CN107855533A - A kind of method that combination injection molding technology prepares diamond/copper composite - Google Patents

A kind of method that combination injection molding technology prepares diamond/copper composite Download PDF

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CN107855533A
CN107855533A CN201711136474.9A CN201711136474A CN107855533A CN 107855533 A CN107855533 A CN 107855533A CN 201711136474 A CN201711136474 A CN 201711136474A CN 107855533 A CN107855533 A CN 107855533A
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diamond
copper
powder
plating
injection molding
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CN107855533B (en
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何新波
潘彦鹏
任淑彬
吴茂
曲选辉
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • B22F3/10—Sintering only
    • B22F3/1035—Liquid phase sintering
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/006—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes with additional metal compounds being carbides

Abstract

A kind of method that combination injection molding technology prepares diamond/copper composite, using salt bath coating technology in one layer of uniform Mo of diamond surface plating2C is used for improving the wetability of diamond and copper, is then continued using chemical plating method in Mo2C layer surface copper facing, by controlling Cu in plating solution2+Content controls thickness of coated copper layer, so as to prepare the double coating Cu Mo that cupric volume fraction is 1%~10%2C Diamond powder.Then by quantitative Cu Mo2C Diamond powder is mixed into uniform feeding with heteropolymer constituent element paraffin based binder, after granulation on injection machine injection moulding, gained preform carries out pre-sintered after solvent and thermal debinding under high temperature, obtained base substrate is penetrated into copper liquid in diamond framework by the capillarity of hole by vacuum pressureless infiltration technology, so as to obtain the diamond/copper composite material parts with high-volume fractional.The present invention can directly prepare Diamond/Cu composite material parts with complex shape, and diamond volume fraction is high, even tissue is fine and close, can be mass, production cost is low.

Description

A kind of method that combination injection molding technology prepares diamond/copper composite
Technical field
The invention belongs to the forming technique of metal-based composite parts, in particular, provides one kind and combines injection moulding The method that technology prepares Diamond/Cu (diamond/copper) composite.Realize low cost, high-performance metal based composites The preparation of parts.
Background technology
The characteristics of thermal management materials are due to its high heat conduction, the heat in high-temperature region can be transferred to rapidly low-temperature space Domain, reach the purpose for coordinating the temperature difference between high power device and system environments.Meanwhile by the high-efficiency heat conduction of thermal management materials, Its mismatch problem with chip material thermal coefficient of expansion can be improved.Wherein, granule reinforced copper base composite material is heat management Most study, a kind of most widely used composite in Material Field.High-volume fractional (>50vol%) Diamond/Cu is compound Material excellent dimensional stability, can match because it has excellent physical and mechanical properties with semiconductor chips such as Si, GaAs Low linear expansion coefficient, the thermal conductivity far above most composites, it has also become one of ideal thermal management materials, There is tempting application background in the field such as Aeronautics and Astronautics and national defence, therefore, the research of the material in recent years is always that material is ground Study carefully a big focus in field.At present, preparing the more ripe method of high-volume fractional Diamond/Cu composites mainly has powder Metallurgy method and copper liquid infiltration method.Traditional powder metallurgic method is using simply mixed powder-swaging-sintering three step process, Ke Yiling Select the type of matrix alloy composition and reinforcement livingly, performance can scope of design it is larger.But this method produces Diamond/ Cu maximum volume fractions are only 55% or so, and low production efficiency, and production cost is high.Copper liquid infiltration method can prepare high body The composite (up to 70%) of fraction, this method be first by a certain proportion of diadust and binder (such as paraffin, Water etc.) by powder metallurgy be molded technology prepare diamond preform, then binder is removed and carries out pre-sintered system For the diamond framework with certain porosity is gone out, Cu liquations are penetrated into the hole of diamond framework finally by pressure, So as to prepare the Diamond/Cu composites of high-volume fractional.Because this method is using powder metallurgy molding technology preparation gold Hard rock preform, so shaping base Density inhomogeneity, the complex-shaped degree of part are also very restricted.Due to Buddha's warrior attendant Do not moistened between stone and Cu, even if also being difficult to reach complete infiltration using various forms of osmosis technologies, often leave one Quantitative stomata.In addition, the machining of the Diamond/Cu composites of high-volume fractional is extremely difficult in matrix, turn into the material Expect the bottleneck of practical application.This technique is directed to these shortcomings, using Cu-Mo2The double coating diamond dusts of C-Diamond are injected into Shape can prepare the high high-volume fractional of even tissue, consistency with the technique that vacuum pressureless infiltration technology is combined Diamond/Cu composites.Double coating of wherein diamond surface do not moisten during avoiding infiltration between diamond and copper liquid It is wet, make infiltration process fully and completely will not remaining pore.In addition, power injection molding is a kind of near-net-shape technique, because This can directly prepare high-volume fractional diamond/copper composite material parts, compound so as to thoroughly solve Diamond/Cu The Problems in forming of material parts so that high-volume fractional Diamond/Cu composite material parts can inexpensive continuous production.
The content of the invention
It is an object of the invention to provide a kind of method that combination injection molding technology prepares diamond/copper composite, Inexpensive it can directly prepare the high-performance Diamond/Cu composite material parts with net shape and higher dimensional precision.
The present invention is using salt bath coating technology in one layer of uniform Mo of diamond surface plating2C be used for improve diamond with The wetability of copper, then continued using chemical plating method in Mo2C layer surface copper facing, by controlling Cu in plating solution2+Content is controlled Thickness of coated copper layer processed, so as to prepare double coating Cu-Mo that cupric volume fraction is 1%~10%2C-Diamond powder.So Afterwards by quantitative Cu-Mo2C-Diamond prepares preform using Powder Injection Molding Technology, obtained base substrate is passed through true Empty pressureless infiltration technology penetrates into copper liquid in diamond framework by the capillarity of hole, so as to obtain with high volume The diamond/copper composite material parts of fraction.Being prepared using powder injection forming-pressureless infiltration technique has high volume integral Several diamond/copper composite material parts.Concrete technology step is：
1) diamond dust, the MoO that crystal formation degree is MBD10 and particle mean size is 100 μm are chosen3Powder and salt-mixture NaCl-KCl, mechanical batch mixing is carried out, then carry out reaction-sintered in logical being rapidly heated in electric tube furnace for Ar gas, make at high temperature MoO in fused salt3Powder reacts to form Mo with the graphited diamond in surface2C layers, NaCl:KCl mol ratio=1:1；
2) after furnace cooling, obtained product is subjected to ultrasonic alcohol washes and screens out plating Mo2The bortz powder of C layers Body, in plating Mo2The diamond powder surface of C layers carries out electroless copper and obtains double coating Cu-Mo2C-Diamond powder；
3) by double coating Cu-Mo2C-Diamond powder and the binding agent prepared are according to certain ratio on kneading machine 1.5~2 hours are kneaded in 110 DEG C~130 DEG C, powder loading is 55.56~70.71.vol%, is being injected into after granulation Injection moulding on shape machine, the diamond preform of required shape is obtained, the then degreasing in vacuum degreasing stove, removes binding agent And carry out pre-sintering and obtain that there is certain porosity and the diamond framework of intensity.
4) copper billet for accounting for the corresponding pore volume of part (28.58~38.88.vol.%) is placed in one above diamond framework Rise be put into be warming up to 1100~1200 DEG C in infiltration in vacuum stove after carry out pressureless infiltration, be incubated 1~4 hour, naturally cool to Room temperature, as composite material parts.
Wherein the step 1) diamond and MoO3Mol ratio be 10:1~3, the mass ratio of diamond and salt-mixture is 1:3~5；Reaction-sintered temperature is 1000 DEG C~1100 DEG C, and the time is 1~3h.
Step 2) the electroless copper process is as follows：Diamond powder is placed in the SnCl that concentration is 30g/L2Deionized water Surface sensitizing is carried out in solution, is subsequently placed in the PdCl that concentration is 0.25g/L2Surface active is carried out in deionized water solution, most Electroless copper is carried out in the copper sulfate bath prepared afterwards；Wherein copper sulfate bath formula is：CuSO4·5H2O (15g/L), 37% aqueous solution HCHO (14ml/L), EDTA (14.5g/L), C4O6H4KNa (14g/L), second bipyridine (0.02g/L), ferrous cyanogen Change potassium (0.01g/L)；The acid-base value of plating solution is controlled in PH>11, reaction temperature is controlled at 43 ± 0.5 DEG C；By controlling copper sulphate The dosage of plating solution prepares the different double coating Cu-Mo of cupric volume fraction2C-Diamond powder.Cu-Mo2C-Diamond is double Coating diamond dust cupric volume fraction is 1~10vol.%, the amount of copper sulfate bath needed for copper facing process be 0.007~ 0.074L/g, Plating times are 10~30min.
The binding agent that step 3) is prepared is heteropolymer constituent element paraffinic base (PW) binding agent, with high density polyethylene (HDPE) (HDPE), ethene-vinyl acetate resin copolymer (EVA) is used as plasticizer, with stearic acid (SA) for surfactant, each constituent element Percentage by weight is PW：HDPE：EVA：SA=(70~80)：(10~15)：(5~10)：(0~5).Injected after feeding granulation Shaped on forming machine, on injection machine forming temperature be 140~160 DEG C, pressure be 100~120MPa, pre-sintering temperature For 1000~1150 DEG C.Present invention process flow is as shown in Figure 1.
Prepared by the technique being combined using double coating Cu-Mo2C-Diamond injection mouldings-pressureless infiltrations have high volume The advantages of diamond/copper composite material parts of fraction have concentrated both techniques, it is possible to achieve the near net of complicated shape part Shaping, overcomes and subsequently machines the shortcomings that difficult, and its production equipment is simple, and production efficiency is high, thus life can be greatly reduced Produce cost.More importantly double coating of Cu-Mo2C-Diamond particle surfaces avoid diamond and copper liquid during infiltration Between it is nonwetting, make infiltration process fully and completely will not remaining pore.In addition, diamond can flexibly be adjusted using this technology Volume fraction, distribution of the diamond particles in Copper substrate also very uniformly, degreasing and it is pre-sintered during, pass through adjustment Sintering temperature so that the binding agent all perforates of hole left after being removed, can so ensure copper liquid in capillary It is substantially filled in the presence of power in hole, therefore prepared composite material parts consistency is very high, close to solid density.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Embodiment
Embodiment 1：Prepare the Diamond/Cu composite material parts that diamond volume fraction is 70%
Step 1：Weigh diamond dust 10g, MoO3Powder 12g, salt-mixture NaCl-KCl (mol ratio NaCl:KCl=1: 1) 30g, it is well mixed using mixed powder machine.By mixed-powder be rapidly heated in electric tube furnace be heated to 1000 DEG C insulation 3h, the phase Between be passed through Ar atmosphere protection.Reaction product is cleaned, dried, sieving obtains coating surface Mo2The diamond dust of C layers.
Step 2：Weigh plating Mo2The diamond dust 8g of C layers is placed in 0.4L SnCl2In (30g/L) deionized water solution Surface sensitizing is carried out, is subsequently placed in 0.4L PdCl2Surface active is carried out in (0.25g/L) deionized water solution.Finally will place The diamond dust managed carries out electroless copper, prepares copper sulfate bath 0.056L, and wherein copper sulfate bath formula is： CuSO4·5H2O (15g/L), HCHO (37% aqueous solution, 14ml/L), EDTA (14.5g/L), C4O6H4KNa (14g/L), bigeminy Pyridine (0.02g/L), potassium ferrocyanide (0.01g/L).Plating temperature is 43.5 DEG C, PH=12, Plating times 10min, finally Prepare 1Cu-99Diamond (Mo2C) double coating diamond dusts.
Step 3：Heteropolymer constituent element paraffin based binder is chosen, its each constituent element percentage by weight is PW：HDPE：EVA：SA =79：10：6：5.After the binding agent is kneaded 1.5 hours on kneading machine at a temperature of 130 DEG C with double coating Cu-Mo2C- Diamond powder is kneaded 2 hours, powder loading 70.71vol.% on kneading machine at a temperature of 110 DEG C, after granulation Injection moulding in injector, injection temperature are 150 DEG C, injection pressure 105MPa.By gained preform first in three chloroethenes Degreasing is dissolved in alkene, solution temperature is 40 DEG C, and subsequent preform is warming up to 200 DEG C in vacuum degreasing stove and is incubated 1 hour, then It is warming up to 500 DEG C and is incubated 2 hours to remove binding agent completely.
Step 4：Preform after degreasing is continuously heating to 1000 DEG C, and is incubated 2 hours progress pre-sinterings, is obtained Porous diamond framework.Finally the copper billet for accounting for part 28.58vol.% is placed in above diamond framework and is put into vacuum together 1100 DEG C are warming up in tungsten filament infiltration stove and is incubated 4 hours, produces Diamond/Cu composite material parts.
Embodiment 2：Prepare the Diamond/Cu composite material parts that diamond volume fraction is 60%
Step 1：Weigh diamond dust 10g, MoO3Powder 24g, salt-mixture NaCl-KCl (mol ratio NaCl:KCl=1: 1) 40g, it is well mixed using mixed powder machine.By mixed-powder be rapidly heated in electric tube furnace be heated to 1050 DEG C insulation 2h, the phase Between be passed through Ar atmosphere protection.Reaction product is cleaned, dried, sieving obtains coating surface Mo2The diamond dust of C layers.
Step 2：Weigh plating Mo2The diamond dust 8g of C layers is placed in 0.4L SnCl2In (30g/L) deionized water solution Surface sensitizing is carried out, is subsequently placed in 0.4L PdCl2Surface active is carried out in (0.25g/L) deionized water solution.Finally will place The diamond dust managed carries out electroless copper, prepares copper sulfate bath 0.280L, and wherein copper sulfate bath formula is： CuSO4·5H2O (15g/L), HCHO (37% aqueous solution, 14ml/L), EDTA (14.5g/L), C4O6H4KNa (14g/L), bigeminy Pyridine (0.02g/L), potassium ferrocyanide (0.01g/L).Plating temperature is 43.5 DEG C, PH=12, Plating times 20min, finally Prepare 5Cu-95Diamond (Mo2C) double coating diamond dusts.
Step 3：Heteropolymer constituent element paraffin based binder is chosen, its each constituent element percentage by weight is PW：HDPE：EVA：= 75：15：10.After the binding agent is kneaded 1.5 hours on kneading machine at a temperature of 130 DEG C with double coating Cu-Mo2C- Diamond powder is kneaded 2 hours, powder loading 63.16vol.% on kneading machine at a temperature of 110 DEG C, after granulation Injection moulding in injector, injection temperature are 150 DEG C, injection pressure 110MPa.By gained preform first in three chloroethenes Degreasing is dissolved in alkene, solution temperature is 40 DEG C, and subsequent preform is warming up to 200 DEG C in vacuum degreasing stove and is incubated 1 hour, then It is warming up to 500 DEG C and is incubated 2 hours to remove binding agent completely.
Step 4：Preform after degreasing is continuously heating to 1150 DEG C, and is incubated 2 hours progress pre-sinterings, is obtained Porous diamond framework.Finally the copper billet for accounting for part 33.68vol.% is placed in above diamond framework and is put into vacuum together 1200 DEG C are warming up in tungsten filament infiltration stove and is incubated 2 hours, produces Diamond/Cu composite material parts.
Embodiment 3：Prepare the Diamond/Cu composite material parts that diamond volume fraction is 50%
Step 1：Weigh diamond dust 10g, MoO3Powder 36g, salt-mixture NaCl-KCl (mol ratio NaCl:KCl=1: 1) 50g, it is well mixed using mixed powder machine.By mixed-powder be rapidly heated in electric tube furnace be heated to 1100 DEG C insulation 1h, the phase Between be passed through Ar atmosphere protection.Reaction product is cleaned, dried, sieving obtains coating surface Mo2The diamond dust of C layers.
Step 2：Weigh plating Mo2The diamond dust 8g of C layers is placed in 0.4L SnCl2In (30g/L) deionized water solution Surface sensitizing is carried out, is subsequently placed in 0.4L PdCl2Surface active is carried out in (0.25g/L) deionized water solution.Finally will place The diamond dust managed carries out electroless copper, prepares copper sulfate bath 0.592L, and wherein copper sulfate bath formula is： CuSO4·5H2O (15g/L), HCHO (37% aqueous solution, 14ml/L), EDTA (14.5g/L), C4O6H4KNa (14g/L), bigeminy Pyridine (0.02g/L), potassium ferrocyanide (0.01g/L).Plating temperature is 43.5 DEG C, PH=12, Plating times 30min, finally Prepare 10Cu-90Diamond (Mo2C) double coating diamond dusts.
Step 3：Heteropolymer constituent element paraffin based binder is chosen, its each constituent element percentage by weight is PW：HDPE：EVA：SA =72：15：10：3.After the binding agent is kneaded 1.5 hours on kneading machine at a temperature of 130 DEG C with double coating Cu-Mo2C- Diamond powder is kneaded 1.5 hours on kneading machine at a temperature of 130 DEG C, powder loading 55.56vol.%, after granulation The injection moulding in injector, injection temperature are 160 DEG C, injection pressure 120MPa.By gained preform first in trichlorine Degreasing is dissolved in ethene, solution temperature is 40 DEG C, and subsequent preform is warming up to 200 DEG C in vacuum degreasing stove and is incubated 1 hour, 500 DEG C are warming up to again is incubated 2 hours to remove binding agent completely.
Step 4：Preform after degreasing is continuously heating to 1150 DEG C, and is incubated 2 hours progress pre-sinterings, is obtained Porous diamond framework.Finally the copper billet for accounting for part 38.88.vol% is placed in above diamond framework and is put into vacuum together 1200 DEG C are warming up in tungsten filament infiltration stove and is incubated 2 hours, produces Diamond/Cu composite material parts.

Claims (5)

1. a kind of method that combination injection molding technology prepares diamond/copper composite, it is characterised in that：Using salt bath plating Technology is in one layer of uniform Mo of diamond surface plating2C is used for improving the wetability of diamond and copper, then using chemical plating Method continues in Mo2C layer surface copper facing, and double coating Buddha's warrior attendants of different thickness of coated copper layer are prepared according to the difference of plating copper mass Stone powder；Then by quantitative Cu-Mo2C-Diamond prepares preform using Powder Injection Molding Technology, the base that will be obtained Body is penetrated into copper liquid in diamond framework by the capillarity of hole by vacuum pressureless infiltration technology, so as to be had There are the diamond/copper composite material parts of high-volume fractional；
Concrete technology step is：
1) diamond dust, the MoO that crystal formation degree is MBD10 and particle mean size is 100 μm are chosen3Powder and salt-mixture NaCl- KCl carries out mechanical batch mixing, then carries out reaction-sintered in logical being rapidly heated in electric tube furnace for Ar gas, makes at high temperature in fused salt MoO3Powder reacts to form Mo with the graphited diamond in surface2C layers, NaCl:KCl mol ratio=1:1；
2) after furnace cooling, obtained product is subjected to ultrasonic alcohol washes and screens out plating Mo2The diamond powder of C layers, is being plated Cover Mo2The diamond powder surface of C layers carries out electroless copper and obtains double coating Cu-Mo2C-Diamond powder；
3) by double coating Cu-Mo2C-Diamond powder and the binding agent prepared according to certain ratio on kneading machine in 110 DEG C~130 DEG C of 1.5~2 hours of mixing, powder loading is 55.56~70.71.vol%, after granulation on injection machine Injection moulding, the diamond preform of required shape is obtained, the then degreasing in vacuum degreasing stove, binding agent is removed and simultaneously carries out Pre-sintering obtains having certain porosity and the diamond framework of intensity；
4) copper billet for accounting for the corresponding 28.58~38.88.vol.% of pore volume of part is placed in above diamond framework and be put into together Heating carries out pressureless infiltration, insulation in infiltration in vacuum stove, naturally cools to room temperature, as composite material parts.
2. the method that a kind of combination injection molding technology according to claim 1 prepares diamond/copper composite, it is special Sign is：Step 1) the diamond dust and MoO3Mol ratio be 10:1~3, the mass ratio of diamond dust and salt-mixture For 1:3~5, reaction-sintered temperature is 1000 DEG C~1100 DEG C, and the time is 1~3h.
3. the method that a kind of combination injection molding technology according to claim 1 prepares diamond/copper composite, it is special Sign is：Step 2) the electroless copper process is as follows：Diamond powder is placed in the SnCl that concentration is 30g/L2Deionized water Surface sensitizing is carried out in solution, is subsequently placed in the PdCl that concentration is 0.25g/L2Surface active is carried out in deionized water solution, most Electroless copper is carried out in the copper sulfate bath prepared afterwards；Wherein copper sulfate bath formula is：CuSO4·5H2O (15g/L), The 37%HCHO aqueous solution (14ml/L), EDTA (14.5g/L), C4O6H4KNa (14g/L), second bipyridine (0.02g/L), ferrous cyanogen Change potassium (0.01g/L)；The acid-base value of plating solution is controlled in PH>11, reaction temperature is controlled at 43 ± 0.5 DEG C；By controlling copper sulphate The dosage of plating solution prepares the different double coating Cu-Mo of cupric volume fraction2C-Diamond powder；Wherein, Cu-Mo2C- The double coating diamond dust cupric volume fractions of Diamond are 1~10vol.%, and the amount of copper sulfate bath is needed for copper facing process 0.007~0.074L/g, Plating times are 10~30min.
4. the method that a kind of combination injection molding technology according to claim 1 prepares diamond/copper composite, it is special Sign is：The binding agent of the step 3) preparation is heteropolymer constituent element paraffinic base (PW) binding agent, with high density polyethylene (HDPE) (HDPE), ethene-vinyl acetate resin copolymer (EVA) is used as plasticizer, with stearic acid (SA) for surfactant, each constituent element Percentage by weight is PW：HDPE：EVA：SA=(70~80)：(10~15)：(5~10)：(0~5)；Injected after feeding granulation Be molded on forming machine, on injection machine forming temperature be 140~160 DEG C, pressure be 100~120MPa, pre-sintering temperature For 1000~1150 DEG C.
5. the method that a kind of combination injection molding technology according to claim 1 prepares diamond/copper composite, it is special Sign is：The temperature that being heated up using vacuum tungsten filament infiltration stove described in step 4) carries out pressureless infiltration is after 1100~1200 DEG C, It is incubated 1~4 hour.
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CN113548909A (en) * 2021-08-12 2021-10-26 有研工程技术研究院有限公司 Diamond-metal interface structure, composite material and preparation method
CN113798496A (en) * 2021-09-16 2021-12-17 南京航空航天大学 Feeding and micro-channel heat sink and preparation method and application thereof
CN113880579A (en) * 2021-11-03 2022-01-04 长沙百川超硬材料工具有限公司 Brazing mixture and method for preparing diamond brazing bead string by using same
CN114192750A (en) * 2021-12-15 2022-03-18 西华大学 Diamond/copper composite heat conducting material and preparation method thereof
CN114231812A (en) * 2021-12-21 2022-03-25 合肥工业大学 AlN-W-Cu composite material and preparation method thereof
CN114749667A (en) * 2022-03-14 2022-07-15 上海喆航航空科技有限公司 Method for manufacturing balance weight alloy of helicopter rotor blade
CN114951607A (en) * 2022-06-09 2022-08-30 北京科技大学广州新材料研究院 Method for preparing graphite foam/Cu composite material by vacuum infiltration method

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1644276A (en) * 2005-01-05 2005-07-27 北京科技大学 Method for producing high-volume fractional silicon-carbide particle reinforced aluminium-base composite material member
CN101845567A (en) * 2010-05-14 2010-09-29 北京科技大学 Method for strengthening diamond powder degreasing blank subjected to injection molding by infiltrating Cu
CN102732764A (en) * 2012-07-20 2012-10-17 哈尔滨工业大学 Preparation method for diamond/copper composite material with high heat conductivity and low thermal expansion coefficient
CN103184363A (en) * 2011-12-28 2013-07-03 北京有色金属研究总院 High-thermal conductivity diamond/copper composite material applicable to wide temperature range and method
CN103981382A (en) * 2014-05-22 2014-08-13 武汉理工大学 Preparation method of high heat-conducting diamond/copper-based composite material
CN104046833A (en) * 2014-06-18 2014-09-17 南昌航空大学 Diamond/copper composite material with high heat-conducting property and preparation method thereof
CN106583735A (en) * 2016-12-22 2017-04-26 北京科技大学 Method for preparing diamond/copper composite material parts with high volume fraction
CN106756906A (en) * 2016-12-22 2017-05-31 北京科技大学 A kind of pair of preparation method of coating diamond dust
CN106756373A (en) * 2016-12-01 2017-05-31 广东正德材料表面科技有限公司 Near net-shaped diamond/copper composite of a kind of high heat conduction and preparation method thereof
CN107312959A (en) * 2017-06-15 2017-11-03 北京科技大学广州新材料研究院 It is a kind of to prepare the method with high-volume fractional diamond/aluminum composite

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1644276A (en) * 2005-01-05 2005-07-27 北京科技大学 Method for producing high-volume fractional silicon-carbide particle reinforced aluminium-base composite material member
CN101845567A (en) * 2010-05-14 2010-09-29 北京科技大学 Method for strengthening diamond powder degreasing blank subjected to injection molding by infiltrating Cu
CN103184363A (en) * 2011-12-28 2013-07-03 北京有色金属研究总院 High-thermal conductivity diamond/copper composite material applicable to wide temperature range and method
CN102732764A (en) * 2012-07-20 2012-10-17 哈尔滨工业大学 Preparation method for diamond/copper composite material with high heat conductivity and low thermal expansion coefficient
CN103981382A (en) * 2014-05-22 2014-08-13 武汉理工大学 Preparation method of high heat-conducting diamond/copper-based composite material
CN104046833A (en) * 2014-06-18 2014-09-17 南昌航空大学 Diamond/copper composite material with high heat-conducting property and preparation method thereof
CN106756373A (en) * 2016-12-01 2017-05-31 广东正德材料表面科技有限公司 Near net-shaped diamond/copper composite of a kind of high heat conduction and preparation method thereof
CN106583735A (en) * 2016-12-22 2017-04-26 北京科技大学 Method for preparing diamond/copper composite material parts with high volume fraction
CN106756906A (en) * 2016-12-22 2017-05-31 北京科技大学 A kind of pair of preparation method of coating diamond dust
CN107312959A (en) * 2017-06-15 2017-11-03 北京科技大学广州新材料研究院 It is a kind of to prepare the method with high-volume fractional diamond/aluminum composite

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109182832A (en) * 2018-11-08 2019-01-11 江苏精研科技股份有限公司 A kind of formula and a kind of powder injection molding process of carbon nanotube reinforced copper-base alloy
CN113548909A (en) * 2021-08-12 2021-10-26 有研工程技术研究院有限公司 Diamond-metal interface structure, composite material and preparation method
CN113798496A (en) * 2021-09-16 2021-12-17 南京航空航天大学 Feeding and micro-channel heat sink and preparation method and application thereof
CN113880579A (en) * 2021-11-03 2022-01-04 长沙百川超硬材料工具有限公司 Brazing mixture and method for preparing diamond brazing bead string by using same
CN114192750A (en) * 2021-12-15 2022-03-18 西华大学 Diamond/copper composite heat conducting material and preparation method thereof
CN114192750B (en) * 2021-12-15 2023-09-22 西华大学 Diamond/copper composite thermal conductive material and preparation method thereof
CN114231812A (en) * 2021-12-21 2022-03-25 合肥工业大学 AlN-W-Cu composite material and preparation method thereof
CN114749667A (en) * 2022-03-14 2022-07-15 上海喆航航空科技有限公司 Method for manufacturing balance weight alloy of helicopter rotor blade
CN114749667B (en) * 2022-03-14 2023-07-21 上海喆航航空科技有限公司 Manufacturing method of helicopter rotor blade balance weight alloy
CN114951607A (en) * 2022-06-09 2022-08-30 北京科技大学广州新材料研究院 Method for preparing graphite foam/Cu composite material by vacuum infiltration method
CN114951607B (en) * 2022-06-09 2023-10-31 北京科技大学广州新材料研究院 Method for preparing graphite foam/Cu composite material by vacuum infiltration method

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