DEG C, 1~3h is incubated, lowered the temperature with stove, obtain three-dimensional grapheme-copper Particles dispersed powder；
7. the dusty material for obtaining by step 6. is placed in graphite jig, is molded using vacuum hot pressing sintering technique, sintering temperature
It is 600~800 DEG C to spend, 0.2~1h of sintered heat insulating time, and obtaining three-dimensional grapheme strengthens copper-based block composite material.
2. preparation method according to claim 1, it is characterised in that atmosphere of the step 3. with step 4. is hydrogen, nitrogen,
One kind in argon gas or hydrogen+nitrogen, hydrogen+argon gas, gas flow rate is 50~200mL/min.
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