CN102285817B - Ti3SiC2 component containing composite foamed material and preparation method thereof - Google Patents

Ti3SiC2 component containing composite foamed material and preparation method thereof Download PDF

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CN102285817B
CN102285817B CN 201110251661 CN201110251661A CN102285817B CN 102285817 B CN102285817 B CN 102285817B CN 201110251661 CN201110251661 CN 201110251661 CN 201110251661 A CN201110251661 A CN 201110251661A CN 102285817 B CN102285817 B CN 102285817B
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powder
sic
skeleton
foam
constituent element
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CN102285817A (en
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张劲松
高勇
杨振明
徐兴祥
张军旗
曹小明
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Institute of Metal Research of CAS
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Abstract

The invention relates to the field of foam materials, in particular to a Ti3SiC2 component containing composite foamed material and a preparation method thereof, solving the problems of poor electrical conductivity and mechanical property and the like of current traditional foamed ceramic materials. The Ti3SiC2 component containing composite foamed material has a three-dimensional communication network structure, and phase composition is mainly formed by Ti3SiC2 and other binary or ternary compounds of Ti, Si and C. The preparation method comprises the following steps of dipping cut foamed plastic in slurry made from raw material powders, resin and absolute ethyl alcohol, taking the dipped foamed plastic and removing excess slurry, carrying out semi-solidification, high-temperature solidification and thermal decomposition, and obtaining a foamed framework, consisting of the raw material powders and pyrolytic carbon, in the same foam shape; and sintering the foamed framework through a high-frequency induction heating reaction, and finally obtaining the Ti3SiC2 component containing composite foamed material. The invention has the advantages of simple process and no requirement on complex equipment. The prepared composite foamed materials have higher density and compression strength and better electric conductivity.

Description

A kind of Ti that contains 3SiC 2Composite foam material of constituent element and preparation method thereof
Technical field
The present invention relates to the foam materials field, specifically a kind of Ti that contains 3SiC 2Composite foam material of constituent element and preparation method thereof.
Background technology
Foam materials is a kind of special porous material.Its geometry feature is to be elementary cell with the Polygons Closed loop, and the three-dimensional networks that each elementary cell is interconnected to form, the material of this class formation have plurality of advantages such as quality is light, porosity is adjustable, high permeability.Yet present foam ceramic material is as foam SiC, foam Al 2O 3Deng, its electric conductivity is lower, causes the electric conductivity of matrix material not high when the preparation metal-ceramic composite material.Ti 3SiC 2As a kind of typical M N+1AX nCompound, its crystalline structure can be regarded [Ti as 6C] carbide lamella and silicon atom layer alternately arrange the laminate structure that forms, and interlamellar spacing is 0.9nm.Since the interlayer bonding force a little less than, therefore splitting can take place, have potential lubricating property.This constitutional features makes Ti 3SiC 2Have the characteristics significantly different with traditional ceramics: high conductivity (4.5 * 10 6Ω -1M -1), high heat conductance (43W/ (mK)), high heat capacity (588J/ (kgK)), high thermal expansion coefficient (10 * 10 -6℃ -1, 25～1000 ℃), and with metal good mutual matching is arranged.Therefore, with advantage and the Ti of foamy structure 3SiC 2The excellent specific property combination, preparation high conductivity, high abrasion oilness contain Ti 3SiC 2Foam materials, have important significance for theories and application prospect.
In the preparation process of titanium compound foam materials, guarantee that under the prerequisite of the foamy structure that obtains good mesh three-dimensional communication, the density that improves in the foam framework muscle is technological difficulties.Up to now, the preparation of titanium compound foam materials mainly contains following several method: skeleton copies sintering process, foaming sintering, electron beam melting method.
Skeleton copies sintering process: at first a certain amount of sintering aid (as Ni) is mixed with titanium compound powder ball milling, slurry with mixed powder and linking agent (as the 5wt% polyvinyl alcohol water solution) furnishing suitable concn, soak then and hang on the polyurethane foam, after the drying, pyrolysis linking agent and polyurethane foam in 200～500 ℃ of scopes.Temperature is raised to 1600～2200 ℃ carries out sintering and just obtain the titanium compound foam materials, this kind method exists sintered density to remain the problem that further improves.
The foaming sintering is the titanium compound powder that will contain sintering aid with after spherical whipping agent evenly mixes, with mold pressing or pouring type moulding.Deviate from whipping agent by fusing or vaporization mode, then carry out high temperature sintering and obtain foam materials.The porous material that this kind method makes, the three-dimensional communication of mesh remain further to be optimized.
Electron beam melting: under vacuum condition, by computer-aided control, utilize electron beam that the titanium compound powder is carried out local sintering at specific position, prepare the foam materials of desired structure feature at last.This kind method required equipment complex and expensive, the manufacturing cost height is unfavorable for large-scale promotion.
Summary of the invention
The object of the present invention is to provide a kind of Ti of containing 3SiC 2Composite foam material of constituent element and preparation method thereof solves problems such as existing conventional foam stupalith poorly conductive, mechanical property are not high.According to the high reaction activity of titanium elements under hot conditions, utilize the high-frequency induction heating reaction sintering method, prepare the Ti that contains with good density and compressive property 3SiC 2The composite foam material of constituent element is for the metal-ceramic composite material for preparing better conductivity and wear-resisting lubricity provides the foam framework material.
Technical scheme of the present invention is:
A kind of Ti that contains 3SiC 2The composite foam material of constituent element, this contains Ti 3SiC 2The composite foam material of constituent element is by Ti 3SiC 2With SiC, TiC 1-x, Ti 5Si 3C 1-x, zero kind, a kind of or more than one compositions in the Ti-Si binary compound, described TiC 1-xIn 0≤x＜1, Ti 5Si 3C 1-xIn 0≤x≤1, this contains Ti 3SiC 2The composite foam material structure of constituent element is to be elementary cell with the Polygons Closed loop, and each elementary cell is interconnected to form the three-dimensional networks structure.Wherein, Ti 3SiC 2Massfraction be that 5wt%～100wt% (is preferably 20～60wt%).
Among the present invention, the mesh size of three-dimensional networks structure is 0.5mm～5mm, and the skeleton volume fraction is 10%～50%, constitutes interior each thing phase particle mean size of skeleton muscle of Polygons Closed loop unit at 1 μ m～200 μ m.
When the skeleton of three-dimensional networks structure by Ti 3SiC 2, SiC and TiC 1-xDuring composition, Ti 3SiC 2Massfraction is 5wt%～90wt%, and the SiC massfraction is 5wt%～90wt%, TiC 1-xMassfraction is 5wt%～90wt%.
When the skeleton of three-dimensional networks structure by Ti 3SiC 2, when SiC and Ti-Si binary compound are formed, Ti 3SiC 2Massfraction is 5wt%～90wt%, SiC massfraction 5wt%～90wt%, Ti-Si binary compound massfraction 5wt%～90wt%.
When the skeleton of three-dimensional networks structure by Ti 3SiC 2, TiC 1-x, Ti 5Si 3C 1-xDuring composition, Ti 3SiC 2Massfraction is 5wt%～90wt%, TiC 1-xMassfraction is 5wt%～90wt%, Ti 5Si 3C 1-xMassfraction is 5wt%～90wt%.
When the skeleton of three-dimensional networks structure by Ti 3SiC 2, Ti 5Si 3C 1-x, when the Ti-Si binary compound is formed, Ti 3SiC 2Massfraction is 5wt%～90wt%, Ti 5Si 3C 1-xMassfraction is 5wt%～90wt%, and Ti-Si binary compound massfraction is 5wt%～90wt%.
When the skeleton of three-dimensional networks structure by Ti 3SiC 2, Ti 5Si 3C 1-xDuring composition, Ti 3SiC 2Massfraction is 5wt%～95wt%, Ti 5Si 3C 1-xMassfraction is 5wt%～95wt%.
Described Ti-Si binary compound specifically refers to compound Ti 3Si, Ti 5Si 3, Ti 5Si 4, TiSi 2, TiSi, Ti 6Si 5In one or more combination.
A kind of Ti that contains 3SiC 2The preparation method of the composite foam material of constituent element is basic raw material with raw material powder, macromolecular material, is masterplate with the porous plastics, adopts the high-frequency induction reaction sintering, and preparation process is as follows:
(1) raw material powder, macromolecular material, dehydrated alcohol are made slip, raw material powder through abundant ball mill mixing: macromolecular material: the proportioning of dehydrated alcohol is 50～500g: 50～200g: 1000mL; Again the porous plastics skeleton is immersed in the slurry, after the taking-up, remove redundant sizing agent with extruding, air-blowing or mode such as centrifugal;
Described raw material powder is selected from Ti powder, TiH 2Powder, TiO 2Powder, TiC powder, C powder, Si powder, SiC powder, Ti 3SiC 2Powder, Ti 3Si powder, Ti 5Si 3Powder, Ti 5Si 4Powder, TiSi 2Powder, TiSi powder, Ti 6Si 5In the powder one or more, and guarantee to contain silicon source, titanium source and carbon source in the raw material powder, granular size is 1 μ m～50 μ m.
Described macromolecular material is selected from one or more of Resins, epoxy, resol, furfuryl resin;
(2) the above-mentioned porous plastics that soaks behind the hanging material is fully solidified in thermal environment;
Polyurethane foam after the cutting is fully immersed in the slurry, in the scumming plastics after the redundant sizing agent, in 80～150 ℃ of semicures; According to the requirement of different skeleton volume fractions, hanging material-semicure circulation is carried out, at last the skeleton foam is solidified fully in 200～300 ℃;
(3) the foam pyrolysis after will solidifying, pyrolysis is carried out under protection of inert gas, 1～10 ℃/min of temperature rise rate, 600～1400 ℃ of pyrolysis temperatures, soaking time 10～300min;
(4) foam framework after the pyrolysis is cut into the skeleton sample of desired shape and size; then sample is placed plumbago crucible, carry out high-frequency induction heating under high-purity argon gas protection or vacuum condition, frequency is 30KHz～100KHz; 1000～1800 ℃ of temperature, soaking time 1～5min.
Wherein, step (4) can substitute with following two kinds of methods:
(1) when the Ti source is in shortage in the raw material powder; take following steps; foam framework after the pyrolysis is cut into the skeleton sample of desired shape and size; with titaniferous powder and dehydrated alcohol or other volatilizable organic solvent; be modulated to slurry by adding 10～50g titaniferous powder in every 100mL dehydrated alcohol or other the volatilizable organic solvent; the skeleton sample is fully oven dry after soaking this slurry of extension; then sample is placed plumbago crucible; under high-purity argon gas protection or vacuum condition, carry out high-frequency induction heating; frequency is 30KHz～100KHz; 1400～1800 ℃ of temperature, soaking time 1～3min.The titaniferous powder of sneaking in the described slurry is the titanium valve of mean particle size 1 μ m～50 μ m, in the titanium hydride powder one or both.According to the requirement that the material of required preparation is formed, the described hanging material-oven dry-high-frequency induction heating of soaking can circulate and carries out several times.In this step, the foam framework after the pyrolysis further soaks hangs the titaniferous slurry, and its effect is for the skeleton sample provides the titanium source that adds, and guarantees Ti in the foam framework 3SiC 2, TiC etc. contains the generation of the thing phase of titanium elements.
(2) when no Ti source in the raw material powder or Ti source are in shortage; take following steps; foam framework after the pyrolysis is cut into the skeleton sample of desired shape and size; with titaniferous powder and dehydrated alcohol or other volatilizable organic solvent; be modulated to slurry by adding 10～50g titaniferous powder in every 100mL dehydrated alcohol or other the volatilizable organic solvent; the mesh of skeleton sample is fully oven dry after slurry is filled; bury with graphite granule around then sample being placed plumbago crucible order sample; under high-purity argon gas protection or vacuum condition, carry out high-frequency induction heating; frequency is 30KHz～100KHz; 1400～1800 ℃ of temperature, soaking time 1～3min.Described graphite granule size is 0.2mm～6mm; The titaniferous powder of sneaking in the described slurry is the titanium valve of mean particle size 1 μ m～50 μ m, in the titanium hydride powder one or both.According to the requirement that the material of required preparation is formed, described filling paste-oven dry-high-frequency induction heating circulates as required and carries out.In this step, the foam framework after the pyrolysis is further filled the titaniferous slurry, and its effect is for the skeleton sample provides the titanium source that adds, and guarantees Ti in the foam framework 3SiC 2, TiC etc. contains the generation of the thing phase of titanium elements.Bury with graphite granule when high-frequency induction heating, its effect is to guarantee that the macropore of foam framework is not blocked.
Among the present invention, Ti 3SiC 2Constituent element can derive from the Ti of direct adding 3SiC 2Powder also can derive from the Ti that titanium source powder, silicon source powder, carbon source powder three solid state reaction at high temperature generates 3SiC 2Possible reaction mechanism is as follows:
Ti+C＝TiC
Ti+SiC＝TiC+Si
5Ti+3Si＝Ti 5Si 3
Ti+2Si＝TiSi 2
Ti 5Si 3+10TiC+2Si＝5Ti 3SiC 2
TiSi 2+2TiC＝Ti 3SiC 2+Si
(1-z)(3Ti+Si+2C)+(z)TiC→Ti 3SiC 2+Si+TiC 1-x(+Ti 5Si 3C 1-x)
Wherein, 0≤z≤1, TiC 1-xIn 0≤x＜1, Ti 5Si 3C 1-xIn 0≤x≤1.
The present invention has following beneficial effect:
1, the present invention adopts the reaction sintering method of high-frequency induction heating, need not to add the Ti that contains that sintering aid can obtain higher-density and ultimate compression strength 3SiC 2The foam materials of constituent element.In the high-frequency induction heating process, the titaniferous particle under the high temperature in the raw material powder, contain to react to each other between silicon grain, the carbonaceous particles isoreactivity component and generate Ti 3SiC 2Etc. new thing phase particle, and reach good combination simultaneously between the newly-generated thing phase particle, compare with the method for utilizing sintering aid direct sintering powder preparing foam materials, density is higher in the foam materials skeleton muscle of the method for the invention preparation, and ultimate compression strength is also higher.
2, compare the prepared Ti that contains with general foamed ceramics (as foam silicon carbon) 3SiC 2The composite foam material of constituent element has conductivity preferably.
3, the present invention is prepared contains Ti 3SiC 2The thermal expansivity of the composite foam material of constituent element is greater than the conventional foam pottery, and has hot matched performance preferably between the metal.
Description of drawings
Fig. 1 is for containing Ti 3SiC 2The macro morphology of the composite foam material of constituent element.
Fig. 2 is for containing Ti 3SiC 2The XRD figure spectrum of the composite foam material of constituent element.
Fig. 3 is for containing Ti 3SiC 2The compression behavior curve of the composite foam material of constituent element.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
The present invention contains Ti 3SiC 2Composite foam material of constituent element and preparation method thereof comprises the steps:
(1) selection of raw material powder
Be specially the SiC powder in the raw material powder, granular size is 5 μ m.
(2) preparation of slurry
Resin is dissolved in the dehydrated alcohol by a certain percentage, and full and uniform back adds a certain amount of SiC powder.In ball grinder, resin, dehydrated alcohol, raw material powder fully ground even prepare slurry.
(3) soak extension
Polyurethane foam after the cutting is fully immersed in the slurry, in the scumming hole after the redundant sizing agent, in 80～150 ℃ of semicures.According to the requirement of different skeleton volume fractions, hanging material-semicure several times that can circulate.At last the skeleton foam is solidified fully in 200～300 ℃, make raw material powder-resin composite foam skeleton.
(4) pyrolysis
With the raw material powder-resin composite foam skeleton pyrolysis under inert atmosphere protections such as high-purity argon after solidifying fully, pyrolysis temperature is 800～1200 ℃, and temperature rise rate is 1～4 ℃/min, makes original foam framework.
(5) high-frequency induction heating reaction sintering
Original foam framework placed plumbago crucible and buried with graphite granule, cover the have centre hole plumbago crucible lid of (being used for thermometric) after, place silica tube, feed the high-purity argon gas protection.By the high-frequency induction plumbago crucible foam is heated, make and contain Ti 3SiC 2The composite foam material of constituent element.
In the present embodiment, by raw material powder: ammonia resol: the dehydrated alcohol proportioning is 200g: 100g: 1000mL, is specially the SiC powder in the raw material powder.Contain the SiC in the pyrogenous origin amorphous C of resin and raw material powder in the pyrolysis back skeleton, wherein to account for the weight percent of pyrolysis back skeleton be 75wt% to SiC.Foam framework after the pyrolysis is cut into the skeleton sample of desired shape and size; with titanium hydride powder and dehydrated alcohol or other volatilizable organic solvent; be modulated to slurry by adding 10～50g titaniferous powder in every 100mL dehydrated alcohol or other the volatilizable organic solvent; the mesh of skeleton sample is fully oven dry after slurry is filled; then sample being placed around plumbago crucible and the sample with particle diameter is that the graphite granule of 0.7～1.4mm is buried; under high-purity argon gas protection or vacuum condition, carry out high-frequency induction heating; frequency is 30KHz～100KHz; 1750 ℃ of temperature, soaking time 30 seconds.The circulation of filling-oven dry-high-frequency induction heating is carried out 2-3 time, makes to contain Ti 3SiC 2The composite foam material of constituent element.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is by TiC, Ti 3SiC 2And a small amount of Ti 5Si 3Form, this contains Ti 3SiC 2The composite foam material structure of constituent element is to be elementary cell with the Polygons Closed loop, and each elementary cell is interconnected to form the three-dimensional networks structure; This contains Ti 3SiC 2The skeleton of the composite foam material three-dimensional networks structure of constituent element is by TiC, Ti 3SiC 2And a small amount of Ti 5Si 3Form, the TiC massfraction is 60wt%, Ti 3SiC 2Massfraction is 30wt%, Ti 5Si 3Massfraction is 10wt%.
The mesh size of three-dimensional networks structure is 1.5mm, and the skeleton volume fraction is 30%; The skeleton muscle that constitutes Polygons Closed loop unit is interior by TiC, Ti 3SiC 2And a small amount of Ti 5Si 3Form, its mean sizes is at 40 μ m.Interface between the particle is in conjunction with good, and density is higher in the skeleton muscle, and delthyrium is filled in the muscle.
As shown in Figure 1, with the Ti that contains of this method preparation 3SiC 2The composite foam material of constituent element has sintered density in the good skeleton muscle, and its weave construction is: be TiC, Ti in the muscle 3SiC 2And a small amount of Ti 5Si 3Compound phase.As shown in Figure 2, X-ray diffraction analysis, the whole Ti that contains 3SiC 2The thing of the composite foam material of constituent element is TiC, Ti mutually 3SiC 2And a small amount of Ti 5Si 3
As shown in Figure 3, from the prepared Ti that contains 3SiC 2The compression behavior curve of the composite foam material of constituent element as can be seen, present embodiment contain Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 21.6MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 90% in the foam muscle, and resistance is 100m Ω.
Embodiment 2
(1) selection of raw material powder
In order to guarantee that density is further enhanced in the reaction sintering process, the Ti powder is preferentially selected in the Ti source in the powder, or at high temperature can be decomposed into the TiH of Ti powder 2Powder (or both mixing), next selects TiH 2Powder is or/and Ti powder and Ti 3SiC 2, TiC, Ti 5Si 3C 1-x, one or more the mixing in the Ti-Si binary compound; The Si source can be selected from Si powder, Ti in the powder 5Si 3C 1-x, zero kind, one or more mixing in the SiC powder, Ti-Si binary compound powder; The C source can be selected from Ti in the powder 3SiC 2, zero kind, one or more mixing among SiC, TiC, C powder or the pyrogenous origin amorphous C of resin.
(2) preparation of slurry
Resin is dissolved in the dehydrated alcohol by a certain percentage, and full and uniform back adds a certain amount of raw material powder.In ball grinder, resin, dehydrated alcohol, raw material powder fully ground even prepare slurry.
(3) soak extension
Polyurethane foam after the cutting is fully immersed in the slurry, in the scumming hole after the redundant sizing agent, in 80～150 ℃ of semicures.According to the requirement of different skeleton volume fractions, hanging material-semicure several times that can circulate.At last the skeleton foam is solidified fully in 200～300 ℃, make raw material powder-resin composite foam skeleton.
(4) pyrolysis
With the raw material powder-resin composite foam skeleton pyrolysis under inert atmosphere protections such as high-purity argon after solidifying fully, pyrolysis temperature is 800～1200 ℃, and temperature rise rate is 1～4 ℃/min, makes original foam framework.
(5) high-frequency induction heating reaction sintering
Original foam framework is placed plumbago crucible, cover and have centre hole the plumbago crucible lid of (being used for thermometric) after, place silica tube, feed the high-purity argon gas protection.By the high-frequency induction plumbago crucible foam is heated, make and contain Ti 3SiC 2The composite foam material of constituent element.
Be 200g: 100g: 1000mL by raw material powder, ammonia resol, dehydrated alcohol proportioning.Be specially Ti powder, SiC powder in the raw material powder, granular size is～5 μ m, Ti powder: SiC powder=173g: 26g.Contain Ti powder, SiC powder in the pyrogenous origin amorphous C of resin and raw material powder in the pyrolysis back skeleton.Foam framework after the pyrolysis is cut into the skeleton sample of desired shape and size, places plumbago crucible, in high-purity argon gas protection high-frequency induction heating down, frequency is 30KHz～100KHz, and 1700 ℃ of temperature are incubated 15 seconds, make to contain Ti 3SiC 2The composite foam material of constituent element.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is by TiC, Ti 3SiC 2And a small amount of Ti 5Si 3Form, this contains Ti 3SiC 2The composite foam material structure of constituent element is to be elementary cell with the Polygons Closed loop, and each elementary cell is interconnected to form the three-dimensional networks structure, and mesh size is 1.5mm, and the skeleton volume fraction is 30%; This contains Ti 3SiC 2The skeleton of the composite foam material three-dimensional networks structure of constituent element is by TiC, Ti 3SiC 2And a small amount of Ti 5Si 3Form, average grain size is 50 μ m, and the TiC massfraction is 50wt%, Ti 3SiC 2Massfraction is 40wt%, Ti 5Si 3Massfraction is 10wt%.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 23MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 92% in the foam muscle, and resistance is 105m Ω.
Embodiment 3
(1) selection of raw material powder
In order to guarantee that density is further enhanced in the reaction sintering process, the Ti powder is preferentially selected in the Ti source in the powder, or at high temperature can be decomposed into the TiH of Ti powder 2Powder (or both mixing), next selects TiH 2Powder is or/and Ti powder and Ti 3SiC 2, TiC, Ti 5Si 3C 1-x, one or more the mixing in the Ti-Si binary compound; The Si source can be selected from Si powder, Ti in the powder 5Si 3C 1-x, zero kind, one or more mixing in the SiC powder, Ti-Si binary compound powder; The C source can be selected from Ti in the powder 3SiC 2, zero kind, one or more mixing among SiC, TiC, C powder or the pyrogenous origin amorphous C of resin.
(2) preparation of slurry
Resin is dissolved in the dehydrated alcohol by a certain percentage, and full and uniform back adds a certain amount of raw material powder.In ball grinder, resin, dehydrated alcohol, raw material powder fully ground even prepare slurry.
(3) soak extension
Polyurethane foam after the cutting is fully immersed in the slurry, in the scumming hole after the redundant sizing agent, in 80～150 ℃ of semicures.According to the requirement of different skeleton volume fractions, hanging material-semicure several times that can circulate.At last the skeleton foam is solidified fully in 200～300 ℃, make raw material powder-resin composite foam skeleton.
(4) pyrolysis
With the raw material powder-resin composite foam skeleton pyrolysis under inert atmosphere protections such as high-purity argon after solidifying fully, pyrolysis temperature is 800～1200 ℃, and temperature rise rate is 1～4 ℃/min, makes original foam framework.
(5) high-frequency induction heating increases the titanium reaction sintering
With TiH 2Powder impregnated in the TiC foam framework in the slurry with dehydrated alcohol furnishing slurry, takes out the unnecessary slurry in the scumming macropore of back, and 100～150 ℃ of oven dry 20～40min remove unnecessary dehydrated alcohol in the baking oven.To be loaded with TiH 2The foam of powder places plumbago crucible; after covering and have centre hole the plumbago crucible lid of (being used for thermometric); place plumbago crucible; high-frequency induction heating under the high-purity argon gas protection; frequency is 30KHz～100KHz, and 1700 ℃ of temperature are incubated 15 seconds; by circulation flood-dry-high-frequency induction heating increases titanium, can prepare and contain Ti 3SiC 2The composite foam material of constituent element.
In the present embodiment, be 200g: 100g: 1000mL by raw material powder, ammonia resol, dehydrated alcohol proportioning.Be specially TiH in the raw material powder 2Powder, SiC powder, granular size are～5 μ m, TiH 2Powder: SiC powder=150g: 50g.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is by TiC, Ti 3SiC 2And a small amount of Ti 5Si 3Form, this contains Ti 3SiC 2The composite foam material structure of constituent element is to be elementary cell with the Polygons Closed loop, and each elementary cell is interconnected to form the three-dimensional networks structure, and mesh size is 1.5mm, and the skeleton volume fraction is 30%; This contains Ti 3SiC 2The skeleton of the composite foam material three-dimensional networks structure of constituent element is by TiC, Ti 3SiC 2And a small amount of Ti 5Si 3Form, average grain size is 35 μ m, and the TiC massfraction is 50wt%, Ti 3SiC 2Massfraction is 30wt%, Ti 5Si 3Massfraction is 20wt%.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 22MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 91% in the foam muscle, and resistance is 112m Ω.
Embodiment 4
Difference from Example 1 is, is specially Ti powder, SiC powder in the raw material powder, and the Ti powder: SiC powder=160g: 40g.The prepared Ti that contains 3SiC 2The volume fraction of the composite foam material of constituent element is 25%.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 25MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 90% in the foam muscle, and resistance is 103m Ω.
Embodiment 5
Difference from Example 1 is, is specially TiC powder, SiC powder in the raw material powder, and the TiC powder: SiC powder=100g: 100g.The prepared Ti that contains 3SiC 2The volume fraction of the composite foam material of constituent element is 40%.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 24MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 92% in the foam muscle, and resistance is 106m Ω.
Embodiment 6
Difference from Example 1 is, is specially SiC powder, Ti in the raw material powder 3SiC 2Powder, and SiC powder: Ti 3SiC 2Powder=100g: 100g.The prepared Ti that contains 3SiC 2The volume fraction of the composite foam material of constituent element is 20%.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 26MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 90% in the foam muscle, and resistance is 110m Ω.
Embodiment 7
Difference from Example 1 is, is specially TiC powder, SiC powder, Ti in the raw material powder 3SiC 2Powder, and TiC powder: SiC powder: Ti 3SiC 2Powder=100g: 60g: 40g.The prepared Ti that contains 3SiC 2The mesh size average out to 2mm of the composite foam material of constituent element.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 21MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 91% in the foam muscle, and resistance is 100m Ω.
Embodiment 8
Difference from Example 2 is, is specially Ti powder, Si powder in the raw material powder, and the Ti powder: Si powder=150g: 50g, carbon source comes from the carbon that the resin pyrolysis produces.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 23MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 89% in the foam muscle, and resistance is 101m Ω.
Embodiment 9
Difference from Example 2 is, is specially Ti powder, Si powder, C powder in the raw material powder, and the Ti powder: Si powder: C powder=170g: 20g: 10g.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 27MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 91% in the foam muscle, and resistance is 118m Ω.
Embodiment 10
Difference from Example 2 is, is specially Ti powder, TiC powder, SiC powder in the raw material powder, and the Ti powder: TiC powder: SiC powder=100g: 70g: 30g.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 24MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 90% in the foam muscle, and resistance is 103m Ω.
Embodiment 11
Difference from Example 2 is, is specially Ti powder, Ti in the raw material powder 3SiC 2Powder, and Ti powder: Ti 3SiC 2Powder=50g: 150g.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 23MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 91% in the foam muscle, and resistance is 100m Ω.
Embodiment 12
Difference from Example 3 is, is specially Ti powder, Si powder, C powder in the raw material powder, and the Ti powder: Si powder: C powder=150g: 30g: 20g.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 25MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 90% in the foam muscle, and resistance is 107m Ω.
Embodiment 13
Difference from Example 3 is, is specially TiC powder, SiC powder, Ti in the raw material powder 3SiC 2Powder, and TiC powder: SiC powder: Ti 3SiC 2Powder=30g: 20g: 150g.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 21MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 91% in the foam muscle, and resistance is 116m Ω.
Embodiment 14
Difference from Example 3 is, is specially TiC powder, Si powder, Ti in the raw material powder 3SiC 2Powder, and TiC powder: Si powder: Ti 3SiC 2Powder=40g: 10g: 150g.
Present embodiment contains Ti 3SiC 2The performance index of the composite foam material of constituent element are: the prepared Ti that contains 3SiC 2The apparent ultimate compression strength of the composite foam material of constituent element reaches 26MPa.
In the present embodiment, contain Ti 3SiC 2The composite foam material of constituent element is of a size of 12mm * 12mm * 24mm, and density is 89% in the foam muscle, and resistance is 103m Ω.
The result shows that the present invention contains Ti 3SiC 2The composite foam material of constituent element is the three-dimensional networks structure, and phase composite is mainly by Ti 3SiC 2The binary or the ternary compound that reach other Ti, Si, C constitute.Porous plastics after cutting out is immersed in the slurry that is mixed and made into by raw material powder, high carbon residue rate resin, dehydrated alcohol, remove unnecessary slurry after the taking-up, through semicure-hot setting-pyrolysis, obtain consistent with original foam shape, the spumescence skeleton of being formed by raw material powder and RESEARCH OF PYROCARBON.Above-mentioned foam framework is through high-frequency induction heating (increasing titanium) reaction sintering, finally makes to contain Ti 3SiC 2The composite foam material of constituent element.This technical matters is simple, need not complex apparatus.Prepared composite foam material density and ultimate compression strength are higher, have excellent conducting performance.

Claims (6)

1. one kind contains Ti 3SiC 2The composite foam material of constituent element is characterized in that: this contains Ti 3SiC 2The composite foam material of constituent element contains Ti 3SiC 2, this contains Ti 3SiC 2The composite foam material structure of constituent element is to be elementary cell with the Polygons Closed loop, and each elementary cell is interconnected to form the three-dimensional networks structure;
The mesh size of three-dimensional networks structure is 1.5mm～5mm, and the skeleton volume fraction is 30%～50%; The skeleton muscle that constitutes Polygons Closed loop unit contains Ti 3SiC 2Particle, its mean sizes is at 35 μ m～200 μ m;
This contains Ti 3SiC 2The composite foam material of constituent element is by Ti 3SiC 2With SiC, TiC 1-x, Ti 5Si 3C 1-x, a kind of or more than one compositions in the Ti-Si binary compound, described TiC 1-xIn 0≤x＜1, Ti 5Si 3C 1-xIn 0≤x≤1;
When the skeleton of three-dimensional networks structure by Ti 3SiC 2, SiC and TiC 1-xDuring composition, Ti 3SiC 2Massfraction is 5wt%～90wt%, and the SiC massfraction is 5wt%～90wt%, TiC 1-xMassfraction is 5wt%～90wt%;
When the skeleton of three-dimensional networks structure by Ti 3SiC 2, when SiC and Ti-Si binary compound are formed, Ti 3SiC 2Massfraction is 5wt%～90wt%, SiC massfraction 5wt%～90wt%, Ti-Si binary compound massfraction 5wt%～90wt%;
When the skeleton of three-dimensional networks structure by Ti 3SiC 2, TiC 1-x, Ti 5Si 3C 1-xDuring composition, Ti 3SiC 2Massfraction is 5wt%～90wt%, TiC 1-xMassfraction is 5wt%～90wt%, Ti 5Si 3C 1-xMassfraction is 5wt%～90wt%;
When the skeleton of three-dimensional networks structure by Ti 3SiC 2, Ti 5Si 3C 1-x, when the Ti-Si binary compound is formed, Ti 3SiC 2Massfraction is 5wt%～90wt%, Ti 5Si 3C 1-xMassfraction is 5wt%～90wt%, and Ti-Si binary compound massfraction is 5wt%～90wt%;
When the skeleton of three-dimensional networks structure by Ti 3SiC 2, Ti 5Si 3C 1-xDuring composition, Ti 3SiC 2Massfraction is 5wt%～95wt%, Ti 5Si 3C 1-xMassfraction is 5wt%～95wt%.
2. according to the described Ti that contains of claim 1 3SiC 2The composite foam material of constituent element is characterized in that: described Ti-Si binary compound specifically refers to compound Ti 3Si, Ti 5Si 3, Ti 5Si 4, TiSi 2, TiSi, Ti 6Si 5In one or more combination; In the skeleton muscle of the Polygons Closed loop unit of formation three-dimensional networks structure, SiC, TiC 1-x, Ti 5Si 3C 1-x, Ti 3Si, Ti 5Si 3, Ti 5Si 4, TiSi 2, TiSi, Ti 6Si 5Particle mean size at 1 μ m～200 μ m.
3. described Ti that contains of claim 1 3SiC 2The preparation method of the composite foam material of constituent element is characterized in that, comprises the steps:
(1) raw material powder, macromolecular material, dehydrated alcohol are made slip, raw material powder through abundant ball mill mixing: macromolecular material: the proportioning of dehydrated alcohol is 50～500g:50～200g:1000mL; Again the porous plastics skeleton is immersed in the slurry, after the taking-up, remove redundant sizing agent with extruding, air-blowing or centrifugation;
Described raw material powder is selected from Ti powder, TiH 2Powder, TiO 2Powder, TiC powder, C powder, Si powder, SiC powder, Ti 3SiC 2Powder, Ti 3Si powder, Ti 5Si 3Powder, Ti 5Si 4Powder, TiSi 2Powder, TiSi powder, Ti 6Si 5In the powder one or more, and guarantee to contain silicon source, titanium source and carbon source in the raw material powder, granular size is 1 μ m～50 μ m;
Described macromolecular material is selected from one or more of Resins, epoxy, resol, furfuryl resin;
(2) the above-mentioned porous plastics that soaks behind the hanging material is fully solidified in thermal environment;
Polyurethane foam after the cutting is fully immersed in the slurry, in the scumming plastics after the redundant sizing agent, in 80～150 ℃ of semicures; According to the requirement of different skeleton volume fractions, hanging material-semicure circulation is carried out, at last the skeleton foam is solidified fully in 200～300 ℃;
(3) the foam pyrolysis after will solidifying, pyrolysis is carried out under protection of inert gas, 1～10 ℃/min of temperature rise rate, 600～1400 ℃ of pyrolysis temperatures, soaking time 10～300min;
(4) foam framework after the pyrolysis is cut into the skeleton sample of desired shape and size; then sample is placed plumbago crucible; under high-purity argon gas protection or vacuum condition, carry out high-frequency induction heating; frequency is 30KHz～100KHz; 1000～1800 ℃ of temperature, soaking time 1～5min.
4. described Ti that contains of claim 1 3SiC 2The preparation method of the composite foam material of constituent element is characterized in that, comprises the steps:
(1) raw material powder, macromolecular material, dehydrated alcohol are made slip, raw material powder through abundant ball mill mixing: macromolecular material: the proportioning of dehydrated alcohol is 50～500g:50～200g:1000mL; Again the porous plastics skeleton is immersed in the slurry, after the taking-up, remove redundant sizing agent with extruding, air-blowing or centrifugation;
Described raw material powder is selected from Ti powder, TiH 2Powder, TiO 2Powder, TiC powder, C powder, Si powder, SiC powder, Ti 3SiC 2Powder, Ti 3Si powder, Ti 5Si 3Powder, Ti 5Si 4Powder, TiSi 2Powder, TiSi powder, Ti 6Si 5In the powder one or more, and guarantee to contain silicon source, titanium source and carbon source in the raw material powder, granular size is 1 μ m～50 μ m;
Described macromolecular material is selected from one or more of Resins, epoxy, resol, furfuryl resin;
(2) the above-mentioned porous plastics that soaks behind the hanging material is fully solidified in thermal environment;
Polyurethane foam after the cutting is fully immersed in the slurry, in the scumming plastics after the redundant sizing agent, in 80～150 ℃ of semicures; According to the requirement of different skeleton volume fractions, hanging material-semicure circulation is carried out, at last the skeleton foam is solidified fully in 200～300 ℃;
(3) the foam pyrolysis after will solidifying, pyrolysis is carried out under protection of inert gas, 1～10 ℃/min of temperature rise rate, 600～1400 ℃ of pyrolysis temperatures, soaking time 10～300min;
(4) foam framework after the pyrolysis is cut into the skeleton sample of desired shape and size, with titaniferous powder and dehydrated alcohol or other volatilizable organic solvent, be modulated to slurry by adding 10～50g titaniferous powder in every 100mL dehydrated alcohol or other the volatilizable organic solvent, the skeleton sample is fully oven dry after soaking this slurry of extension, then sample is placed plumbago crucible, under high-purity argon gas protection or vacuum condition, carry out high-frequency induction heating, frequency is 30KHz～100KHz, 1400～1800 ℃ of temperature, soaking time 1～3min; The described hanging material-oven dry-high-frequency induction heating of soaking circulates as required and carries out.
5. described Ti that contains of claim 1 3SiC 2The preparation method of the composite foam material of constituent element is characterized in that, comprises the steps:
(1) raw material powder, macromolecular material, dehydrated alcohol are made slip, raw material powder through abundant ball mill mixing: macromolecular material: the proportioning of dehydrated alcohol is 50～500g:50～200g:1000mL; Again the porous plastics skeleton is immersed in the slurry, after the taking-up, remove redundant sizing agent with extruding, air-blowing or centrifugation;
Described raw material powder is selected from Ti powder, TiH 2Powder, TiO 2Powder, TiC powder, C powder, Si powder, SiC powder, Ti 3SiC 2Powder, Ti 3Si powder, Ti 5Si 3Powder, Ti 5Si 4Powder, TiSi 2Powder, TiSi powder, Ti 6Si 5In the powder one or more, and guarantee to contain silicon source, titanium source and carbon source in the raw material powder, granular size is 1 μ m～50 μ m;
Described macromolecular material is selected from one or more of Resins, epoxy, resol, furfuryl resin;
(2) the above-mentioned porous plastics that soaks behind the hanging material is fully solidified in thermal environment;
Polyurethane foam after the cutting is fully immersed in the slurry, in the scumming plastics after the redundant sizing agent, in 80～150 ℃ of semicures; According to the requirement of different skeleton volume fractions, hanging material-semicure circulation is carried out, at last the skeleton foam is solidified fully in 200～300 ℃;
(3) the foam pyrolysis after will solidifying, pyrolysis is carried out under protection of inert gas, 1～10 ℃/min of temperature rise rate, 600～1400 ℃ of pyrolysis temperatures, soaking time 10～300min;
(4) foam framework after the pyrolysis is cut into the skeleton sample of desired shape and size, with titaniferous powder and dehydrated alcohol or other volatilizable organic solvent, be modulated to slurry by adding 10～50g titaniferous powder in every 100mL dehydrated alcohol or other the volatilizable organic solvent, the mesh of skeleton sample is fully oven dry after slurry is filled, bury with graphite granule around then sample being placed plumbago crucible and sample, under high-purity argon gas protection or vacuum condition, carry out high-frequency induction heating, frequency is 30KHz～100KHz, 1400～1800 ℃ of temperature, soaking time 1～3min, described graphite granule size is 0.2mm～6mm; Described filling paste-oven dry-high-frequency induction heating circulates as required and carries out.
6. according to claim 4 or the 5 described Ti that contain 3SiC 2The preparation method of the composite foam material of constituent element is characterized in that, the titaniferous powder of sneaking in the described slurry of step (4) is the titanium valve of mean particle size 1 μ m～50 μ m, in the titanium hydride powder one or both.
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