CN102787250A - Preparation method for diphasic nanometer particle dispersion strengthening copper matrix composite material - Google Patents
Preparation method for diphasic nanometer particle dispersion strengthening copper matrix composite material Download PDFInfo
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- CN102787250A CN102787250A CN201210289633XA CN201210289633A CN102787250A CN 102787250 A CN102787250 A CN 102787250A CN 201210289633X A CN201210289633X A CN 201210289633XA CN 201210289633 A CN201210289633 A CN 201210289633A CN 102787250 A CN102787250 A CN 102787250A
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- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 67
- 239000006185 dispersion Substances 0.000 title claims abstract description 28
- 239000011159 matrix material Substances 0.000 title abstract description 33
- 239000002245 particle Substances 0.000 title abstract description 5
- 239000010949 copper Substances 0.000 title abstract 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract 4
- 229910052802 copper Inorganic materials 0.000 title abstract 4
- 238000005728 strengthening Methods 0.000 title abstract 3
- 239000000843 powder Substances 0.000 claims abstract description 216
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 238000003825 pressing Methods 0.000 claims abstract description 33
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 97
- 238000003756 stirring Methods 0.000 claims description 56
- 238000010792 warming Methods 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 44
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 239000002244 precipitate Substances 0.000 claims description 32
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- -1 polyoxyethylene Polymers 0.000 claims description 24
- 238000013019 agitation Methods 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 239000004570 mortar (masonry) Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 239000006228 supernatant Substances 0.000 claims description 16
- 238000004448 titration Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000010891 electric arc Methods 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 abstract 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 229910001679 gibbsite Inorganic materials 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910006404 SnO 2 Inorganic materials 0.000 description 6
- 238000000137 annealing Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
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Abstract
The invention relates to a preparation method for diphasic nanometer particle dispersion strengthening copper matrix composite material and relates to the copper matrix composite material. A sol-gel process is combined with a wet powder mixing and powder metallurgic method in the preparation method, and the preparation method comprises the following steps: Ti4+ ion doped Sn(OH)4 dry powder and Al(OH)3 dry powder are prepared; SnO2-TiO2 nanometer powder and Al2O3 nanometer powder are prepared by calcination; a dispersing agent polyethylene glycol-20000 is added into the two powders to prepare turbid liquid in absolute ethyl alcohol, then electrolytic Cu powder is added and mixed in the turbid liquid to form a heavy paste mixture, and then the mixture is dried to prepare (0.3wt%-2.5wt% of Al2O3 + 0.7wt%-4.5wt% of SnO2-TiO2)/Cu composite powder; and finally the diphasic nanometer particle dispersion strengthening copper matrix composite material with high strength, high conductivity, good high temperature softening resisting performance and electric arc burning loss resisting performance and low surface contact resistance is obtained through pressing and sintering.
Description
Technical field
Technical scheme of the present invention relates to Cu-base composites, specifically the preparation method of the dispersed particle-strengthened Cu-base composites of biphase.
Background technology
Dispersion-strengthened Cu based composites has obtained using widely in industrial circles such as automobile, battery, Electronic Packaging and microwave device as one type of important functional material.Development along with industrial civilization; People will be increasing to the demand of this type of material, touches the dispersion-strengthened Cu based composites that technical fields such as bridge, collector ring of generator, circuit lead frame, electric car and electric power train aerial condutor also all press for excellent property such as resistance welding electrode, electro-engineering switch.Existing result of study shows; The dispersion-strengthened Cu based composites of new generation of high comprehensive performance; Its wild phase size must be nano level, because of the nano level wild phase has the effect of strong obstruction dislocation, crystal boundary and subgrain boundary motion, and therefore can efficient hardening Cu matrix; Simultaneously, the nanometer wild phase must be highly dispersed in the Cu matrix, effectively reduces the scattering that receives in the electronic transmission process with this, thereby can not cause the obvious decline of material electric conductivity.In addition; The nanometer wild phase of Cu based composites also must have high heat-resisting stabilising characteristic; Thereby under the high temperature near the Cu fusing point, the nanometer wild phase still has the effect of strong obstruction dislocation motion and crystal boundary, makes the Cu based composites have high high temperature softening resistance ability.
Al
2O
3/ Cu dispersion-strengthened Cu based composites is one type of material with good comprehensive physicals and mechanical property; Have that recrystallization temperature height, structure stability are good, ys and tensile strength is high, softening temperature is high, the high temperature creep-resisting performance is good, hardness is high and conductivity is high advantage; Field such as electronic technology and electrician has broad application prospects in modern times, thereby becomes one of research and development focus of dispersion-strengthened Cu based composites.Yet work as Al
2O
3/ Cu matrix material is during as the electrical contact material long service, Al
2O
3Gathering in contact surface will cause enlarging markedly of material contact resistance, and then causes material temperature rise aggravation, causes material mechanical performance to descend simultaneously.
In order further to improve Al
2O
3The high-performance of/Cu dispersion-strengthened Cu based composites also enlarges its range of application, and said material preparing method's research and development also are able to development.The preparation method of CN101240387 and the disclosed said material of CN101034635 adopts internal oxidation.Though internal oxidation can make the nano-scale oxide particle distribute in the disperse of Cu matrix camber, the technology of this method is very complicated, and high to the requirement of equipment and technology, input cost is big, thereby has greatly limited the application of these class methods.The above-mentioned type preparation methods that CN1844426 and CN1339613 disclose mainly is to adopt mechanical alloying method; Yet these class methods there are differences with the Cu powder density owing to oxide dispersion intensifying; Simultaneously owing to the strong surface effects of nano-scale particle has the characteristic of very easily reuniting; Feasible disperse distributed degrees with wild phase in the prepared Cu based composites of these class methods is not enough, thereby influences the over-all properties of reinforced effects and matrix material.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method of the dispersed particle-strengthened Cu-base composites of biphase is provided, adopts sol-gel technology to combine wet method to mix the preparation method of powder and powder metallurgic method, in the component of this material with Al
2O
3Nano particle is main wild phase, and adds TiO
2Doping SnO
2Nano particle is to reduce Al
2O
3The surface contacted resistance of/Cu dispersion-strengthened Cu based composites and the anti-electric-arc scaling loss performance that improves material; Overcome simultaneously with the over-all properties that influences reinforced effects and matrix material in the prepared Cu based composites of prior art because of the disperse distributed degrees of wild phase inadequately, and preparation technology is very complicated, to the requirement height and the big shortcoming of input cost of equipment and technology.
The present invention solves this technical problem the technical scheme that is adopted: the preparation method of the dispersed particle-strengthened Cu-base composites of biphase is to adopt sol-gel technology to combine wet method to mix the preparation method of powder and powder metallurgic method, and step is following:
The first step, preparation Ti
4+Ion doping Sn (OH)
4Dried powder and Al (OH)
3Dried powder
SnCl with aequum
45H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.08～0.15mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even, presses ion mol ratio Ti then
4+: (Sn
4++ Ti
4+The TiCl of aequum is got in)=5: 100
4The SnCl that adds above-mentioned preparation
45H
2In the O solution, adding consumption simultaneously is Sn (OH)
42～3% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 60～70 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 8～9, generate Ti
4+Ion doping Sn (OH)
4Gelatinous precipitate is waited to leave standstill after 12～15 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 2～3 times, rotating speed 2500r/min, and each 10 minutes, then with the Ti that makes
4+Ion doping Sn (OH)
4Gel is put into the box-type drying case 60 ℃ of oven dry, grinds with mortar again, makes Ti
4+Ion doping Sn (OH)
4Dried powder;
Other is with the Al (NO of aequum
3)
39H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.06～0.12mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even, and adding consumption simultaneously is Al (OH)
32～3% dispersion agent polyoxyethylene glycol-20000 of quality; Stir; After waiting to be warming up to 60～70 ℃, insulated and stirred is 30 minutes again, must clarify mixing solutions; Then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 8～9, generate Al (OH)
3Gelatinous precipitate is waited to leave standstill after 15～18 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 2～3 times, rotating speed 2500r/min, and each 10 minutes, then with the Al that makes (OH)
3Gel is put into the box-type drying case 60 ℃ of oven dry, grinds with mortar again, makes Al (OH)
3Dried powder;
Second step, preparation SnO
2-TiO
2Nanometer powder and Al
2O
3Nanometer powder
With the prepared Ti of the first step
4+Ion doping Sn (OH)
4Dried powder is warming up to 450～550 ℃ of calcinings 1 hour in chamber type electric resistance furnace, make the SnO that median size is 6～20nm
2-TiO
2Nanometer powder is with the prepared Al of the first step (OH)
3Dried powder is warming up to 500～700 ℃ of calcinings 1 hour in chamber type electric resistance furnace, make the Al that median size is 20～50nm
2O
3Nanometer powder;
The 3rd step, preparation (Al
2O
3+ SnO
2-TiO
2)/Cu composite powder
Used component materials reaches separately, and mass percent is: electrolysis Cu powder 93%～99%, Al
2O
3Nanometer powder 0.3%～2.5%, SnO
2-TiO
2Nanometer powder 0.7%～4.5%, the mass percent sum of used component materials is 100%,
Go on foot prepared SnO by said components quality of material per-cent with second
2-TiO
2Nanometer powder, Al
2O
3Nanometer powder and with two kinds of powder total mass ratios be that 3～4% dispersion agent polyoxyethylene glycol-20000 joins in the absolute ethyl alcohol that consumption is 1.8～2.0ml/1.0gCu powder jointly; And stir and made it even in 10 minutes; And then sonic oscillation 30～40 minutes, form stable SnO
2-TiO
2Nanometer powder and Al
2O
3The suspension liquid of nanometer powder; Add electrolysis Cu powder by said components quality of material per-cent again; Stirred simultaneously 3～4 hours, and do not have the even dense thick paste mixture of clear liquid, at last this even dense thick paste mixture is placed 50～60 ℃ baking oven until forming the upper strata; Absolute ethyl alcohol to wherein volatilizees fully, makes (0.3wt%～2.5wt%Al
2O
3+ 0.7wt%～4.5wt% SnO
2-TiO
2)/Cu composite powder;
The 4th step, the dispersed particle-strengthened Cu-base composites product of preparation biphase
With prepared (Al of the 3rd step
2O
3+ SnO
2-TiO
2)/Cu composite powder through 580～620MPa first pressing, is warming up to the moulding in 2～3 hours of 930～950 ℃ of sintering then under the high-purity argon gas protection in sintering oven on pressing machine; On pressing machine, press again again through 1000～1100MPa; And in sintering oven, be warming up to 960～980 ℃ of resinterings 2～3 hours down in high-purity argon gas protection, at last on the pressing machine in carrying out making the dispersed particle-strengthened Cu-base composites product of biphase after cold deformation is suppressed under the 1200MPa.
The preparation method of the dispersed particle-strengthened Cu-base composites of above-mentioned biphase, wherein used starting material are all through being purchased acquisition, and used equipment and technology all are that those skilled in the art knows and can grasp.
The invention has the beneficial effects as follows: the preparing method's of the dispersed particle-strengthened Cu-base composites of the biphase of the present invention outstanding substantive distinguishing features that has is: 1. research shows and makes Ti
4+Ion partly replaces SnO
2In Sn
4+Ion forms with SnO
2SnO for solvent
2-TiO
2Behind the sosoloid, can make SnO
2Become to comprise much and play the N-type semiconductor material that the alms giver acts on the oxygen room, thereby can make SnO
2Specific conductivity be significantly improved, work as SnO
2-TiO
2When Cu base electric contact material surface aggregation, than Al
2O
3Can effectively reduce the surface contacted resistance of electrical contact material, thereby the viscosity that can effectively increase the contact surface molten bath again makes contact material have good anti-electric-arc scaling loss performance; 2. with Al
2O
3Nano particle is main wild phase, and adds SnO
2-TiO
2Nano particle is because Al
2O
3And SnO
2-TiO
2Be tiny nano particle, engage thereby be prone to form good interface, simultaneously because Al with the Cu matrix
2O
3Nano particle and SnO
2Nano particle distributes in the disperse of Cu matrix camber; And heat-resistant stability with height; Thereby effective refinement matrix grain; The rearrangement of strong pinning dislocation, obstruction deforming alloy dislocation when high temperature annealing makes matrix material when high temperature annealing, be difficult to take place recrystallize, thereby has excellent high temperature resistance softening power.
The inventive method make with Al
2O
3And SnO
2-TiO
2The dispersed particle-strengthened Cu-base composites of biphase has further promoted Al
2O
3The over-all properties of/Cu matrix material has high intensity, hardness, specific conductivity, high temperature softening resistance ability and anti-electric-arc scaling loss ability, and low surface contacted resistance.This material is applied to low-voltage apparatus with the electrical contact field except that being particularly suitable for, and the fields such as bridge, collector ring of generator, electric car and electric power train aerial condutor of touching at resistance welding electrode, electro-engineering switch also have broad application prospects.The Technology that the inventive method adopted is simple to operation, and production cost is low short with the cycle.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Fig. 1 is for containing different mass mark wild phase (Al
2O
3+ SnO
2-TiO
2The SEM photo of the crooked fracture of)/Cu matrix material wherein, (a) is (1.0wt%Al
2O
3+ 2.0wt% SnO
2-TiO
2The SEM photo of the crooked fracture of)/Cu matrix material; (b) be (1.5wt%Al
2O
3+ 3.5wt% SnO
2-TiO
2The SEM photo of the crooked fracture of)/Cu matrix material.
Fig. 2 is that wild phase content is to (Al
2O
3+ SnO
2-TiO
2The influence curve figure of)/Cu matrix material specific conductivity.
Fig. 3 is that wild phase content is to (Al
2O
3+ SnO
2-TiO
2The influence curve figure of)/Cu composite hardness.
Embodiment
Embodiment 1
The first step, preparation Ti
4+Ion doping Sn (OH)
4Dried powder and Al (OH)
3Dried powder
SnCl with aequum
45H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.08mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even, presses ion mol ratio Ti then
4+: (Sn
4++ Ti
4+The TiCl of aequum is got in)=5: 100
4The SnCl that adds above-mentioned preparation
45H
2O solution, adding consumption simultaneously is Sn (OH)
42% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 60 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 8, generate Ti
4+Ion doping Sn (OH)
4Gelatinous precipitate is waited to leave standstill after 12 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 2 times, rotating speed 2500r/min, and each 10 minutes, then with the Ti that makes
4+Ion doping Sn (OH)
4Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Ti
4+Ion doping Sn (OH)
4Dried powder;
Other is with the Al (NO of aequum
3)
39H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.06mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even; Adding consumption simultaneously is Al (OH)
32% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 60 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 8, generate Al (OH)
3Gelatinous precipitate is waited to leave standstill after 15 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 2 times, rotating speed 2500r/min, and each 10 minutes, then with the Al that makes (OH)
3Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Al (OH)
3Dried powder;
Second step, preparation SnO
2-TiO
2Nanometer powder and Al
2O
3Nanometer powder
With the prepared Ti of the first step
4+Ion doping Sn (OH)
4Dried powder is warming up to 450 ℃ of calcinings 1 hour in chamber type electric resistance furnace, make the SnO that median size is 6nm
2-TiO
2Nanometer powder; With the prepared Al of the first step (OH)
3Dried powder is warming up to 500 ℃ of calcinings 1 hour in chamber type electric resistance furnace, obtain the Al that median size is 20nm
2O
3Nanometer powder;
The 3rd step, preparation (Al
2O
3+ SnO
2-TiO
2)/Cu composite powder
Used component materials reaches separately, and mass percent is: electrolysis Cu powder 99%, Al
2O
3Nanometer powder 0.3%, SnO
2-TiO
2Nanometer powder 0.7%;
Go on foot prepared SnO by said components quality of material per-cent with second
2-TiO
2Nanometer powder, Al
2O
3Nanometer powder and with two kinds of powder total mass ratios be that 3% dispersion agent polyoxyethylene glycol-20000 joins in the absolute ethyl alcohol that consumption is the 1.8ml/1.0gCu powder jointly, and stir and made it even in 10 minutes, and then sonic oscillation 30 minutes, form stable SnO
2-TiO
2Nanometer powder and Al
2O
3The suspension liquid of nanometer powder; Add electrolysis Cu powder by said components quality of material per-cent again; Stirred simultaneously 3 hours, and do not have the even dense thick paste mixture of clear liquid, at last this even dense thick paste mixture is placed 50 ℃ baking oven until forming the upper strata; Absolute ethyl alcohol to wherein volatilizees fully, makes (0.3wt%Al
2O
3+ 0.7wt% SnO
2-TiO
2)/Cu composite powder;
The 4th step, the dispersed particle-strengthened Cu-base composites product of preparation biphase
With prepared (0.3wt%Al of the 3rd step
2O
3+ 0.7wt% SnO
2-TiO
2)/Cu composite powder through the 580MPa first pressing, is warming up to the moulding in 2 hours of 930 ℃ of sintering then under the high-purity argon gas protection in sintering oven on pressing machine; On pressing machine, press again again, and in sintering oven, be warming up to 960 ℃ of resinterings 2 hours down in high-purity argon gas protection through 1000MPa, at last on the pressing machine in carrying out making the dispersed particle-strengthened Cu-base composites product of biphase after cold deformation is suppressed under the 1200MPa.
The first step, preparation Ti
4+Ion doping Sn (OH)
4Dried powder and Al (OH)
3Dried powder
SnCl with aequum
45H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.10mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even, presses ion mol ratio Ti then
4+: (Sn
4++ Ti
4+The TiCl of aequum is got in)=5: 100
4The SnCl that adds above-mentioned preparation
45H
2O solution, adding consumption simultaneously is Sn (OH)
42% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 65 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 9, generate Ti
4+Ion doping Sn (OH)
4Gelatinous precipitate is waited to leave standstill after 13 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 3 times, rotating speed 2500r/min, and each 10 minutes, then with the Ti that makes
4+Ion doping Sn (OH)
4Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Ti
4+Ion doping Sn (OH)
4Dried powder;
Other is with the Al (NO of aequum
3)
39H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.08mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even; Adding consumption simultaneously is Al (OH)
32% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 65 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 9, generate Al (OH)
3Gelatinous precipitate is waited to leave standstill after 16 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 3 times, rotating speed 2500r/min, and each 10 minutes, then with the Al that makes (OH)
3Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Al (OH)
3Dried powder;
Second step, preparation SnO
2-TiO
2Nanometer powder and Al
2O
3Nanometer powder
With the prepared Ti of the first step
4+Ion doping Sn (OH)
4Dried powder is warming up to 500 ℃ of calcinings 1 hour in chamber type electric resistance furnace, make the SnO that median size is 13nm
2-TiO
2Nanometer powder; With the prepared Al of the first step (OH)
3Dried powder is warming up to 600 ℃ of calcinings 1 hour in chamber type electric resistance furnace, obtain the Al that median size is 30nm
2O
3Nanometer powder;
The 3rd step, preparation (Al
2O
3+ SnO
2-TiO
2)/Cu composite powder
Used component materials reaches separately, and mass percent is: electrolysis Cu powder 97%, Al
2O
3Nanometer powder 0.3%, SnO
2-TiO
2Nanometer powder 2.7%;
Go on foot prepared SnO by said components quality of material per-cent with second
2-TiO
2Nanometer powder, Al
2O
3Nanometer powder and with two kinds of powder total mass ratios be that 3% dispersion agent polyoxyethylene glycol-20000 joins in the absolute ethyl alcohol that consumption is the 1.8ml/1.0gCu powder jointly, and stir and made it even in 10 minutes, and then sonic oscillation 35 minutes, form stable SnO
2-TiO
2Nanometer powder and Al
2O
3The suspension liquid of nanometer powder; Add electrolysis Cu powder by said components quality of material per-cent again; Stirred simultaneously 3 hours, and do not have the even dense thick paste mixture of clear liquid, at last this even dense thick paste mixture is placed 55 ℃ baking oven until forming the upper strata; Absolute ethyl alcohol to wherein volatilizees fully, makes (0.3wt%Al
2O
3+ 2.7wt% SnO
2-TiO
2)/Cu composite powder;
The 4th step, the dispersed particle-strengthened Cu-base composites product of preparation biphase
With prepared (0.3wt%Al of the 3rd step
2O
3+ 2.7wt% SnO
2-TiO
2)/Cu composite powder through the 600MPa first pressing, is warming up to the moulding in 2 hours of 940 ℃ of sintering then under the high-purity argon gas protection in sintering oven on pressing machine; On pressing machine, press again again, and in sintering oven, be warming up to 970 ℃ of resinterings 2 hours down in high-purity argon gas protection through 1000MPa, at last on the pressing machine in carrying out making the dispersed particle-strengthened Cu-base composites product of biphase after cold deformation is suppressed under the 1200MPa.Embodiment 3
The first step, preparation Ti
4+Ion doping Sn (OH)
4Dried powder and Al (OH)
3Dried powder
SnCl with aequum
45H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.12mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even, presses ion mol ratio Ti then
4+: (Sn
4++ Ti
4+The TiCl of aequum is got in)=5: 100
4The SnCl that adds above-mentioned preparation
45H
2O solution, adding consumption simultaneously is Sn (OH)
42% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 70 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 8, generate Ti
4+Ion doping Sn (OH)
4Gelatinous precipitate is waited to leave standstill after 14 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 3 times, rotating speed 2500r/min, and each 10 minutes, then with the Ti that makes
4+Ion doping Sn (OH)
4Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Ti
4+Ion doping Sn (OH)
4Dried powder;
Other is with the Al (NO of aequum
3)
39H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.10mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even; Adding consumption simultaneously is Al (OH)
32% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 70 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 8, generate Al (OH)
3Gelatinous precipitate is waited to leave standstill after 17 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 3 times, rotating speed 2500r/min, and each 10 minutes, then with the Al that makes (OH)
3Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Al (OH)
3Dried powder;
Second step, preparation SnO
2-TiO
2Nanometer powder and Al
2O
3Nanometer powder
With the prepared Ti of the first step
4+Ion doping Sn (OH)
4Dried powder is warming up to 500 ℃ of calcinings 1 hour in chamber type electric resistance furnace, make the SnO that median size is 13nm
2-TiO
2Nanometer powder; With the prepared Al of the first step (OH)
3Dried powder is warming up to 600 ℃ of calcinings 1 hour in chamber type electric resistance furnace, obtain the Al that median size is 30nm
2O
3Nanometer powder;
The 3rd step, preparation (Al
2O
3+ SnO
2-TiO
2)/Cu composite powder
Used component materials reaches separately, and mass percent is: electrolysis Cu powder 97%, Al
2O
3Nanometer powder 1.0%, SnO
2-TiO
2Nanometer powder 2.0%;
Go on foot prepared SnO by said components quality of material per-cent with second
2-TiO
2Nanometer powder, Al
2O
3Nanometer powder and with two kinds of powder total mass ratios be that 3% dispersion agent polyoxyethylene glycol-20000 joins in the absolute ethyl alcohol that consumption is the 1.9ml/1.0gCu powder jointly, and stir and made it even in 10 minutes, and then sonic oscillation 35 minutes, form stable SnO
2-TiO
2Nanometer powder and Al
2O
3The suspension liquid of nanometer powder; Add electrolysis Cu powder by said components quality of material per-cent again; Stirred simultaneously 3 hours, and do not have the even dense thick paste mixture of clear liquid, at last this even dense thick paste mixture is placed 55 ℃ baking oven until forming the upper strata; Absolute ethyl alcohol to wherein volatilizees fully, makes (1.0wt%Al
2O
3+ 2.0wt%SnO
2-TiO
2)/Cu composite powder;
The 4th step, the dispersed particle-strengthened Cu-base composites product of preparation biphase
With prepared (1.0wt%Al of the 3rd step
2O
3+ 2.0wt% SnO
2-TiO
2)/Cu composite powder through the 600MPa first pressing, is warming up to the moulding in 2 hours of 940 ℃ of sintering then under the high-purity argon gas protection in sintering oven on pressing machine; On pressing machine, press again again, and in sintering oven, be warming up to 970 ℃ of resinterings 2 hours down in high-purity argon gas protection through 1000MPa, at last on the pressing machine in carrying out making the dispersed particle-strengthened Cu-base composites product of biphase after cold deformation is suppressed under the 1200MPa.
Embodiment 4
The first step, preparation Ti
4+Ion doping Sn (OH)
4Dried powder and Al (OH)
3Dried powder
SnCl with aequum
45H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.15mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even, presses ion mol ratio Ti then
4+: (Sn
4++ Ti
4+The TiCl of aequum is got in)=5: 100
4The SnCl that adds above-mentioned preparation
45H
2O solution, adding consumption simultaneously is Sn (OH)
43% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 70 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 9, generate Ti
4+Ion doping Sn (OH)
4Gelatinous precipitate is waited to leave standstill after 15 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 3 times, rotating speed 2500r/min, and each 10 minutes, then with the Ti that makes
4+Ion doping Sn (OH)
4Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Ti
4+Ion doping Sn (OH)
4Dried powder;
Other is with the Al (NO of aequum
3)
39H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.12mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even; Adding consumption simultaneously is Al (OH)
33% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 70 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 9, generate Al (OH)
3Gelatinous precipitate is waited to leave standstill after 18 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 3 times, rotating speed 2500r/min, and each 10 minutes, then with the Al that makes (OH)
3Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Al (OH)
3Dried powder;
Second step, preparation SnO
2-TiO
2Nanometer powder and Al
2O
3Nanometer powder
With the prepared Ti of the first step
4+Ion doping Sn (OH)
4Dried powder is warming up to 500 ℃ of calcinings 1 hour in chamber type electric resistance furnace, make the SnO that median size is 13nm
2-TiO
2Nanometer powder; With the prepared Al of the first step (OH)
3Dried powder is warming up to 600 ℃ of calcinings 1 hour in chamber type electric resistance furnace, obtain the Al that median size is 30nm
2O
3Nanometer powder;
The 3rd step, preparation (Al
2O
3+ SnO
2-TiO
2)/Cu composite powder
Used component materials reaches separately, and mass percent is: electrolysis Cu powder 95%, Al
2O
3Nanometer powder 1.5%, SnO
2-TiO
2Nanometer powder 3.5%;
Go on foot prepared SnO by said components quality of material per-cent with second
2-TiO
2Nanometer powder, Al
2O
3Nanometer powder and with two kinds of powder total mass ratios be that 4% dispersion agent polyoxyethylene glycol-20000 joins in the absolute ethyl alcohol that consumption is the 2.0ml/1.0gCu powder jointly, and stir and made it even in 10 minutes, and then sonic oscillation 40 minutes, form stable SnO
2-TiO
2Nanometer powder and Al
2O
3The suspension liquid of nanometer powder; Add electrolysis Cu powder by said components quality of material per-cent again; Stirred simultaneously 4 hours, and do not have the even dense thick paste mixture of clear liquid, at last this even dense thick paste mixture is placed 60 ℃ baking oven until forming the upper strata; Absolute ethyl alcohol to wherein volatilizees fully, makes (1.5wt%Al
2O
3+ 3.5wt% SnO
2-TiO
2)/Cu composite powder;
The 4th step, the dispersed particle-strengthened Cu-base composites product of preparation biphase
With prepared (1.5wt%Al of the 3rd step
2O
3+ 3.5wt% SnO
2-TiO
2)/Cu composite powder through the 600MPa first pressing, is warming up to the moulding in 2 hours of 940 ℃ of sintering then under the high-purity argon gas protection in sintering oven on pressing machine; On pressing machine, press again again, and in sintering oven, be warming up to 970 ℃ of resinterings 2 hours down in high-purity argon gas protection through 1000MPa, at last on the pressing machine in carrying out making the dispersed particle-strengthened Cu-base composites product of biphase after cold deformation is suppressed under the 1200MPa.
Fig. 1 (a) has shown (1.0wt%Al that adopts the embodiment of the invention 3 preparations
2O
3+ 2.0wt% SnO
2-TiO
2The crooked fracture apperance of)/Cu matrix material, Fig. 1 (b) have shown (1.5wt%Al that adopts the embodiment of the invention 4 preparations
2O
3+ 3.5wt%SnO
2-TiO
2The crooked fracture apperance of)/Cu matrix material.Can find out as (Al by Fig. 1
2O
3+ SnO
2-TiO
2) when wild phase content was low, fracture contained a large amount of tiny dimples, demonstrates the certain toughness fracture characteristic; And work as (Al
2O
3+ SnO
2-TiO
2) when wild phase content was higher, dimple quantity and size reduced, fragility increases.The nano level white small-particle that visible Cu matrix camber disperse distributes among Fig. 1 is Al
2O
3Or SnO
2-TiO
2
Embodiment 5
The first step, preparation Ti
4+Ion doping Sn (OH)
4Dried powder and Al (OH)
3Dried powder
SnCl with aequum
45H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.15mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even, presses ion mol ratio Ti then
4+: (Sn
4++ Ti
4+The TiCl of aequum is got in)=5: 100
4The SnCl that adds above-mentioned preparation
45H
2O solution, adding consumption simultaneously is Sn (OH)
43% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 70 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 9, generate Ti
4+Ion doping Sn (OH)
4Gelatinous precipitate is waited to leave standstill after 15 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 3 times, rotating speed 2500r/min, and each 10 minutes, then with the Ti that makes
4+Ion doping Sn (OH)
4Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Ti
4+Ion doping Sn (OH)
4Dried powder;
Other is with the Al (NO of aequum
3)
39H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.12mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even; Adding consumption simultaneously is Al (OH)
33% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 70 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 9, generate Al (OH)
3Gelatinous precipitate is waited to leave standstill after 18 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 3 times, rotating speed 2500r/min, and each 10 minutes, then with the Al that makes (OH)
3Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Al (OH)
3Dried powder;
Second step, preparation SnO
2-TiO
2Nanometer powder and Al
2O
3Nanometer powder
With the prepared Ti of the first step
4+Ion doping Sn (OH)
4Dried powder is warming up to 520 ℃ of calcinings 1 hour in chamber type electric resistance furnace, make the SnO that median size is 15nm
2-TiO
2Nanometer powder; With the prepared Al of the first step (OH)
3Dried powder is warming up to 650 ℃ of calcinings 1 hour in chamber type electric resistance furnace, obtain the Al that median size is 40nm
2O
3Nanometer powder;
The 3rd step, preparation (Al
2O
3+ SnO
2-TiO
2)/Cu composite powder
Used component materials reaches separately, and mass percent is: electrolysis Cu powder 95%, Al
2O
3Nanometer powder 0.5%, SnO
2-TiO
2Nanometer powder 4.5%;
Go on foot prepared SnO by said components quality of material per-cent with second
2-TiO
2Nanometer powder, Al
2O
3Nanometer powder and with two kinds of powder total mass ratios be that 4% dispersion agent polyoxyethylene glycol-20000 joins in the absolute ethyl alcohol that consumption is the 2.0ml/1.0gCu powder jointly, and stir and made it even in 10 minutes, and then sonic oscillation 40 minutes, form stable SnO
2-TiO
2Nanometer powder and Al
2O
3The suspension liquid of nanometer powder; Add electrolysis Cu powder by said components quality of material per-cent again; Stirred simultaneously 4 hours, and do not have the even dense thick paste mixture of clear liquid, at last this even dense thick paste mixture is placed 60 ℃ baking oven until forming the upper strata; Absolute ethyl alcohol to wherein volatilizees fully, makes (0.5wt%Al
2O
3+ 4.5wt% SnO
2-TiO
2)/Cu composite powder;
The 4th step, the dispersed particle-strengthened Cu-base composites product of preparation biphase
With prepared (0.5wt%Al of the 3rd step
2O
3+ 4.5wt% SnO
2-TiO
2)/Cu composite powder through the 610MPa first pressing, is warming up to the moulding in 3 hours of 940 ℃ of sintering then under the high-purity argon gas protection in sintering oven on pressing machine; On pressing machine, press again again, and in sintering oven, be warming up to 975 ℃ of resinterings 2 hours down in high-purity argon gas protection through 1100MPa, at last on the pressing machine in carrying out making the dispersed particle-strengthened Cu-base composites product of biphase after cold deformation is suppressed under the 1200MPa.
Shown in Figure 2 for adopting (the Al of the embodiment of the invention 2,3 or 4,5 said prepared
2O
3+ SnO
2-TiO
2) the wild phase total content is that the specific conductivity of Cu based composites of 3wt% or 5wt% is with Al
2O
3The changing conditions of content.Can find out as (Al by Fig. 2
2O
3+ SnO
2-TiO
2) total massfraction one timing of wild phase, with Al
2O
3The reduction of content, (Al
2O
3+ SnO
2-TiO
2The specific conductivity of)/Cu matrix material raises.(1.0wt%Al like embodiment 3 preparations
2O
3+ 2.0wt%SnO
2-TiO
2The specific conductivity of)/Cu matrix material is 79.3%IACS, and (the 0.3wt%Al of embodiment 2 preparations
2O
3+ 2.7wt%SnO
2-TiO
2The specific conductivity of)/Cu matrix material is 89.7%IACS; (1.5wt%Al for another embodiment 4 preparations
2O
3+ 3.5wt%SnO
2-TiO
2The specific conductivity of)/Cu matrix material is 77.6%IACS, and (the 0.5wt%Al of embodiment 5 preparations
2O
3+ 4.5wt%SnO
2-TiO
2The specific conductivity of)/Cu matrix material raises and is 80.2%IACS.In the time of can also finding out that by Fig. 2 the wild phase total content reduces, (Al
2O
3+ SnO
2-TiO
2The specific conductivity of)/Cu matrix material obviously raises.
Shown in Figure 3 for adopting (the Al of the embodiment of the invention 2 and 3 or 4 and 5 said prepared
2O
3+ SnO
2-TiO
2) the wild phase total content is that the hardness of Cu based composites of 3wt% or 5wt% is with Al
2O
3The changing conditions of content.Can find out by Fig. 3, at (Al
2O
3+ SnO
2-TiO
2) one timing of wild phase total amount, along with Al
2O
3The increase of proportion, (Al
2O
3+ SnO
2-TiO
2The hardness of)/Cu matrix material rises.(0.3wt%Al like embodiment 2 preparations
2O
3+ 2.7wt%SnO
2-TiO
2The hardness of)/Cu matrix material is 92.1HV, and (the 1.0wt%Al of embodiment 3 preparations
2O
3+ 2.0wt%SnO
2-TiO
2The hardness of)/Cu matrix material is 123.7HV; (0.5wt%Al for another embodiment 5 preparations
2O
3+ 4.5wt%SnO
2-TiO
2The hardness of)/Cu matrix material is 98.7HV, and (the 1.5wt%Al of embodiment 4 preparations
2O
3+ 3.5wt%SnO
2-TiO
2The hardness of)/Cu matrix material is increased to 135.0HV, for adopting more than 2 times of pure Cu hardness of same process preparation.This shows Al
2O
3In this Cu based composites, played the effect of " skeleton " as main wild phase.And SnO
2-TiO
2, plays this Cu based composites the effect that reduces material surface contact resistance and anti-electric-arc scaling loss when being used for electrical contact device.Can find out (Al by Fig. 3 in addition
2O
3+ SnO
2-TiO
2) when the wild phase total content raise, its hardness also obviously raise.
Embodiment 6
The first step, preparation Ti
4+Ion doping Sn (OH)
4Dried powder and Al (OH)
3Dried powder
SnCl with aequum
45H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.15mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even, presses ion mol ratio Ti then
4+: (Sn
4++ Ti
4+The TiCl of aequum is got in)=5: 100
4The SnCl that adds above-mentioned preparation
45H
2O solution, adding consumption simultaneously is Sn (OH)
43% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 70 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 9, generate Ti
4+Ion doping Sn (OH)
4Gelatinous precipitate is waited to leave standstill after 15 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 3 times, rotating speed 2500r/min, and each 10 minutes, then with the Ti that makes
4+Ion doping Sn (OH)
4Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Ti
4+Ion doping Sn (OH)
4Dried powder;
Other is with the Al (NO of aequum
3)
39H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.12mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even; Adding consumption simultaneously is Al (OH)
33% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 70 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 9, generate Al (OH)
3Gelatinous precipitate is waited to leave standstill after 18 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 3 times, rotating speed 2500r/min, and each 10 minutes, then with the Al that makes (OH)
3Gel is put into 60 ℃ of oven dry of box-type drying case, grinds with mortar again, makes Al (OH)
3Dried powder;
Second step, preparation SnO
2-TiO
2Nanometer powder and Al
2O
3Nanometer powder
With the prepared Ti of the first step
4+Ion doping Sn (OH)
4Dried powder is warming up to 550 ℃ of calcinings 1 hour in chamber type electric resistance furnace, make the SnO that median size is 20nm
2-TiO
2Nanometer powder; With the prepared Al of the first step (OH)
3Dried powder is warming up to 700 ℃ of calcinings 1 hour in chamber type electric resistance furnace, obtain the Al that median size is 50nm
2O
3Nanometer powder;
The 3rd step, preparation (Al
2O
3+ SnO
2-TiO
2)/Cu composite powder
Used component materials reaches separately, and mass percent is: electrolysis Cu powder 93%, Al
2O
3Nanometer powder 2.5%, SnO
2-TiO
2Nanometer powder 4.5%;
Go on foot prepared SnO by said components quality of material per-cent with second
2-TiO
2Nanometer powder, Al
2O
3Nanometer powder and with two kinds of powder total mass ratios be that 4% dispersion agent polyoxyethylene glycol-20000 joins in the absolute ethyl alcohol that consumption is the 2.0ml/1.0gCu powder jointly, and stir and made it even in 10 minutes, and then sonic oscillation 40 minutes, form stable SnO
2-TiO
2Nanometer powder and Al
2O
3The suspension liquid of nanometer powder; Add electrolysis Cu powder by said components quality of material per-cent again; Stirred simultaneously 4 hours, and do not have the even dense thick paste mixture of clear liquid, at last this even dense thick paste mixture is placed 60 ℃ baking oven until forming the upper strata; Absolute ethyl alcohol to wherein volatilizees fully, makes (2.5wt%Al
2O
3+ 4.5wt% SnO
2-TiO
2)/Cu composite powder;
The 4th step, the dispersed particle-strengthened Cu-base composites product of preparation biphase
With prepared (2.5wt%Al of the 3rd step
2O
3+ 4.5wt% SnO
2-TiO
2)/Cu composite powder through the 620MPa first pressing, is warming up to the moulding in 3 hours of 950 ℃ of sintering then under the high-purity argon gas protection in sintering oven on pressing machine; On pressing machine, press again again, and in sintering oven, be warming up to 980 ℃ of resinterings 3 hours down in high-purity argon gas protection through 1100MPa, at last on the pressing machine in carrying out making the dispersed particle-strengthened Cu-base composites product of biphase after cold deformation is suppressed under the 1200MPa.
The wherein used starting material of the foregoing description are all through being purchased acquisition, and used equipment and technology all are that those skilled in the art knows and can grasp.
Claims (1)
1. the preparation method of the dispersed particle-strengthened Cu-base composites of biphase is characterized in that: be to adopt sol-gel technology to combine wet method to mix the preparation method of powder and powder metallurgic method, step is following:
The first step, preparation Ti
4+Ion doping Sn (OH)
4Dried powder and Al (OH)
3Dried powder
SnCl with aequum
45H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.08～0.15mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even, presses ion mol ratio Ti then
4+: (Sn
4++ Ti
4+The TiCl of aequum is got in)=5: 100
4The SnCl that adds above-mentioned preparation
45H
2In the O solution, adding consumption simultaneously is Sn (OH)
42～3% dispersion agent polyoxyethylene glycol-20000 of quality stirs, wait to be warming up to 60～70 ℃ after; Insulated and stirred is 30 minutes again; Must clarify mixing solutions, then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 8～9, generate Ti
4+Ion doping Sn (OH)
4Gelatinous precipitate is waited to leave standstill after 12～15 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 2～3 times, rotating speed 2500r/min, and each 10 minutes, then with the Ti that makes
4+Ion doping Sn (OH)
4Gel is put into the box-type drying case 60 ℃ of oven dry, grinds with mortar again, makes Ti
4+Ion doping Sn (OH)
4Dried powder;
Other is with the Al (NO of aequum
3)
39H
2It is in ethanol/zero(ppm) water mixed solvent of 3: 2, to be mixed with the solution of 0.06～0.12mol/L concentration that the O powder is dissolved in volume ratio, and places to stir on the magnetic agitation machine platform and make it even, and adding consumption simultaneously is Al (OH)
32～3% dispersion agent polyoxyethylene glycol-20000 of quality; Stir; After waiting to be warming up to 60～70 ℃, insulated and stirred is 30 minutes again, must clarify mixing solutions; Then under the stirring of magnetic stirrer in this solution the titration concentration of volume percent be that 35% ammoniacal liquor to pH value is 8～9, generate Al (OH)
3Gelatinous precipitate is waited to leave standstill after 15～18 hours and is poured out supernatant liquid, and this gelatinous precipitate is adopted the absolute ethyl alcohol centrifuge washing 2～3 times, rotating speed 2500r/min, and each 10 minutes, then with the Al that makes (OH)
3Gel is put into the box-type drying case 60 ℃ of oven dry, grinds with mortar again, makes Al (OH)
3Dried powder;
Second step, preparation SnO
2-TiO
2Nanometer powder and Al
2O
3Nanometer powder
With the prepared Ti of the first step
4+Ion doping Sn (OH)
4Dried powder is warming up to 450～550 ℃ of calcinings 1 hour in chamber type electric resistance furnace, make the SnO that median size is 6～20nm
2-TiO
2Nanometer powder is with the prepared Al of the first step (OH)
3Dried powder is warming up to 500～700 ℃ of calcinings 1 hour in chamber type electric resistance furnace, make the Al that median size is 20～50nm
2O
3Nanometer powder;
The 3rd step, preparation (Al
2O
3+ SnO
2-TiO
2)/Cu composite powder
Used component materials reaches separately, and mass percent is: electrolysis Cu powder 93%～99%, Al
2O
3Nanometer powder 0.3%～2.5%, SnO
2-TiO
2Nanometer powder 0.7%～4.5%, the mass percent sum of used component materials is 100%.
Go on foot prepared SnO by said components quality of material per-cent with second
2-TiO
2Nanometer powder, Al
2O
3Nanometer powder and with two kinds of powder total mass ratios be that 3～4% dispersion agent polyoxyethylene glycol-20000 joins in the absolute ethyl alcohol that consumption is 1.8～2.0ml/1.0gCu powder jointly; And stir and made it even in 10 minutes; And then sonic oscillation 30～40 minutes, form stable SnO
2-TiO
2Nanometer powder and Al
2O
3The suspension liquid of nanometer powder; Add electrolysis Cu powder by said components quality of material per-cent again; Stirred simultaneously 3～4 hours, and do not have the even dense thick paste mixture of clear liquid, at last this even dense thick paste mixture is placed 50～60 ℃ baking oven until forming the upper strata; Absolute ethyl alcohol to wherein volatilizees fully, makes (0.3wt%～2.5wt%Al
2O
3+ 0.7wt%～4.5wt% SnO
2-TiO
2)/Cu composite powder;
The 4th step, the dispersed particle-strengthened Cu-base composites product of preparation biphase
With prepared (Al of the 3rd step
2O
3+ SnO
2-TiO
2)/Cu composite powder through 580～620MPa first pressing, is warming up to the moulding in 2～3 hours of 930～950 ℃ of sintering then under the high-purity argon gas protection in sintering oven on pressing machine; On pressing machine, press again again through 1000～1100MPa; And in sintering oven, be warming up to 960～980 ℃ of resinterings 2～3 hours down in high-purity argon gas protection, at last on the pressing machine in carrying out making the dispersed particle-strengthened Cu-base composites product of biphase after cold deformation is suppressed under the 1200MPa.
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| CN103752841A (en) * | 2014-01-24 | 2014-04-30 | 合肥工业大学 | Preparing method for nano-copper powder |
| CN104388741A (en) * | 2014-11-20 | 2015-03-04 | 江苏财经职业技术学院 | Ti3SiC2/Al2O3 hybrid reinforcing copper-based composite sliding plate material and preparation method thereof |
| CN105039768A (en) * | 2015-08-26 | 2015-11-11 | 付亚波 | Preparation method for preparing high-strength high-conductivity nano dispersion strengthened copper through sol-gel method |
| CN105603245A (en) * | 2016-01-15 | 2016-05-25 | 黑龙江省科学院高技术研究院 | Transition metal oxide carried graphene enhanced copper-based composite electrocontact material and preparation method thereof |
| CN106435237A (en) * | 2016-09-20 | 2017-02-22 | 天津大学 | Preparation method of nano titania reinforced copper-based composite material |
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| CN1641055A (en) * | 2005-01-04 | 2005-07-20 | 华南理工大学 | Method for preparing nano composite material by infiltration |
| CN101709398A (en) * | 2009-11-11 | 2010-05-19 | 昆明理工大学 | Self-propagating high temperature synthesis preparation method of titanium carbide dispersion strengthening copper-based composite material |
| CN101824559A (en) * | 2009-03-04 | 2010-09-08 | 中国科学院金属研究所 | Zirconium-aluminum-carbon ceramic particle-reinforced copper matrix composite material and preparation method thereof |
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| CN1641055A (en) * | 2005-01-04 | 2005-07-20 | 华南理工大学 | Method for preparing nano composite material by infiltration |
| CN101824559A (en) * | 2009-03-04 | 2010-09-08 | 中国科学院金属研究所 | Zirconium-aluminum-carbon ceramic particle-reinforced copper matrix composite material and preparation method thereof |
| CN101709398A (en) * | 2009-11-11 | 2010-05-19 | 昆明理工大学 | Self-propagating high temperature synthesis preparation method of titanium carbide dispersion strengthening copper-based composite material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752841A (en) * | 2014-01-24 | 2014-04-30 | 合肥工业大学 | Preparing method for nano-copper powder |
| CN103752841B (en) * | 2014-01-24 | 2016-03-09 | 合肥工业大学 | A kind of preparation method of copper nanoparticle |
| CN104388741A (en) * | 2014-11-20 | 2015-03-04 | 江苏财经职业技术学院 | Ti3SiC2/Al2O3 hybrid reinforcing copper-based composite sliding plate material and preparation method thereof |
| CN105039768A (en) * | 2015-08-26 | 2015-11-11 | 付亚波 | Preparation method for preparing high-strength high-conductivity nano dispersion strengthened copper through sol-gel method |
| CN105603245A (en) * | 2016-01-15 | 2016-05-25 | 黑龙江省科学院高技术研究院 | Transition metal oxide carried graphene enhanced copper-based composite electrocontact material and preparation method thereof |
| CN106435237A (en) * | 2016-09-20 | 2017-02-22 | 天津大学 | Preparation method of nano titania reinforced copper-based composite material |
| CN106435237B (en) * | 2016-09-20 | 2018-04-06 | 天津大学 | A kind of preparation method of nano titanium oxide enhancing Cu-base composites |
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