CN103981392B - A kind of preparation method of high-volume fractional diamond/metal-base composites - Google Patents
A kind of preparation method of high-volume fractional diamond/metal-base composites Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of high-volume fractional diamond/metal-base composites, comprise the preparation of hydrolyzed solution, the preparation of slurry, prefabricated component calcining, each unit process of vacuum low-pressure infiltration: be first presoma with tetraethoxy, dehydrated alcohol is as reaction solvent, acid, as catalyzer, prepares teos hydrolysis liquid; Using teos hydrolysis liquid as sizing agent, adopt casting mode to prepare prefabricated biscuit, after high-temperature calcination, obtain diamond porous preform; Adopt the mode of vacuum low-pressure power infiltration to infiltrated metal liquid in diamond porous preform subsequently, achieve the near-net-shape of diamond/metal-base composites.Diamond/metal-base composites prepared by the present invention possesses the advantages such as high heat conduction, low bulk, high-air-tightness, and preparation technology is simple, cost is low, be applicable to batch production.
Description
One, technical field
The present invention relates to a kind of preparation method of matrix material, specifically a kind of preparation method of high-volume fractional diamond/metal-base composites.
Two, background technology
Along with the develop rapidly of semiconductor material, the proposition of particularly high frequency wide bandgap semiconductor evolutionary operation(EVOP), the integrated level of semiconductor components and devices and thermal value will increase greatly.This just needs thermal management materials used for electronic packaging to possess higher thermal conductivity and the thermal expansivity of coupling, causes electronic devices and components temperature component failure that is too high and that cause with the thermal mismatching of packaged material to prevent heat accumulation.Diamond/aluminum (copper/silver) based composites belongs to third generation thermal management materials.Compared with front two generation thermal management materials, the advantage that diamond/aluminum (copper/silver) based composites has that thermal conductivity is high, thermal expansivity and semiconductor material match.Particularly diamond/aluminum based composites also have that density is lower, technique and the advantage such as raw materials cost is lower, will the thermal management materials of new generation having industrialization prospect most be become.
The method preparing aluminium (silver/copper) base diamond matrix material in prior art can be summarized as " single stage method " and " two-step approach "." single stage method " comprises High Temperature High Pressure, conventional hot-press, plasma agglomeration and extrusion casting, and above-mentioned technical matters process is simple, but existence is difficult to prepare complex-shaped heat sink component, the shortcomings such as dimensional precision is low, process costs is high.Wherein high temperature and high pressure method is high and process costs is high to equipment requirements, and conventional hot press method is suitable for preparing the material of lower diamond volume fraction and can not realizes full densification, and extrusion casting required equipment requires higher." two-step approach " mainly refers to diamond prefabricated Infiltration Technics, comprises pressure-free impregnation and Pressure Infiltration.There is the long and temperature of soaking time and cross the shortcomings such as high in pressure-free impregnation technique, this will cause surface reaction excessively and diamond graphitization.The Pressure Infiltration process time is short, can ensure that material interface is controlled, but diamond prefabricated needs to possess certain intensity.
The gordian technique of " two-step approach " is the preparation of diamond prefabricated.The technology of preparing of diamond prefabricated mainly contains die forming, gel injection, injection forming, slurry casting etc., adopts above-mentioned technology to prepare and unavoidably brings impurity in prefabricated component process and the change causing composite property.CN1686945A discloses a kind of method of silicon sol solidification forming ceramic component: adopt tetraethoxy and sodium hydroxide solution to be mixed with water silica sol, then adopts casting legal system for ceramic component using silicon sol as caking agent.US2011/0198771A1 adopts water silica sol mixing diamond particles to prepare slurry, then the mode of slurry casting and calcining is adopted to prepare prefabricated component, achieve diamond particle surfaces modification in the process of body formation simultaneously, finally by liquid forging (the i.e. pressure infiltration of aluminium liquid, pressure is greater than 20MPa), not only eliminate SiO
2dephasign, and improve interface cohesion, significantly improve thermal conductivity.Because water silica sol is poor in diamond particle surfaces wettability, can produce degasification difficulty when applying this technology in slurry preparation process, the shape of final impact cast precast billet and dimensional precision, precast billet needs later stage machining.The pressure higher (being greater than 20MPa) of liquid forging simultaneously, also can affect precast billet shape and dimensional precision.
Three, summary of the invention
The present invention aims to provide the preparation method of a kind of high-volume fractional diamond/metal-base composites.Matrix material of the present invention have that thermal conductivity is high, linear expansivity is adjustable and can with the advantage such as semiconductor components and devices mates.
The preparation method of high-volume fractional diamond/metal-base composites of the present invention, comprises the preparation of hydrolyzed solution, the preparation of slurry, prefabricated component calcining, each unit process of vacuum low-pressure infiltration:
The preparation of described hydrolyzed solution is under 30-60 DEG C of condition, tetraethoxy is slowly added in the mixing solutions of dehydrated alcohol, deionized water and an acidic catalyst composition, under whipped state, be hydrolyzed 0.5-2 hour, then still aging 24-72 hour obtains hydrolyzed solution; Wherein the mol ratio of tetraethoxy, dehydrated alcohol, deionized water, an acidic catalyst (calculating with monoprotic acid) is for 1:(2-6): (0.6-2.4): (0.03-0.06); Described an acidic catalyst is selected from hydrochloric acid, nitric acid, oxalic acid or Glacial acetic acid;
The preparation of described slurry diamond fine powder, carborundum powder or silica flour and diamond meal is loaded in container to mix to obtain mixed powder, mixed by hydrolyzed solution and stir, obtain slurry after dehydrated alcohol dilution with described mixed powder;
Described prefabricated component calcining is that described slurry is transferred to casting in mould, and obtain prefabricated biscuit through air-ammonia two-stage drying, prefabricated biscuit obtains diamond porous preform after high-temperature calcination; The volume fraction that be ensure that reinforcement in porous preform (reinforcement refers to the summation of diamond, silicon carbide and silicon) by grain size distribution is 50%-80%.Calcining can ensure SiO
2gel conversion is amorphous silica or quartz crystal.
Described vacuum low-pressure infiltration is that described diamond porous preform and metal block are loaded graphite jig and be placed in vacuum pressure infiltration stove, by vacuum low-pressure power infiltration, molten metal is infiltrated to enter in the hole of diamond porous preform, obtain diamond/metal-base composites; Described metal block is aluminium alloy, copper alloy or silver alloys.
The granularity of diamond meal described in the preparation process of slurry is 60-300 μm, and the granularity of described diamond fine powder, carborundum powder or silica flour is 10-60 μm; Volume percent >=30% of diamond meal in mixed powder.
In the preparation process of slurry, the volume ratio that mixed powder mixes with the hydrolyzed solution after dilution is 1:(3-5), SiO in the hydrolyzed solution after dilution
2quality account for the 1-5% (content referred to as binding agent) of mixed powder quality.
In prefabricated component calcination process, the mode of casting is without pressure grouting or slip casing by pressure; Be resin mold, metal pattern or mould of plastics without pressure grouting mould; Slip casing by pressure mould is micro-porous resin mould, and grouting pressure is 0.5-1MPa.
Air in prefabricated component calcination process-ammonia two-stage drying refer to first in air atmosphere under normal temperature dry 2-6 hour, then in ammonia atmosphere under normal temperature dry 1-3 hour.
In prefabricated component calcination process, the temperature of prefabricated biscuit high-temperature calcination is 700-1200 DEG C, calcination time 0.5-2 hour, and calcination atmosphere is nitrogen or argon gas.
In vacuum low-pressure infiltration process, each optimum configurations is: vacuum tightness 1Pa-10
-3pa, mechanical pressure 0.1-18MPa.
In vacuum low-pressure infiltration process, when described metal block is aluminium alloy, infiltration temperature is 650-850 DEG C, and the infiltration time is 1-30min; When described metal block is copper alloy, infiltration temperature is 1100-1300 DEG C, and the infiltration time is 1-30min; When described metal block is silver alloys, infiltration temperature is 1000-1200 DEG C, and the infiltration time is 1-30min.
In 300-800 DEG C of annealing 1-4 hour after the process of vacuum low-pressure infiltration process.
The composition of described aluminium alloy is configured to by mass percentage: silicon 0.1-30%, one or more 0.1%-5% in magnesium, copper, titanium, chromium, tungsten, molybdenum, and surplus is aluminium;
The composition of described copper alloy is configured to by mass percentage: silicon 0.1%-20%, one or more 0.1%-5% in magnesium, silver, titanium, boron, chromium, tungsten, molybdenum, aluminium, and surplus is copper;
The composition of described silver alloys is configured to by mass percentage: silicon 0.1-10%, one or more 0.1%-5% in magnesium, copper, titanium, boron, chromium, tungsten, molybdenum, and surplus is Ag.
The present invention adopts the hydrolyzed solution being dissolved in the tetraethoxy of ethanol as sizing agent.Relative to water silica sol system, tetraethoxy system effectively can improve the wettability of caking agent and diamond particle surfaces in casting process, improves precast billet forming accuracy and biscuit intensity; The present invention adopts vacuum low-pressure infiltration mode, ensure that prefabricated component is not damaged in infiltration process.
The detailed process of vacuum low-pressure infiltration is as follows: take metal block as aluminium alloy be example, first described diamond porous preform and Al alloy block are together put into the graphite jig scribbling boron nitride parting agent, then load in pressure infiltration stove and vacuumize, vacuum tightness is 1Pa ~ 10
-3pa; According to the ramp of 10 DEG C/min to after 650-850 DEG C, by mechanical presses the pressure of 1-18MPa applied to melt and maintain 1-30min; 300-800 DEG C of annealing 1-4 hour is cooled to after release; Last furnace cooling.After the demoulding, aluminium alloy unnecessary for composite material surface removed and polish polishing, just obtaining required heat sink component.When metal block be copper alloy and silver alloys time the concrete technology of vacuum low-pressure infiltration and aluminium alloy similar, infiltration temperature is respectively 1100-1300 DEG C and 1000-1200 DEG C.
The bortz powder (diamond meal and fine powder) that the present invention uses is commercially available MBD type bortz powder, and wherein added diamond meal plays main conductive force in heat sink component, and ratio is no less than 30vt%; The diamond fine powder, silica flour or the carborundum powder that added play secondary conductive force, improve the volume fraction of reinforcement, reduce linear expansivity; Add fine powder and diamond meal, point cantact between fine powder and fine powder adding of diamond fine powder, silica flour or carborundum powder in addition, contribute to the bonding effect playing caking agent, improve surface quality and the blank strength of porous preform.
Selected diamond meal and diamond fine powder (or silica flour, carborundum powder) adopt grain size distribution mode ensure that, and in porous preform, reinforcement volume fraction is 50-80%.Because the tap density of reinforcement volume fraction in the precast billet that casting obtains and powder is close, after can adopting grating, the tap density of powder predicts reinforcement volume fraction.
The drying process of slip casting base substrate used is air-ammonia drying process, and concrete mode is first dry air 2-6 hour, rear ammonia Air drying 1-3 hour at normal temperatures.Drying temperature needs strict control, cracks to prevent precast billet.
Diamond/metal-base composites prepared by the present invention have that thermal conductivity is high, linear expansivity is adjustable and can with the advantage such as semiconductor components and devices mates.Wherein, the thermal conductivity of diamond/aluminum based composites can reach 470W/mK, and thermal expansivity is only 5.9ppm/K; The thermal conductivity of diamond/copper based composites can reach 643W/mK, and thermal expansivity is only 5.4ppm/K; The thermal conductivity of diamond/silver-based composite material can reach 679W/mK, and thermal expansivity is only 5.5ppm/K.Can be applicable to the heat sink material of high power semi-conductor LED, microwave electronic device, power electronic devices, can realize mass production, industrialization prospect is wide.
Compared with the prior art, technical superiority of the present invention is embodied in:
(1) complex-shaped heat sink component can be prepared, realize the near-net-shape of precast billet and matrix material;
(2) realize diamond and metallic matrix surface reaction is controlled and metallurgical binding, thermal conductivity is high;
(3) required processing unit requires low, simple to operate, and energy consumption is few.
Four, accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention prepares diamond/metal-base composites.
Fig. 2 is the scale diagrams of diamond porous preform and diamond/aluminum based composites.
Fig. 3 is field emission scanning electron microscope (FE-SEM) photo of diamond porous preform fracture.Wherein the magnification of left figure is 100 times, and the magnification of right figure is 1000 times.As can be seen from Figure 3 in diamond porous preform, diamond meal is closest packing state, and diamond fine powder is filled in meal gap, and adamantine volume fraction is higher; Meal and fine powder, formed by the binding agent of point of contact between fine powder and fine powder and sinter neck, make prefabricated component have certain intensity.
Fig. 4 is the X-ray analysis figure of diamond porous preform (left side) and diamond/aluminum based composites (right side).As can be seen from Figure 4 in diamond, silica dioxide gel changes quartzy phase into after calcining; Prepared matrix material main component is diamond phase and aluminium phase, and containing a certain amount of silicon phase.
Fig. 5 is the fracture apperance photo of diamond/aluminum based composites.As can be seen from Figure 5 the microtexture of diamond/aluminum based composites is fine and close, and interface cohesion is good; Part diamond coarse particles is higher because of interface bond strength, and brittle rupture occurs.
Fig. 6 is energy spectrum analysis (EDS) the line sweep figure of the micro interface of diamond/aluminum based composites.The interface Elemental redistribution of diamond and aluminium as seen from Figure 6.
Five, embodiment
The following describes embodiments of the present invention, but protection scope of the present invention is not limited with embodiment, should be as the criterion with claims.
Embodiment 1:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 150-180 micron), diamond fine powder (particle diameter 8-20 micron) and Al alloy block (silicon 7%, magnesium 0.5%, surplus is Al).
1, the preparation of hydrolyzed solution
At normal temperatures 3mol dehydrated alcohol, 1mol water and 0.05mol concentrated hydrochloric acid (mass concentration 36.5%) are mixed, be warming up to 45 DEG C of insulations, then add 1mol tetraethoxy under magnetic stirring, after hydrolysis 1h, stop heating; Leave standstill 24h after being down to room temperature and obtain hydrolyzed solution.
2, the preparation of slurry
Diamond fine powder 1.5g and diamond meal 3.5g are loaded in container to mix and obtain mixed powder, measure the hydrolyzed solution of 0.6mL step 1 preparation, after the volume ratio dilution of hydrolyzed solution and dehydrated alcohol 1:1, add mixing in mixed powder and obtain slurry.
3, prefabricated component calcining
Slurry step 2 obtained is transferred to degasification in the square metal mould of 30 × 30 and shakes flat, is placed in air dry 3 hours at normal temperatures, and to be placed in ammonia loft drier dry 2h at normal temperatures, and then the demoulding obtains prefabricated biscuit, and size is about 30*30*2.5; Prefabricated biscuit being placed horizontally at corundum burns in boat, and then under an argon atmosphere in 850 DEG C of calcinings 1 hour, the volume fraction of the body that is enhanced is the diamond porous preform of 76%.
4, vacuum low-pressure infiltration
Diamond porous preform step 3 obtained and Al alloy block load in the graphite jig scribbling boron nitride parting agent in the lump, then be placed in vacuum pressure infiltration stove to vacuumize, vacuum tightness is 1Pa, according to 10 DEG C/min ramp to 740 DEG C, then pressure infiltration is carried out, added mechanical pressure is 8MPa, maintains 30min; Be cooled to 450 DEG C of annealing 4 hours, then furnace cooling; Remove remained on surface aluminium alloy after the demoulding, polishing polishes, and obtains diamond/aluminum based composites.Be processed into numerical control laser cutter
with the sample of 25 × 2.5 × 2.5, adopting the resistance to LFA457 of speeding laser heat conducting instrument and the resistance to DIL402C of speeding thermal dilatometer to measure its normal temperature thermal conductivity is respectively 448W/mK, and average coefficient of linear expansion is 6.1ppm/K (30-200 DEG C).
Embodiment 2:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 150-180 micron), diamond fine powder (particle diameter 8-20 micron) and Al alloy block (silicon 7%, magnesium 0.5%, surplus is aluminium).
The present embodiment preparation process is with embodiment 1, and be 750 DEG C unlike the calcining temperature of biscuit prefabricated in step 3 in argon gas atmosphere, in the diamond porous preform prepared, the volume fraction of reinforcement is 76%; In step 4, the infiltration time of vacuum pressure infiltration is 15min.The normal temperature thermal conductivity of the diamond/aluminum based composites that the present embodiment prepares is 362W/mK, and average coefficient of linear expansion is 6.5ppm/K (30-200 DEG C).
Embodiment 3:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 150-180 micron), diamond fine powder (particle diameter 8-20 micron) and Al alloy block (titanium 0.5%, surplus is aluminium).
The present embodiment preparation process is with embodiment 1, and difference is that in step 3, the calcining temperature of prefabricated biscuit in argon gas atmosphere is 950 DEG C, and in the diamond porous preform prepared, the volume fraction of reinforcement is 76%.The normal temperature thermal conductivity of the diamond/aluminum based composites that the present embodiment prepares is 470W/mK, and average coefficient of linear expansion is 6.0ppm/K (30-200 DEG C).
Embodiment 4:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 150-180 micron), diamond fine powder (particle diameter 8-20 micron) and Al alloy block (silicon 12%, copper 1%, surplus is aluminium).
The present embodiment preparation process is with embodiment 1, and difference is the infiltration temperature of vacuum pressure infiltration in step 4 is 700 DEG C.The normal temperature thermal conductivity of the diamond/aluminum based composites that the present embodiment prepares is 438W/mK, and average coefficient of linear expansion is 5.9ppm/K (30-200 DEG C).
Embodiment 5:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 150-180 micron), diamond fine powder (particle diameter 8-20 micron) and fine aluminium block (99.9%).
The present embodiment preparation process is with embodiment 1, and difference is the infiltration temperature of vacuum pressure infiltration in step 4 is 780 DEG C.The normal temperature thermal conductivity of the diamond/aluminum based composites that the present embodiment prepares is 298W/mK, and average coefficient of linear expansion is 7.1ppm/K (30-200 DEG C).Comparative example 1-4, the heat conductivity showing to adopt the aluminum substrate not adding alloying element to prepare is lower.
Embodiment 6:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 90-106 micron), diamond fine powder (particle diameter 8-20 micron) and Al alloy block (silicon 7%, magnesium 0.5%, surplus is aluminium).
The present embodiment preparation process with embodiment 1, difference be in step 2 to add binder amount be 1.3%, in the diamond porous preform that step 3 prepares, the volume fraction of reinforcement is 71%.The diamond/aluminum based composites that the present embodiment prepares normal temperature thermal conductivity be 496W/mK, average coefficient of linear expansion is 4.8ppm/K (30-200 DEG C).Comparative example 1, illustrates can prepare volume fraction and the adjustable diamond/aluminum matrix material of linear expansivity by different grain size distributions.
Embodiment 7:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 90-106 micron), carbide fine powder (particle diameter 8-20 micron) and Al alloy block (silicon 7%, magnesium 0.5%, surplus is aluminium).
The present embodiment preparation process with embodiment 1, difference be in step 3 to add binder amount be 1.3%, in the diamond porous preform that step 3 prepares, the volume fraction of reinforcement is 68%.The diamond/aluminum based composites that the present embodiment prepares normal temperature thermal conductivity be 405W/mK, average coefficient of linear expansion is 7.6ppm/K (30-200 DEG C).Comparative example 6, illustrate that the thermal conductivity of matrix material is still higher, illustrates that diamond meal plays main enhanced thermal conduction effect in the composite by adopting carbide fine powder to substitute diamond fine powder; Linear expansivity is higher, is because the linear expansivity of silicon carbide is larger than the adamantine coefficient of expansion.
Embodiment 8:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 90-106 micron), silica fine powder (particle diameter 8-20 micron) and Al alloy block (silicon 7%, magnesium 0.5%, surplus is aluminium).
The present embodiment preparation process with embodiment 1, difference be in step 3 to add binder amount be 1.3%, the calcining temperature of prefabricated biscuit is 1200 DEG C, and calcination atmosphere is nitrogen, and in the diamond porous preform prepared, the volume fraction of reinforcement is 69%.The normal temperature thermal conductivity of the diamond/aluminum based composites that the present embodiment prepares is 405W/mK, and average coefficient of linear expansion is 7.5ppm/K (30-200 DEG C).Comparative example 6 and 7, illustrate that the thermal conductivity of matrix material is still higher, illustrates that diamond meal plays main enhanced thermal conduction effect in the composite by adopting silica fine powder to substitute diamond or carbide fine powder; Linear expansivity is higher, is because the linear expansivity of silicon is larger than the adamantine coefficient of expansion.
Embodiment 9:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 150-180 micron), diamond fine powder (particle diameter 8-20 micron) and copper alloy block (chromium 0.5%, surplus is Cu).
The present embodiment preparation process, with embodiment 1, is copper alloy block unlike metal block in step 4, and the infiltrating temperature of vacuum low-pressure infiltration is 1150 DEG C, and infiltration pressure is 12MPa and maintains 5min, then anneals 4 hours under 600 DEG C of conditions, furnace cooling.The normal temperature thermal conductivity of the diamond/copper based composites that the present embodiment prepares is 625W/mK, and average coefficient of linear expansion is 5.8ppm/K (30-200 DEG C).
Embodiment 10:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 150-180 micron), diamond fine powder (particle diameter 8-20 micron) and copper alloy block (boron 0.4%, surplus is Cu).
The present embodiment preparation process, with embodiment 1, is copper alloy block unlike metal block in step 4, and the infiltrating temperature of vacuum low-pressure infiltration is 1150 DEG C, and infiltration pressure is 12MPa and maintains 10min, then anneals 4 hours under 600 DEG C of conditions, furnace cooling.The normal temperature thermal conductivity of the diamond/copper based composites that the present embodiment prepares is 643W/mK, and average coefficient of linear expansion is 5.4ppm/K (30-200 DEG C).
Embodiment 11:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 150-180 micron), diamond fine powder (particle diameter 8-20 micron) and silver alloys block (titanium 2%, surplus is silver).
The present embodiment preparation process, with embodiment 1, is silver alloys block unlike metal block in step 4, and the infiltrating temperature of vacuum low-pressure infiltration is 1100 DEG C, and infiltration pressure is 10MPa and maintains 10min, then anneals 4 hours under 500 DEG C of conditions, furnace cooling.The normal temperature thermal conductivity of diamond/silver-based composite material that the present embodiment prepares is 679W/mK, and average coefficient of linear expansion is 5.5ppm/K (30-200 DEG C).
Embodiment 12:
Raw material: adopt analytical pure tetraethoxy (dioxide-containing silica is 28.8%), commercially available MBD6 type diamond meal (particle diameter 150-180 micron), diamond fine powder (particle diameter 8-20 micron) and silver alloys block (silicon 3%, surplus is silver).
The present embodiment preparation process, with embodiment 1, is silver alloys block unlike metal block in step 4, and the infiltrating temperature of vacuum low-pressure infiltration is 1100 DEG C, and infiltration pressure is 10MPa and maintains 10min, then anneals 4 hours under 500 DEG C of conditions, furnace cooling.The normal temperature thermal conductivity of diamond/silver-based composite material that the present embodiment prepares is 658W/mK, and average coefficient of linear expansion is 5.8ppm/K (30-200 DEG C).
Table 1 is the preparation technology parameter of diamond porous preform in embodiment 1-12, and table 2 is the performance of Infiltration Technics parameter and matrix material in embodiment 1-12.
The preparation technology parameter of diamond porous preform in table 1 embodiment 1-12
* binder content refers to SiO in the hydrolyzed solution after diluting
2quality account for the mass percent of mixed powder.
The performance of Infiltration Technics parameter and matrix material in table 2 embodiment 1-12
Claims (7)
1. a preparation method for high-volume fractional diamond/metal-base composites, comprises the preparation of hydrolyzed solution, the preparation of slurry, prefabricated component calcining, each unit process of vacuum low-pressure infiltration, it is characterized in that:
The preparation of described hydrolyzed solution is under 30-60 DEG C of condition, and added by tetraethoxy in the mixing solutions of dehydrated alcohol, deionized water and an acidic catalyst composition, under whipped state, be hydrolyzed 0.5-2 hour, then still aging 24-72 hour obtains hydrolyzed solution; Wherein the mol ratio of tetraethoxy, dehydrated alcohol, deionized water, an acidic catalyst is 1:(2-6): (0.6-2.4): (0.03-0.06); Described an acidic catalyst is selected from hydrochloric acid, nitric acid, oxalic acid or Glacial acetic acid;
The preparation of described slurry diamond fine powder, carborundum powder or silica flour and diamond meal is loaded in container to mix to obtain mixed powder, mixed by hydrolyzed solution and stir, obtain slurry after dehydrated alcohol dilution with described mixed powder; The granularity of diamond meal described in the preparation process of slurry is 60-300 μm, and the granularity of described diamond fine powder, carborundum powder or silica flour is 10-60 μm; Volume percent >=30% of diamond meal in mixed powder;
Described prefabricated component calcining is that described slurry is transferred to casting in mould, and obtain prefabricated biscuit through air-ammonia two-stage drying, prefabricated biscuit obtains diamond porous preform after high-temperature calcination;
Described vacuum low-pressure infiltration is that described diamond porous preform and metal block are loaded graphite jig and be placed in vacuum pressure infiltration stove, by vacuum low-pressure power infiltration, molten metal is infiltrated to enter in the hole of diamond porous preform, obtain diamond/metal-base composites; Described metal block is aluminium alloy, copper alloy or silver alloys; In vacuum low-pressure infiltration process, each optimum configurations is: vacuum tightness 1Pa-10
-3pa, mechanical pressure 0.1-18MPa; In vacuum low-pressure infiltration process, when described metal block is aluminium alloy, infiltration temperature is 650-850 DEG C, and the infiltration time is 1-30min; When described metal block is copper alloy, infiltration temperature is 1100-1300 DEG C, and the infiltration time is 1-30min; When described metal block is silver alloys, infiltration temperature is 1000-1200 DEG C, and the infiltration time is 1-30min.
2. preparation method according to claim 1, is characterized in that:
In the preparation process of slurry, the volume ratio that mixed powder mixes with the hydrolyzed solution after dilution is 1:(3-5), SiO in the hydrolyzed solution after dilution
2quality account for the 1-5% of mixed powder quality.
3. preparation method according to claim 1, is characterized in that:
In prefabricated component calcination process, the mode of casting is without pressure grouting or slip casing by pressure; Be resin mold, metal pattern or mould of plastics without pressure grouting mould; Slip casing by pressure mould is micro-porous resin mould, and grouting pressure is 0.5-1MPa.
4. preparation method according to claim 1, is characterized in that:
Air in prefabricated component calcination process-ammonia two-stage drying refer to first in air atmosphere under normal temperature dry 2-6 hour, then in ammonia atmosphere under normal temperature dry 1-3 hour.
5. preparation method according to claim 1, is characterized in that:
In prefabricated component calcination process, the temperature of prefabricated biscuit high-temperature calcination is 700-1200 DEG C, calcination time 0.5-2 hour, and calcination atmosphere is nitrogen or argon gas.
6. preparation method according to claim 1, is characterized in that:
In 300-800 DEG C of annealing 1-4 hour after the process of vacuum low-pressure infiltration process.
7. preparation method according to claim 1, is characterized in that:
The composition of described aluminium alloy is configured to by mass percentage: silicon 0.1-30%, one or more 0.1%-5% in magnesium, copper, titanium, chromium, tungsten, molybdenum, and surplus is aluminium;
The composition of described copper alloy is configured to by mass percentage: silicon 0.1%-20%, one or more 0.1%-5% in magnesium, silver, titanium, boron, chromium, tungsten, molybdenum, aluminium, and surplus is copper;
The composition of described silver alloys is configured to by mass percentage: silicon 0.1-10%, one or more 0.1%-5% in magnesium, copper, titanium, boron, chromium, tungsten, molybdenum, and surplus is Ag.
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| CN104174814A (en) * | 2014-09-16 | 2014-12-03 | 沈阳飞机工业（集团）有限公司 | Ethyl silicate hydrolysate and preparation method and application thereof |
| CN104611590B (en) * | 2015-01-21 | 2017-06-13 | 上海交通大学 | High-volume fractional primary silicon reinforced aluminum matrix composites dilution extruding filtering preparation method |
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