CN100591644C - High heat conductivity and high strength density heterogeneous foamed SiC/Cu material and its preparing method - Google Patents
High heat conductivity and high strength density heterogeneous foamed SiC/Cu material and its preparing method Download PDFInfo
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Abstract
The present invention relates to heterogeneous foamed ceramic/metal material, and is especially a kind of high strength, high density and high heat conductivity heterogeneous foamed SiC/Cu material and its preparation process. The foamed SiC/Cu material has basic units of closed polygonal ring to form connected 3D network structure, and each of the closed polygonal ring units is heterogeneous foamed ribs comprising SiC in 50-95 vol% and metal Cu in 5-50 vol% and with the relative density not lower than 99 %. The foamed SiC/Cu material is prepared through organic foam soaking, hot pressing to densify, pressure injection filling, thermal decomposition and reaction sintering. The preparation process is simple and low in cost.
Description
Technical field
The invention belongs to ceramic/metal complex phase mesh perforated foams and technology of preparing thereof, foam materials (being called for short the SiC/Cu foam materials) of high-strength, the high densification that a profit is made up of silicon carbide and metal Cu, high heat conduction and preparation method thereof is provided especially.
Technical background
The mesh perforated foams by the body material skeleton, can change the aperture, higher porosity is formed, such material has the three-dimensional network skeleton structure and pore is interconnected, and is a kind of important multifunctional material.Such foam materials mainly contains foamed metal and foamed ceramics two big classes at present.Foamed metal has multiple functions such as damping, sound, heat, electromagnetic shielding, and its appearance meets this material new development trend of structured material multifunction, thereby nearly ten years are developed rapidly.Foamed ceramics is except the general characteristic that has porous ceramics and have, it also has high permeability, high-ratio surface and complicated characteristics such as pore passage structure, these characteristics make it can be used as high temperature filtration, purification, absorption, separation, mixing, heat insulation and heat exchange device in industries such as metallurgy, chemical industry, machinery, environmental protection, the energy, use very extensive.
The preparation method of foam metal material mainly contains metal deposition, powder metallurgy (PM) method, casting etc.Metal deposition be by the atomic state metal after organic porous matrix internal surface deposition, removing organism and sintering forms, this class porous metal porosity communication, porosity height (＞80%), has three-dimensional net structure, say it is a kind of type material of excellent performance in a sense, but its characteristic has determined its strength property to be very restricted, and production efficiency is not high; Powder metallurgy (PM) method is development a kind of method early, and this method is as raw material, through the process of moulding and sintering manufacturing porous metal with metal-powder (or powder mix of metal-powder and non-metal powder).But such porous metal aperture is mostly less than 0.3mm, and porosity generally is not higher than 30%, and article shape, size are very restricted; Casting prepares porous metal and is mostly to be formed after the foam process cooled and solidified by molten metal or alloy; Or rare gas element is blown into molten metal forms a large amount of bubble postcooling and solidify formation; Or make model with the organic foam of three-dimensional net structure, molten metal is flowed into remove organism in the model hole after the cooled and solidified and obtain, but goods mostly are the porous material of closed pore crack or half through hole greatly, and the material preparation cost is very high.
The foam silicon carbon pottery has following four kinds of methods preparation: powder sintering, solid state reaction sintering process, contain silicone resin pyrolysis method and vapour deposition process.Powder sintering is divided into two kinds of different processes again.After the first will contain the slip of the carborundum powder of a certain amount of sintering aid and linking agent (as ethyl silicate hydrolyzed solution, silicon sol etc.) furnishing suitable concn, soak and hang on the polyurethane foam, after solidifying drying, deviate from linking agent and polyurethane foam 200～600 ℃ of scopes.Then, temperature is elevated to carries out sintering between 1500～2200 ℃ and just obtain foamed silicon carbide ceramics; Another kind method is with after containing the carborundum powder and strain shape whipping agent uniform mixing of sintering aid, with mold pressing or pouring procedure moulding.Deviate from whipping agent by fusing or gasification, carry out high temperature sintering then to obtain the spumescence silicon carbide ceramics; The solid state reaction sintering process is with strain shape whipping agent and silica flour and the moulding of carbon dust uniform mixing.Deviate from whipping agent by fusing or gasification, through promptly obtaining the spumescence silicon carbide ceramics behind the pyroreaction sintering; Containing the silicone resin pyrolysis method is that the organosilicon presoma is made high-molecular gel, obtains the foamed silicone resin that contains after deviating from the organic solvent in the gel, carries out pyrolysis and promptly obtain the spumescence silicon carbide ceramics after fully giving oxidation; To be the method for utilizing chemical vapour deposition with silicon carbide deposit on the netlike carbon fiber knitted body vapour deposition process and obtain the spumescence silicon carbide ceramics.Above-mentioned four kinds of methods all have deficiency separately.First three methods is not owing to there is hot pressing, and initial density is not high, and the spumescence silicon carbide ceramics of preparation is not fine and close, thereby intensity is low, and solid state reaction sintering process and contain silicone resin pyrolysis method volume of voids and size is difficult to control; And vapour deposition process faces the cost of manufacture height, and speed waits problem slowly.These problems make the application of spumescence silicon carbide ceramics, and particularly new application is subjected to restriction in various degree.
Tradition mesh porous foam ceramic is because the unicity that the matrix framework material is formed, or be metal or for ceramic, and makes its performance have limitation, and then limits the multifunctionality of its use.Metal foam is easily oxidation in high temperature, and intensity is reduced greatly, and hardness generally is not very high, and wear resisting property is poor, especially under the washing away of high temperature even high pressure fluid the mis-behave embodiment still be remarkable.Ceramic foam is high temperature resistant, corrosion-resistant, but heat conductivility is not high, poor high temperature stability, especially the intrinsic fragility of ceramic intrinsic become its as structural element biggest obstacle, and processing and install and all to have a technical difficult problem that is difficult to overcome, adopt the Research on Toughening of ZrO2 particle or fiber grade in an imperial examination two relative stupaliths a lot of at present, also have to adopt and prepare the method that ceramic matric composite comes the reinforcing structure pottery, it is very difficult that but these methods are applied in the preparation of porous ceramics, and effect is also not obvious, if in the mesh porous foam, metal and ceramic fusion are got up, form a kind of base material and strengthening phase and be continuous state, and make the two become three-dimensional successive structure separately at micro-scale, the high tenacity that just can utilize metal is to the three-dimensional toughness that increases the mesh porous foam ceramic that connects of ceramic phase base material, improve anti-brittle failure ability of foamed ceramics and thermostability, the lot of advantages of metallic substance is (as Cu simultaneously, Al etc. have high heat conduction, high electricity is led) also can in pottery, play a role and improve the relevant characteristic of foamed ceramics, it is high tough to make foamed ceramics obtain under dystectic situation like this, hardness is big, strong anti-oxidant and wear resistance, and have certain ductility and good thermal stability.
Summary of the invention
The object of the present invention is to provide SiC/Cu complex phase foam materials of a kind of high heat conduction, high-strength high-density and preparation method thereof, the SiC/Cu complex phase foam materials of the present invention's preparation has the characteristics of high heat conduction, and pore structure (aperture and void content) can be regulated and control, structural uniformity is good, has high-compactness, high strength and high reliability concurrently.Preparation method's technology provided by the invention is simple, easy to operate, need not complex apparatus, low cost of manufacture.
Technical scheme of the present invention is:
The invention provides the SiC/Cu complex phase foam materials of a kind of high heat conduction, high-strength high-density, wherein said SiC/Cu complex phase foam materials is an elementary cell with polygonal Closed loop, and each elementary cell is interconnected to form three-dimensional networks; Constitute the unitary three-dimensional network muscle of Polygons Closed loop and comprise silicon carbide and copper metallographic phase, and form to regulate and control, percentage ratio meter by volume, silicon carbide can change 95～50%, and the copper metallographic phase can change 5～50%; The relative density of three-dimensional network muscle 〉=99%, average grain size is at 1 μ m-15 μ m.
The present invention also provides the preparation method of the SiC/Cu complex phase foam materials of above-mentioned high heat conduction, high-strength high-density, it is characterized in that: with the mixed powder of carborundum powder, silica flour or carborundum powder and silica flour and the macromolecular material that has than high carbon output rate is raw material, with the urethane foam is template, and preparation process is as follows:
(1) slip preparation
Powder of solid particles, macromolecular material, solidifying agent and organic solvent are mixed in proportion, weight percent is 70wt%～20wt%: 20wt%～70wt%: 1wt%～10wt% between powder of solid particles, macromolecular material and the solidifying agent, ball milling after mechanical stirring, filter, get slip, described slurry solution solute is 5～70% of a gross weight;
(2) soak extension
Urethane foam is cut into desired shape and size, immerse in the slip equably, take out afterwards to squeeze and go unnecessary slip, employing air-blowing or centrifugal mode to remove unnecessary slip, the heating semicure, under 50～80 ℃ of temperature, solidify, 5～60 minutes time, the above-mentioned material, material extrusion, solidification process of soaking repeats repeatedly, reaches needed percent by volume 5-85%, obtains the foamed ceramics precast body;
(3) hot-pressing densification
Foamed ceramics prefabricated skeleton body is put into high pressure vessel, charge into nitrogen or argon gas high temperature, high pressure curing, obtain fine and close foamed ceramics presoma.
(4) pyrolysis
The foamed ceramics presoma of densification under the protection of argon gas, nitrogen or other rare gas element or pyrolysis under vacuum condition, is generated the foamy carbon skeleton; Wherein the temperature rise rate per minute is 1～10 ℃, is warming up to 800～1200 ℃, is incubated 0.5～2 hour;
(5) liquid phase reaction infiltration
The foamy carbon skeleton of the densification after the pyrolysis is required accurate geomery through being machined to; carry out the reaction sintering infiltration then; infiltration carries out under protection of inert gas atmosphere or vacuum condition; temperature rise rate is 1～50 ℃ of per minute (being preferably 5～20 ℃); melt temperature is: 1400～1900 ℃; be incubated 0.5～5 hour, get foam SiC/Cu complex phase foam materials.
Macromolecular material of the present invention can be selected from one or more of Resins, epoxy, resol, furfuryl resin; Organic solvent can be acetone, ethanol or formaldehyde etc., solvent volume concentration 〉=75%, the powder of solid particles that can also sneak in described macromolecular material can be the mixed powder of carborundum powder, silica flour or carborundum powder and silica flour, the mean particle size of powder can be between 10nm～25 μ m, silica flour and carborundum powder purity are more than 95%, add-on is 5～90% (percent by volumes), is good with 40～60% percent by volumes.When adopting carborundum powder and silica flour mixed powder, the two part by weight is 20～80%: 80～20%.
Solidifying agent of the present invention is: product, oxalic acid or citric acid etc. are taken off in tosic acid, five Lip rivers, and content is 1～40% of amount of resin, is good with 2～8%, heat curing temperature between 100～250 ℃, 10 minutes～2 hours time.
In hot-pressing densification process of the present invention, pressure is that 5～22MPa, temperature are that heat-up rate is 1～5 ℃/min, is incubated 10 minutes～3 hours at 100～300 ℃.
In pyrolytic process of the present invention, 1～10 ℃ of temperature rise rate per minute, best 800～1200 ℃ of pyrolysis temperature is incubated 0.5～2 hour; Best 2～4 ℃/min of temperature rise rate.
The raw material of selecting for use in the reaction sintering infiltration of the present invention is a cupro silicon, and the content of Si can also add other useful metallic elements at 90～10% (by weight percentage) in the alloy, as: Al, Ni, Co, Ti, Zr, Cr, Mo, Be etc.A conventional oven or shrinking machine are adopted in curing in the sluny impregnation process of the present invention; The high pressure vessel that foam framework precast body hot-pressing densification adopts is reactor or hot isostatic press; The pyrolysis stove is carbon tube furnace or vacuum induction process furnace; The sintering stove is vacuum induction sintering oven, vacuum carbon tube furnace or vacuum resistance furnace.
The present invention is particularly: the polymer of powder of solid particles (carborundum powder, silica flour or the two mixed powder) and high carbon output rate is mixed and made into slip.Select the urethane foam in suitable aperture, and be cut into needed shape and size, then it is immersed in the slip, after the taking-up, remove unnecessary slip with extruding, wind, mode such as centrifugal, semicure repeats repeatedly, to reaching needed percent by volume, obtain the foamed ceramics precast body.High temperature, high pressure solidify in high pressure vessel, to improve the initial density of foamed ceramics prefabricated skeleton body.Foams after solidifying are carried out urethane remove and the resin pyrolysis in vacuum or inert atmosphere furnace, obtain and the equiform spumescence carbon skeleton of forming by solid powder particle and RESEARCH OF PYROCARBON of original foamed polyurethane.
In the reaction sintering infiltration; it is overheated that the cupro silicon melt is melted under vacuum or protective atmosphere; and then the carbon in the carbon skeleton and gas phase or liquid-phase silicone reaction generation silicon carbide; and combine with original silicon-carbide particle in the foam framework; wherein the space that produces after the organic polymer pyrolysis is then filled by the cupro silicon melt, the SiC/Cu complex phase foam materials that cools down like this and obtain high heat conduction, high-strength high-density.
The present invention prepares in organic foam body impregnation technology on the technology basis of foamed ceramics and has developed a kind of high reliability SiC/Cu complex phase foam materials for preparing high heat conduction, high strength, high-compactness, has following advantage:
1, the SiC/Cu foam materials has characteristics such as the easy control of porous, high-ratio surface, high through-hole rate, aperture and voidage.
Urethane foam is the primary template that obtains final SiC/Cu foam materials, thereby by selecting different templates just can control pore size in the three-dimensional net structure; For same template, can hang number of times and pulp density by selecting to soak to soak in the extension process, realize control, and eliminate closed pores the thickness of ceramic volumetric percentage ratio in the foam preform and prefabricated skeleton body muscle.Fig. 1 is the SiC/Cu foam materials photo in kind that is made by the present invention.
2, high strength, high-compactness, good mechanical performance
The present invention adopts the method for the organic compound prefabricated skeleton body of hot-press solidifying foam, can significantly improve its initial density and homogeneity of structure, eliminates demixing phenomenon, and then avoids " dead skin is hollow " problem of causing because of layering; Adopt the liquid phase reaction infiltration that the network muscle of SiC/Cu foam materials is had near 100% relative density and the even fine and closely woven microstructure of 0.5-15 μ m, can also make simultaneously silicon and the reaction of the carbon in the carbon skeleton in the metal solution generate silicon carbide, and the original silicon-carbide particle in the foam framework is firmly bonded to together in chemically combined mode, have very high bonding strength in the network muscle between ceramic phase thereby make.Meanwhile, the Cu silicon alloy is filled in the space that stays after the prefabricated skeleton body heat is separated, and forms the three-dimensional net structure of mutual perforation on micro-meter scale with silicon carbide.Above factor makes the SiC/Cu foam materials possess higher intensity simultaneously.(seeing accompanying drawing 2,3).
3, pottery, metallographic phase adjustable ratio, the metallographic phase composition is adjustable
In the slip layoutprocedure, the ratio of SiC powder and organic polymer resin can be produced the even hole of different volumes ratio in the adjusting powder of solid particles in the carbon skeleton precast body, these uniform holes are filled by the infiltrated metal raw material in the liquid phase reaction infiltration, and then can obtain the metallographic phase of different volumes ratio; The infiltrated metal raw material is selected cupro silicon for use, and the content of Si can also add other useful metallic elements at 90～10% (by weight percentage) in the alloy, as: Al, Ni, Co, Ti, Zr, Cr, Mo, Be etc., the metallographic phase composition is realized adjustable.
4, high heat conduction, high-temperature behavior is good
It consists of SiC and remaining Si traditional foam silicon carbon stupalith, and it is not high that this kind one-tenth is grouped into its heat conductivility of decision, and the foam SiC/Cu sintering metal that the present invention makes consists of SiC and Cu metallographic phase, thereby high heat conductivility is arranged; Traditional metal foam is by its raw-material restriction (as foam Al), and the high temperature use properties is not good, and the foam SiC/Cu sintering metal that the present invention makes can be base by the SiC pottery, and the high temperature use properties is good.
5, good formability and processibility
First, as the primary template of composite material of foamed metal, urethane foam very easily is processed into arbitrary shape; Second, precast body has favorable mechanical and electromachining performance through the carbon skeleton that contains ceramic raw material of pyrolysis or acquisition, the very easy part body that is processed into different shape and dimensional requirement; Three, the liquid phase reaction infiltration almost is a process of not having distortion, and the SiC/Cu foam materials that obtains needn't carry out post-treatment.Above-mentioned 3 factors make the SiC/Cu foam materials possess good formability and processing characteristics, make tooling cost thereby reduce it greatly.
In sum, the invention provides a kind of new, cheap high heat conduction, SiC/Cu complex phase foam materials of high-strength high-density and preparation method thereof.In the method, hot-press solidifying, polymer pyrolysis and reaction sintering are combined, making the SiC/Cu complex phase foam materials of preparing have pore structure can regulate and control, and the characteristics that aperture, voidage are easy to control, ceramic muscle density height (can reach nearly 100%), muscle condition of surface can arbitrarily design, characteristics such as material heat conduction is good, foams intensity height.
Description of drawings
Fig. 1 is the macro morphology of foam SiC/Cu cermet material.
Fig. 2 is the fracture apperance of foam SiC/Cu sintering metal muscle.
Fig. 3 is the microstructure of foam SiC/Cu sintering metal muscle inside.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
The mean particle size 2 μ m carborundum powders, ammonia resol, the tosic acid that mass ratio are respectively 60%: 35%: 5% are dissolved in the dehydrated alcohol altogether, make slip, and described slurry solution solute is 70% of a gross weight; The polyurethane foam of aperture 1mm cut into require to immerse equably in the described slip after the size, soaked 1 minute, squeeze after taking out and remove unnecessary slip, air-dry back 50 ℃ of semicures 10 minutes, the said process repeated multiple times is up to the pre-determined volume percentage ratio (percent by volume of complex phase foam muscle in the finished product) that reaches 70%.Then, put into high pressure vessel, charge into nitrogen and make air pressure reach 12MPa, 2 ℃ of temperature rise rate per minutes are warming up to 250 ℃, are incubated curing in 1 hour.Pyrolysis under argon shield generates carbon skeleton; Wherein the temperature rise rate per minute is 2 ℃, is warming up to 800 ℃, is incubated 0.5 hour.After the pyrolysis, carry out the vacuum reaction infiltration, 1550 ℃ of temperature of reaction, temperature rise rate is 10 ℃/minute, is incubated 1 hour, and the infiltration raw material is Cu78Si20Ti2 (Wt%) alloy, obtain SiC/Cu complex phase foam materials, complex phase foam muscle relative density is 99%, and silicon carbide average crystal grain granularity is 5 μ m, the metallographic phase mean sizes is 5 μ m, complex phase foam muscle consist of SiC, Cu alloy phase, percentage ratio meter by volume is in the complex phase foam muscle, SiC accounts for 85%, and the Cu alloy phase accounts for 15%; Gained SiC/Cu complex phase foam materials thermal conductivity is 55W/ (m*k), and ultimate compression strength is 62MPa.
Embodiment 2
Weight ratio was respectively 45%: 15%: 35%: 5% mean particle size 2 μ m carborundum powders, silica flour, ammonia resol, tosic acid are dissolved in the dehydrated alcohol altogether, make slip, and described slurry solution solute is 60% of a gross weight; The polyurethane foam of aperture 1mm cut into require to immerse equably in the described slip after the size, soaked 1 minute, squeeze after taking out and remove unnecessary slip, air-dry back 50 ℃ of semicures 10 minutes, the said process repeated multiple times is up to the pre-determined volume percentage ratio (percent by volume of complex phase foam muscle in the finished product) that reaches 60%.Then, put into high pressure vessel, charge into nitrogen and make air pressure reach 12MPa, 5 ℃ of temperature rise rate per minutes are warming up to 250 ℃, are incubated curing in 1 hour.Pyrolysis under argon shield generates carbon skeleton; Wherein the temperature rise rate per minute is 2 ℃, is warming up to 800 ℃, is incubated 0.5 hour.After the pyrolysis, carry out the vacuum reaction infiltration, 1550 ℃ of temperature of reaction, temperature rise rate is 10 ℃/minute, is incubated 1 hour, and the infiltration raw material is Cu80Si20 (Wt%) alloy, get SiC/Cu complex phase foam materials, complex phase foam muscle relative density is 99%, and silicon carbide average crystal grain granularity is 5 μ m, the metallographic phase mean sizes is 7 μ m, complex phase foam muscle consist of SiC, Cu alloy phase, percentage ratio meter by volume is in the complex phase foam muscle, SiC accounts for 82%, and the Cu alloy phase accounts for 18%; Gained SiC/Cu complex phase foam materials thermal conductivity is 46W/ (m*k), and ultimate compression strength is 51MPa.
Embodiment 3
The mean particle size 2 μ m carborundum powders, Resins, epoxy (trade mark is EP0141-310), the tosic acid that weight ratio are respectively 40%: 55%: 5% are dissolved in the dehydrated alcohol altogether, make slip, and described slurry solution solute is 50% of a gross weight; The polyurethane foam of aperture 2mm cut into require to immerse equably in the described slip after the size, soaked 1 minute, squeeze after taking out and remove unnecessary slip, air-dry back 50 ℃ of semicures 10 minutes, the said process repeated multiple times is up to the pre-determined volume percentage ratio (percent by volume of complex phase foam muscle in the finished product) that reaches 50%.Then, put into high pressure vessel, charge into nitrogen and make air pressure reach 10MPa, 4 ℃ of temperature rise rate per minutes are warming up to 200 ℃, are incubated curing in 1 hour.Pyrolysis under argon shield generates carbon skeleton; Wherein the temperature rise rate per minute is 2 ℃, is warming up to 900 ℃, is incubated 0.5 hour.After the pyrolysis, carry out the vacuum reaction infiltration, 1650 ℃ of temperature of reaction, temperature rise rate is 20 ℃/minute, is incubated 1 hour, and the infiltration raw material is Cu85Si15 (Wt%) alloy, obtain SiC/Cu complex phase foam materials, complex phase foam muscle relative density is 99%, and silicon carbide average crystal grain granularity is 6 μ m, the metallographic phase mean sizes is 7 μ m, complex phase foam muscle consist of SiC, Cu alloy phase, percentage ratio meter by volume is in the complex phase foam muscle, SiC accounts for 75%, and the Cu alloy phase accounts for 25%; Gained SiC/Cu complex phase foam materials thermal conductivity is 44.5W/ (m*k), and ultimate compression strength is 39MPa.
Embodiment 4
Weight ratio is respectively 40% and 55% heat-reactive phenolic resin and furfuryl resin (wherein, heat-reactive phenolic resin weight ratio 60%, furfuryl resin weight ratio 40%) be dissolved in the dehydrated alcohol altogether with 5% citric acid, make slurry solution, the carborundum powder and the silica flour (part by weight is 30: 80) that with mean particle size are 10 μ m again evenly add in the above-mentioned solution, forming resin/powder volume ratio is 5: 5 slip, and described slurry solution solute is 40% of a gross weight; The polyurethane foam of aperture 1mm cut into require to immerse equably in the described slip after the size, soaked 1 minute, squeeze after taking out and remove unnecessary slip, air-dry back 50 ℃ of semicures 10 minutes, the said process repeated multiple times is up to the pre-determined volume percentage ratio (percent by volume of complex phase foam muscle in the finished product) that reaches 30%.Then, put into high pressure vessel, charge into nitrogen and make air pressure reach 10MPa, 1.5 ℃ of temperature rise rate per minutes are warming up to 200 ℃, are incubated curing in 1 hour.Pyrolysis under argon shield generates carbon skeleton; Wherein the temperature rise rate per minute is 2 ℃, is warming up to 1000 ℃, is incubated 0.5 hour.After the pyrolysis, infiltration under argon shield atmosphere, 1750 ℃ of temperature of reaction, temperature rise rate is 20 ℃/minute, is incubated 1 hour, and the infiltration raw material is Cu87Si10Cr2Zr1 (Wt%) alloy, obtain SiC/Cu complex phase foam materials, complex phase foam muscle relative density is 99%, and silicon carbide average crystal grain granularity is 5 μ m, the metallographic phase mean sizes is 10 μ m, complex phase foam muscle consist of SiC, Cu alloy phase, percentage ratio meter by volume is in the complex phase foam muscle, SiC accounts for 65%, and metallographic phase accounts for 35%; Gained SiC/Cu complex phase foam materials thermal conductivity is 47W/ (m*k), and ultimate compression strength is 19MPa.
Embodiment 5
Weight ratio is respectively 30% and 65% heat-reactive phenolic resin and furfuryl resin (wherein, heat-reactive phenolic resin weight ratio 50%, furfuryl resin weight ratio 50%) taking off product with 5% 5 Lip river is dissolved in the dehydrated alcohol altogether, make slurry solution, the carborundum powder and the silica flour (part by weight is 50: 50) that with mean particle size are 5 μ m again evenly add in the above-mentioned solution, forming resin/powder volume ratio is 6/4 slip, and described slurry solution solute is 45% of a gross weight; The polyurethane foam of aperture 3mm cut into require to immerse equably in the described slip after the size, soaked 1 minute, squeeze after taking out and remove unnecessary slip, air-dry back 50 ℃ of semicures 30 minutes, the said process repeated multiple times is up to the pre-determined volume percentage ratio (percent by volume of complex phase foam muscle in the finished product) that reaches 25%.Then, put into high pressure vessel, charge into nitrogen and make air pressure reach 15MPa, 3.5 ℃ of temperature rise rate per minutes are warming up to 240 ℃, are incubated curing in 1 hour.Pyrolysis under argon shield generates carbon skeleton; Wherein the temperature rise rate per minute is 2 ℃, is warming up to 1200 ℃, is incubated 0.5 hour.Infiltration under argon atmosphere, 1500 ℃ of temperature of reaction, temperature rise rate is 20 ℃/minute, be incubated 1 hour, the infiltration raw material is Cu50Si50 (Wt%) alloy, obtains SiC/Cu complex phase foam materials, complex phase foam muscle relative density is 99%, silicon carbide average crystal grain granularity is 4.5 μ m, and the metallographic phase mean sizes is 10.5 μ m, complex phase foam muscle consist of SiC, Cu alloy phase, percentage ratio meter by volume, in the complex phase foam muscle, SiC accounts for 70%, and the Cu alloy phase accounts for 30%; Gained SiC/Cu complex phase foam materials thermal conductivity is 37.8W/ (m*k), and ultimate compression strength is 26MPa.
Claims (9)
1. the SiC/Cu complex phase foam materials of a high heat conduction, high-strength high-density, it is characterized in that: described foam materials is an elementary cell with polygonal Closed loop, and each elementary cell is interconnected to form three-dimensional networks; The complex phase foam muscle that constitutes three-dimensional networks comprises silicon carbide and copper metallographic phase, percentage ratio meter by volume, and silicon carbide is in 95～50% scopes, and the copper metallographic phase is in 5～50% scopes; Relative density 〉=99% of complex phase foam muscle, average grain size is at 1 μ m-15 μ m.
2. preparation method by the SiC/Cu complex phase foam materials of the described high heat conduction of claim 1, high-strength high-density, it is characterized in that: is raw material with powder of solid particles with the macromolecular material that has than high carbon output rate, with the urethane foam is template, wherein, powder of solid particles is carborundum powder, silica flour or the two powder mix, and concrete preparation process is as follows:
(1) slip preparation
Powder of solid particles, macromolecular material, solidifying agent and organic solvent are mixed in proportion, weight percent is 70wt%～20wt%:20wt%～70wt%:1wt%～10wt% between powder of solid particles, macromolecular material and the solidifying agent, ball milling after mechanical stirring, filter, get slip, described slurry solution solute is 5～70% of a total mass;
(2) soak extension
Urethane foam is cut into desired shape and size, immerse in the slip equably, take out afterwards to squeeze and go unnecessary slip, employing air-blowing or centrifugal mode to remove unnecessary slip, the heating semicure, under 50～80 ℃ of temperature, solidify, 5～60 minutes time, the above-mentioned material, material extrusion, solidification process of soaking repeats repeatedly, reaches needed percent by volume 5-85%, obtains the foamed ceramics precast body;
(3) hot-pressing densification
Foamed ceramics prefabricated skeleton body is put into high pressure vessel, charge into nitrogen or argon gas, high temperature, high pressure solidify, pressure be 5～22MPa, temperature at 100～300 ℃, 1～5 ℃ of heat-up rate be incubated 10 minutes～3 hours, obtains the foamed ceramics presoma of densification;
(4) pyrolysis
The foamed ceramics presoma of densification under the protection of argon gas, nitrogen or other rare gas element or pyrolysis under vacuum condition, is generated the foamy carbon skeleton; Wherein the temperature rise rate per minute is 1～10 ℃, is warming up to 800～1200 ℃, is incubated 0.5～2 hour;
(5) liquid phase reaction infiltration
The foamy carbon skeleton of the densification after the pyrolysis is required accurate geomery through being machined to; carry out the reaction sintering infiltration then; infiltration carries out under protection of inert gas atmosphere or vacuum condition; temperature rise rate is 1～50 ℃ of a per minute; melt temperature is: 1400～1900 ℃; be incubated 0.5～5 hour, get foam SiC/Cu complex phase foam materials.
3. according to the preparation method of the described SiC/Cu complex phase of claim 2 foam materials, it is characterized in that: described macromolecular material is selected from one or more of Resins, epoxy, resol and furfuryl resin.
4. according to the preparation method of the described SiC/Cu complex phase of claim 2 foam materials, it is characterized in that: described organic solvent is ethanol or formaldehyde, solvent volume concentration 〉=75%.
5. according to the preparation method of the described SiC/Cu complex phase of claim 2 foam materials, it is characterized in that: the mean particle size of described carborundum powder and silica flour is 10mm～25 μ m, and silica flour and carborundum powder purity are more than 95%.
6. according to the preparation method of the described SiC/Cu complex phase of claim 2 foam materials, it is characterized in that: when adopting carborundum powder and silica flour mixed powder, the two part by weight is 20～80%: 80～20%.
7. according to the preparation method of the described SiC/Cu complex phase of claim 3 foam materials, it is characterized in that: described solidifying agent is that product, oxalic acid or citric acid are taken off in tosic acid, five Lip rivers, content is 1～40% of amount of resin, solidifies 10 minutes～2 hours time under 100～250 ℃ of temperature.
8. according to the preparation method of the described SiC/Cu complex phase of claim 2 foam materials, it is characterized in that: a conventional oven or shrinking machine are adopted in the curing that slip soaks in the extension process; The high pressure vessel that foam framework precast body hot-pressing densification adopts is reactor or hot isostatic press; The pyrolysis stove is carbon tube furnace or vacuum induction process furnace; The sintering stove is vacuum induction sintering oven, vacuum carbon tube furnace or vacuum resistance furnace.
9. according to the preparation method of the described SiC/Cu complex phase of claim 2 foam materials, it is characterized in that: in the described step (5), the raw material of selecting for use in the reaction sintering infiltration is a cupro silicon, and by weight percentage, the content of Si is 90～10% in the alloy; Perhaps, add one or more of other useful metallic element: Al, Ni, Co, Ti, Zr, Cr, Mo or Be in the cupro silicon.
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| CN104087806B (en) * | 2014-06-23 | 2016-01-13 | 西安交通大学 | Thermal protection SiC-Cu complex phase transpiration cooling material and preparation method thereof |
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| WO2017032382A1 (en) * | 2015-08-25 | 2017-03-02 | Syddansk Universitet | A method of producing a body comprising porous alpha silicon carbide and the body produced by the method |
| CN105420589A (en) * | 2015-11-10 | 2016-03-23 | 宁波市鸿博机械制造有限公司 | Pump shaft |
| CN105779804B (en) * | 2016-03-21 | 2018-01-02 | 中南大学 | A kind of foam framework structure enhancing metal-base composites and preparation method |
| CN107663101B (en) * | 2016-07-28 | 2020-07-10 | 航天特种材料及工艺技术研究所 | Antioxidant SiC foam and preparation method thereof |
| CN108383101B (en) | 2018-05-18 | 2019-12-10 | 山东大学 | Preparation method of polyacrylonitrile-based three-dimensional macroporous carbon block |
| CN108754207B (en) * | 2018-06-27 | 2020-01-03 | 河南泛锐复合材料研究院有限公司 | Preparation method of silicon carbide/Cu composite material |
| CN108796267A (en) * | 2018-07-05 | 2018-11-13 | 西安航空学院 | A method of CuSiCp composite materials are prepared using differential pressure vacuum foundry engieering |
| CN110002877B (en) * | 2019-05-10 | 2022-01-11 | 张永利 | Metal/ceramic composite material based on silicon titanium carbide ceramic and copper and preparation method thereof |
| CN113737045B (en) * | 2021-09-10 | 2022-08-19 | 河南科技大学 | Method for preparing bicontinuous phase SiC/Cu composite material |
| CN113912416B (en) * | 2021-11-10 | 2022-10-11 | 中国航发北京航空材料研究院 | Method for recycling silicon carbide fibers and application |
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