CN110357632A - A kind of ZrC/SiC complex phase ceramic presoma and preparation method thereof - Google Patents
A kind of ZrC/SiC complex phase ceramic presoma and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of ZrC/SiC complex phase ceramic presoma and preparation method thereof, for the presoma using the poly- zirconium oxygen alkane of nonpolarity as zirconium source, modified phenolic is carbon source, and Polycarbosilane is that silicon source reaction is prepared；Part of hydroxyl in the modified phenolic is etherified, and contains carbon carbon unsaturated functional group.Preparation method then applies high temperature pre-polymerization in the poly- zirconium oxygen alkane preparation process of nonpolarity, and makes zirconium source and the carbon source obtained ZrC presoma of hybrid reaction at a certain temperature.The present invention, which passes through, selects to contain phenolic aldehyde that unsaturated functional group and hydroxyl are etherified as carbon source, particular procedure is carried out to zirconium source simultaneously, so that remaining Zr-OR structural content decline in poly- zirconium oxygen alkane, the stability of zirconium carbide presoma is improved, to further improve complex phase ceramic presoma at normal temperature depot.
Description
Technical field
The invention belongs to composite diphase material fields, specifically, being related to a kind of ZrC/SiC complex phase ceramic presoma and its preparation
Method.
Background technique
Carbide ceramics has the characteristics of high-melting-point, high intensity, high rigidity, and possesses good mechanical property, chemistry
Stability and oxidative resistance.It is wherein more prominent with the carbonization physical performance of Zr, Hf, Ta, Nb, concentrate a large amount of research.Carbonization
The oxide skin(coating) that object can be converted into corresponding densification in aerobic environment be attached to matrix surface prevent the further erosion of oxygen with
Airflow scouring can achieve the effective protection to matrix in extreme environment.However carbide has ceramics intrinsic brittleness big
Disadvantage needs to be modified its toughness.Carbon fiber can pass through winding as the fibre reinforcement for being uniquely resistant to 3000 DEG C of high temperature
The means such as braiding prepare prefabricated component, prepare ceramic matric composite in conjunction with carbide ceramics, reach high-strength, high-ductility, high temperature resistant, resist
The purpose of oxidation.
SiC or ZrC ceramics are widely used as traditional carbide ceramics material, and the SiC ceramic oxidation resistance temperature upper limit is
1700 DEG C, it can occur actively to aoxidize when higher than this temperature and form gaseous state SiO material surface ablating rate is caused to sharply increase；And environment
The reduction of pressure, the erosion of steam can all aggravate oxidation rate；Product is ZrO under ZrC ceramic high temperature aerobic environment2, ZrO2Have
Higher fusing point (2700 DEG C), lower diffusion coefficient and thermal conductivity can effectively prevent extraneous oxygen and steam to material
Further erosion, but that there are thermal shock resistances is poor for ZrC ceramics, thermal expansion coefficient the problem of, can be to material under hot environment
Material causes defect and crackle in itself, makes its mechanical properties decrease.Studies have shown that the ZrC complex phase ceramic base for adulterating a certain amount of SiC is multiple
Condensation material can effectively make up the defect of ZrC material, and have higher anti-oxidant temperature resistant grade.
The method of preparation fiber reinforced ceramic matrix composites mainly has polymer infiltration and pyrolysis method (PIP) at present, chemistry
Vapour deposition process (CVI) reacts infiltration method (RMI) and puddling (SI), wherein using the ceramic matric composite of PIP method preparation
1. having the advantage that can be realized to composite material ceramic matrix composition, microstructure and performance by the design of precursor molecule
Control；2. simple process, forming temperature are low, cracking temperature is low；3. the mechanical damage and thermal damage to fiber are small, fiber is increased
The adaptability of strong body is good；4. can obtain, ingredient is uniform, purity is high single group is first or the ceramic matrix of multicomponent；5. large size can be prepared
The composite material parts of complex-shaped nearly size.However currently, the main method of preparation of industrialization zirconium carbide (ZrC) is solid
Body carbon and metal oxide powder carry out carbothermic reduction reaction, and the reaction temperature that this method needs is higher, usually 1900~
2300 DEG C, the production cycle is longer, and the ZrC diameter of particle prepared is bigger, and sintering activity is poor, answers with C/C and containing silicon precursor
When conjunction, it is difficult to mix, easily with Carbon Materials there are sharp interface, generate stress and concentrate, cause product to crack and influence the burning of material
Corrosion energy.Therefore preparation stablizes compatible ZrC presoma with silicon source and becomes most important, attracted many concerns in the field with
Research.Sol-gel method is to prepare the main method of ZrC ceramic powder, but in the presoma as PIP method in use, depositing
Effective concentration is low, stability is poor, is not easy the shortcomings that storing, and refractory ceramics low yield, so that long preparation period, at high cost,
It is not suitable for preparing large-size ceramic based composite material component；In addition this method is poor with the compatibility of silicon source, it is more difficult to realize multiple
The preparation of phase ceramics.Via Polymeric Precursor Method polymerize to form Zr-C molecular backbone or Zr-O molecular backbone by small molecule containing zirconium
The method that polymer compounds carbon source, obtains stable ZrC ceramic forerunner, stable liquid phase presoma is the same as a variety of silicon source compatibilities
Well, designability is strong.
Chinese patent CN105218099A discloses a kind of preparation method of nonpolar zirconium carbide liquid phase presoma, be related to by
Zirconium alkoxide carries out the poly- zirconium oxygen alkane of controlled hydrolysis preparation nonpolarity under the coordination protection of acetylacetone,2,4-pentanedione, then with carbon source divinyl
Benzene compounding is made.The system has the following problems in actual use: (1) since the extent of reaction inadequate, poly- zirconium oxygen alkane point
The content of remaining Zr-OR and Zr-OH is relatively high in son, causes zirconium carbide presoma stability insufficient, was actually using
Gel easily occurs for the water contact in Cheng Zhongyu air, and storage period only has 1 month.General composite material dipping needs at least tens of wheels
Secondary, the period is up to the several months, and zirconium carbide presoma stability deficiency will lead to dipping repeatability and stability decline, increase simultaneously
The cost of the loss of presoma and composite material preparation.(2) the carbon source divinylbenzene used is small molecule, not with poly- zirconium oxygen alkane
It reacts, therefore in the two co-curing, divinylbenzene is volatile to cause carbon source to be lost, in order to guarantee carbon source abundance, needs
To solidify in closed high-pressure bottle.Bring following disadvantage therewith: the size of one side composite product is usually larger, because
The high-pressure reaction vessel of this correspondingly-sized needed, substantially increases manufacturing cost；On the other hand, curing reaction is in high pressure
Under there are the security risks such as explosive, to limit the engineering application of zirconium carbide presoma.
In view of this, the present invention is specifically proposed.
Summary of the invention
The technical problem to be solved in the present invention is that overcoming the deficiencies of the prior art and provide a kind of ZrC/SiC complex phase ceramic
Presoma and preparation method thereof, using modified phenolic as carbon source, and in preparation method by the way of high temperature pre-polymerization system
Standby nonpolarity zirconium source, and nonpolar zirconium source is reacted at a certain temperature with modified phenolic during preparing ZrC, effectively overcome
The technical issues of ZrC presoma stability is insufficient, and easily generation gel easily contact with the water in air.
In order to solve the above technical problems, the present invention is using the basic conception of technical solution:
The present invention provides a kind of ZrC/SiC complex phase ceramic presoma, the presoma is using the poly- zirconium oxygen alkane of nonpolarity as zirconium
Source, modified phenolic are carbon source, and Polycarbosilane is that silicon source reaction is prepared；Part of hydroxyl in the modified phenolic is etherified,
And contain carbon carbon unsaturated functional group.
In above scheme, the hydroxyl in modified phenolic strand is etherified, and unsaturated functional group is made to be connected with oxygen atom, and
The unsaturated functional group be alkenyl and/or alkynyl, have preferable reactivity, can in the forming process of composite diphase material,
Make to crosslink between ethylene linkage and/or acetylene bond and poly- zirconium oxygen alkane and Polycarbosilane in modified phenolic and react, further by carbon source
It is fixed in composite diphase material, so that Zr, Si and C are evenly distributed in complex phase ceramic presoma, improves the production of precursor ceramic
Rate.
Further scheme of the invention are as follows: in the modified phenolic etherificate rate of hydroxyl be 80~99%, preferably 85~
95%.
In above scheme, the part of hydroxyl in modified phenolic is etherified, and etherificate rate is higher, that is, represent in carbon source can with it is poly-
The carbon carbon unsaturated group mass contg that strand is crosslinked in zirconium oxygen alkane is higher, improves crosslink density, avoids carbon source in subsequent high temperature
It is lost in processing.And turn down the maximum value of preferred etherificate rate, then it is to consider to make a small amount of not etherified phenolic hydroxyl group in carbon source
It is reacted with poly- zirconium oxygen alkane further to remove the active group in poly- zirconium oxygen alkane, improves the stability of presoma.
Further scheme of the invention are as follows: in the complex phase ceramic presoma, the molar ratio of zr element and carbon is 1:1
~3, preferably 1:1~2；The molar ratio of zr element and element silicon is 1:0.1~15, preferably 1:0.3~6.
Further scheme of the invention are as follows: the molar content of Zr-OR is that 0~3%, R is in the poly- zirconium oxygen alkane of nonpolarity
Hydrogen-based and/or alkyl.
Further scheme of the invention are as follows: after the complex phase ceramic presoma is placed 12 months at 25 DEG C, the change of viscosity
Rate is not more than 10%.
The present invention also provides a kind of preparation method of ZrC/SiC complex phase ceramic presoma as described above, the preparations
Method after carrying out coordination protection and hydrolytie polycondensation to zirconium alkoxide, is carrying out the obtained poly- zirconium oxygen alkane of nonpolarity of high temperature pre-polymerization；Later
ZrC presoma is made after the poly- zirconium oxygen alkane of nonpolarity obtained is reacted at a certain temperature with modified phenolic mixing.
In above-mentioned preparation method, high temperature prepolymerization step is increased in the poly- zirconium oxygen alkane preparation step of nonpolarity, this step makes
It obtains most of active Zr-OR and Zr-OH group in original method to be condensed at high temperature, reduces the active group of presoma resin,
Increase the stability in its use process.In addition, increasing the step that the poly- zirconium oxygen alkane of nonpolarity is reacted with modified phenolic carbon source
Suddenly, since the part of hydroxyl in carbon source is etherified, and contain carbon carbon unsaturated group, may make a small amount of not etherified in carbon source
Phenolic hydroxyl group and poly- zirconium oxygen alkane react, further remove the active group in precursor solution；At the same time, passing through of carbon source
It learns reaction to be mutually crosslinked with poly- zirconium oxygen alkane strand, avoids the loss of carbon source in subsequent high temperature treatment process；And unsaturated carbon carbon bond
Introducing then increase the crosslink density of carbon source, its carbon retention rate is improved, to improve ceramic yield.
According to above-mentioned preparation method, the poly- zirconium oxygen alkane of preparation nonpolarity includes the following steps:
(1) coordination protection: 25~100 DEG C at a temperature of, a certain amount of complexing agent is added to the monohydric alcohol of zirconium alkoxide
In solution, 0.5~5h is reacted；
(2) hydrolytie polycondensation: 25~100 DEG C at a temperature of, step (1) reaction after solution in add it is a certain amount of
The mixed liquor of water and monohydric alcohol, is hydrolyzed polycondensation；
(3) high temperature pre-polymerization: the solution after step (2) hydrolytie polycondensation is heated, its pre-polymerization at a temperature of 100~180 DEG C is made
Nonpolar solvent is added later and obtains the poly- zirconium oxygen alkane of nonpolarity by 0.5~5h；
Wherein, the molar ratio of zirconium alkoxide, complexing agent, water and monohydric alcohol is 1:0.5~6:0.5~2:6~20；Preferably,
Reaction temperature in step (1) and (2) is 60~95 DEG C, and the pre-polymerization temperature in step (3) is 120~150 DEG C.
According to above-mentioned preparation method, preparing ZrC presoma includes that the poly- zirconium oxygen alkane of nonpolarity and modified phenolic are blended in 30
0.5~5h is reacted at~130 DEG C；Preferably, the poly- zirconium oxygen alkane of nonpolarity be blended at 50~80 DEG C with modified phenolic react 2~
4h。
According to above-mentioned preparation method, the preparation method further includes that Polycarbosilane is dissolved and stirred in nonpolar solvent
0.5~6h is made SiC precursor solution, and 30 after SiC precursor solution and the ZrC presoma are mixed in a certain ratio
Solidified after reacting 0.5~5h at~130 DEG C；Preferably, SiC precursor solution and the ZrC presoma be by a certain percentage
2~4h is reacted after mixing at 50~80 DEG C.
In above-mentioned preparation method, SiC presoma carries out reacting with ZrC presoma at a certain temperature to be solidified and can further increase
Add the crosslinking degree of carbon source and silicon source.
According to above-mentioned preparation method, described solidify includes that the solidification of 4~normal pressure for 24 hours is carried out under the conditions of 110~300 DEG C,
It is cracked under 1500~1800 DEG C of inert atmosphere later and complex phase ceramic presoma is made；The solidification process includes: at 120 DEG C
2~3h of lower solidification solidifies 2~3h at 160 DEG C later, solidifies 2~3h at 180 DEG C later, solidifies 2 at 220 DEG C later
~3h finally solidifies 2h at 250 DEG C and is made；Alternatively, solidifying 1~2h at 120 DEG C, solidify 1~2h at 140 DEG C later,
Solidify 1~2h at 160 DEG C later, solidify 1~2h at 180 DEG C later, solidifies 1~2h, Zhi Hou at 200 DEG C later
Solidify 1~2h at 220 DEG C, finally solidifies 2~4h at 250 DEG C and be made.
In above-mentioned preparation method, the cracking temperature is preferably 1550~1700 DEG C.
According to above-mentioned preparation method, the complexing agent is acetylacetone,2,4-pentanedione and/or ethyl acetoacetate.
According to above-mentioned preparation method, the monohydric alcohol is isopropanol, normal propyl alcohol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol
One or more of ether.
According to above-mentioned preparation method, the nonpolar solvent is n-hexane, normal heptane, toluene, one of dimethylbenzene
Or it is several.
According to above-mentioned preparation method, the preparation method specifically comprises the following steps:
(1) 25~100 DEG C at a temperature of, a certain amount of complexing agent is added in the unitary alcoholic solution of zirconium alkoxide, instead
Answer 0.5~5h；Later 25~100 DEG C at a temperature of, a certain amount of water and monohydric alcohol will be added in the solution after reaction
Polycondensation is hydrolyzed in mixed liquor；Wherein, the molar ratio of zirconium alkoxide, complexing agent, water and monohydric alcohol is 1:0.5~6:0.5~2:6
~20；
(2) to a certain amount of nonpolar solvent is added in the solution after hydrolytie polycondensation in step (1), heating makes it 100
0.5~5h of pre-polymerization at a temperature of~180 DEG C obtains the poly- zirconium oxygen alkane of nonpolarity；
(3) mix nonpolarity office zirconium oxygen alkane made from step (2) with phenol-formaldehyde resin modified with certain proportion and 30~
0.5~5h is reacted at 130 DEG C, obtains ZrC presoma；
(4) Polycarbosilane is dissolved in nonpolar solvent, 0.5~6h of stirring obtains SiC presoma；
(5) 1~6h is stirred after being mixed in a certain ratio ZrC presoma made from step (3) and (4) and SiC presoma
Mixing, and complex phase presoma is obtained after reacting 0.5~5h at 30~130 DEG C；
(6) complex phase presoma made from step (5) carries out to 4 under the conditions of 110~300 DEG C~normal pressure solidification for 24 hours, it
It is cracked under 1500~1800 DEG C of inert atmosphere afterwards and complex phase ceramic presoma is made.
After adopting the above technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the present invention prepares the poly- zirconium oxygen alkane of nonpolarity using the simple reaction of zirconium alkoxide complexing hydrolysis, by increasing high temperature
Pre-polymerization and the means reacted with carbon source reduce the active group in presoma, significantly increase the stability of presoma, room
Viscosity change is no more than 10% after temperature saves 1 year；
2. the carbon source that the present invention selects is the phenolic resin that part of hydroxyl is etherified, carbon retention rate with higher, and tool
There is the characteristics of stable structure, improves the yield of precursor ceramic；
3. being stablized using presoma chemical property made from preparation method provided by the invention, ceramic yield is high, and viscosity can
It adjusts range wide, dissolves in a variety of organic solvents, and have the characteristic of resin, excellent processability overcomes traditional inorganic method technique
Property difference disadvantage；Meanwhile the additional proportion of silicon source Polycarbosilane PCS can be adjusted arbitrarily according to demand；It is impregnated suitable for presoma
Cracking, the preparation processes such as plasma spraying also have potential application in terms of prepares coating and ceramic fibre.
4. pyrolysis temperature is lower in preparation method of the invention, presoma is converted into ZrC/SiC complex phase pottery at 1600 DEG C
Porcelain；Low temperature can reduce the energy consumption of technical process, reduces to the thermal stress in the high-temperature damage and product of matrix, reduces in sintering
Deformation to improve qualification rate etc. in finished product, while the ceramic crystalline grain prepared is smaller, and particle size uniformity can prevent
The high-temperature behavior of coating declines.
A specific embodiment of the invention is described in further detail with reference to the accompanying drawing.
Detailed description of the invention
Attached drawing is as a part of the invention, and for providing further understanding of the invention, of the invention is schematic
Examples and descriptions thereof are used to explain the present invention, but does not constitute an undue limitation on the present invention.Obviously, the accompanying drawings in the following description
Only some embodiments to those skilled in the art without creative efforts, can be with
Other accompanying drawings can also be obtained according to these attached drawings.In the accompanying drawings:
Fig. 1 is the infrared comparison diagram before presoma blending reaction of the present invention and after reaction；
Fig. 2 is the XRD diagram of ZrC/SiC complex phase ceramic of the present invention；
Fig. 3 is the SEM figure of ZrC/SiC complex phase ceramic of the present invention.
It should be noted that these attached drawings and verbal description are not intended to the design model limiting the invention in any way
It encloses, but illustrates idea of the invention by referring to specific embodiments for those skilled in the art.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical solution in embodiment is clearly and completely described, the following examples are intended to illustrate the invention, but
It is not intended to limit the scope of the invention.
Embodiment 1
In the present embodiment, ZrC/SiC complex phase ceramic presoma is prepared with the following method:
(1) 25 DEG C at a temperature of, 1mol complexing agent acetylacetone,2,4-pentanedione is added to containing 1mol zirconium alkoxide and 5mol positive third
In the zirconium alkoxide normal propyl alcohol solution of alcohol, 2h is reacted；Later 25 DEG C at a temperature of, 1mol water will be added in the solution after reaction
With 1mol normal propyl alcohol, polycondensation is hydrolyzed, wherein the molar ratio of zirconium alkoxide, complexing agent, water and monohydric alcohol is 1:1:1:6；
(2) 7mol dimethylbenzene is added in the solution in step (1) after hydrolytie polycondensation, heating makes it at a temperature of 125 DEG C
Pre-polymerization 1h obtains the poly- zirconium oxygen alkane of nonpolarity；
(3) by nonpolarity office zirconium oxygen alkane made from step (2) and etherificate rate be 97% propargyl phenolic aldehyde with zr element with
The molar ratio of carbon is 1:1 mixing, and reacts 2h at 50 DEG C, obtains ZrC presoma；
(4) Polycarbosilane is dissolved in dimethylbenzene, stirring 3h obtains SiC presoma；
(5) ZrC presoma made from step (3) and (4) and SiC presoma are pressed to the molar ratio 1 of zr element and element silicon:
Stirring 3h mixing after 0.61 mixing, and complex phase presoma is obtained after reacting 2h at 50 DEG C；
(6) by complex phase presoma made from step (5) in 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 250
DEG C each heat preservation 2h is allowed to solidify, and is subsequently placed in graphite furnace, inert atmosphere is heated to 1600 DEG C, obtains ZrC/SiC complex phase ceramic.
Embodiment 2
In the present embodiment, ZrC/SiC complex phase ceramic presoma is prepared with the following method:
(1) 40 DEG C at a temperature of, 0.8mol complexing agent ethyl acetoacetate is added to containing 1mol zirconium alkoxide and
In the zirconium alkoxide butanol solution of 5mol n-butanol, 2h is reacted；Later 40 DEG C at a temperature of, will in the solution after reaction again plus
Enter 1mol water and 2mol n-butanol, polycondensation be hydrolyzed, wherein the molar ratio of zirconium alkoxide, complexing agent, water and monohydric alcohol is 1:
0.8:1:7；
(2) 7mol is added in the solution in step (1) after hydrolytie polycondensation, dimethylbenzene is added, heating makes it in 125 DEG C of temperature
Lower pre-polymerization 1h is spent, the poly- zirconium oxygen alkane of nonpolarity is obtained；
(3) by nonpolarity office zirconium oxygen alkane made from step (2) and etherificate rate be 82% propargyl phenolic aldehyde with zr element with
The mass ratio of the material of carbon is 1:1.2 mixing, and reacts 2h at 50 DEG C, obtains ZrC presoma；
(4) Polycarbosilane is dissolved in dimethylbenzene, stirring 3h obtains SiC presoma；
(5) ZrC presoma made from step (3) and (4) and SiC presoma are pressed to the molar ratio 1 of zr element and element silicon:
Stirring 3h mixing after 0.65 mixing, and complex phase presoma is obtained after reacting 2h at 50 DEG C；
(6) by complex phase presoma made from step (5) in 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 250
DEG C each heat preservation 2h is allowed to solidify, and is subsequently placed in graphite furnace, inert atmosphere is heated to 1600 DEG C, obtains ZrC/SiC complex phase ceramic.
Embodiment 3
In the present embodiment, ZrC/SiC complex phase ceramic presoma is prepared with the following method:
(1) 25 DEG C at a temperature of, 1mol complexing agent acetylacetone,2,4-pentanedione is added to containing 1mol zirconium alkoxide and 5mol isopropyl
In the zirconium alkoxide aqueous isopropanol of alcohol, 2h is reacted；Later 25 DEG C at a temperature of, 1mol will be added in the solution after reaction
Water and 2mol isopropanol, are hydrolyzed polycondensation, wherein the molar ratio of zirconium alkoxide, complexing agent, water and monohydric alcohol is 1:1:1:7；
(2) 7mol dimethylbenzene is added in the solution in step (1) after hydrolytie polycondensation, heating makes it at a temperature of 125 DEG C
Pre-polymerization 1h obtains the poly- zirconium oxygen alkane of nonpolarity；
(3) by nonpolarity office zirconium oxygen alkane made from step (2) and etherificate rate be 82% propargyl phenolic aldehyde with zr element with
The molar ratio of carbon is 1:1 mixing, and reacts 2h at 50 DEG C, obtains ZrC presoma；
(4) Polycarbosilane is dissolved in dimethylbenzene, stirring 3h obtains SiC presoma；
(5) ZrC presoma made from step (3) and (4) and SiC presoma are pressed to the molar ratio 1 of zr element and element silicon:
Stirring 3h mixing after 0.63 mixing, and complex phase presoma is obtained after reacting 2h at 50 DEG C；
(6) by complex phase presoma made from step (5) in 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 250
DEG C each heat preservation 2h is allowed to solidify, and is subsequently placed in graphite furnace, inert atmosphere is heated to 1600 DEG C, obtains ZrC/SiC complex phase ceramic.
Embodiment 4
In the present embodiment, ZrC/SiC complex phase ceramic presoma is prepared with the following method:
(1) 25 DEG C at a temperature of, 1mol complexing agent acetylacetone,2,4-pentanedione is added to containing 1mol zirconium alkoxide and 5mol second two
In the zirconium alkoxide ethylene glycol monomethyl ether solution of alcohol methyl ether, 2h is reacted；Later 40 DEG C at a temperature of, by the solution after reaction again
1mol water and 2mol ethylene glycol monomethyl ether is added, polycondensation is hydrolyzed, wherein the molar ratio of zirconium alkoxide, complexing agent, water and monohydric alcohol
For 1:1:1:7；
(2) 7mol dimethylbenzene is added in the solution in step (1) after hydrolytie polycondensation, heating makes it at a temperature of 125 DEG C
Pre-polymerization 1h obtains the poly- zirconium oxygen alkane of nonpolarity；
(3) by nonpolarity office zirconium oxygen alkane made from step (2) and etherificate rate be 82% propargyl phenolic aldehyde with zr element with
The mass ratio of carbon is 1:1.2 mixing, and reacts 2h at 50 DEG C, obtains ZrC presoma；
(4) Polycarbosilane is dissolved in dimethylbenzene, stirring 3h obtains SiC presoma；
(5) ZrC presoma made from step (3) and (4) and SiC presoma are pressed to the molar ratio 1 of zr element and element silicon:
Stirring 3h mixing after 0.71 mixing, and complex phase presoma is obtained after reacting 2h at 50 DEG C；
(6) by complex phase presoma made from step (5) in 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 250
DEG C each heat preservation 2h is allowed to solidify, and is subsequently placed in graphite furnace, inert atmosphere is heated to 1600 DEG C, obtains ZrC/SiC complex phase ceramic.
Embodiment 5
In the present embodiment, ZrC/SiC complex phase ceramic presoma is prepared with the following method:
(1) 100 DEG C at a temperature of, 0.5mol complexing agent acetylacetone,2,4-pentanedione is added to containing 1mol zirconium alkoxide and 16mol
In the zirconium alkoxide unitary alcoholic solution of normal propyl alcohol and n-butanol mixed solution (molar ratio 1:1), 0.5h is reacted；Later in 95 DEG C of temperature
Under degree, 0.5mol water and 4mol normal propyl alcohol and n-butanol mixed solution (molar ratio 1:1) will be added in the solution after reaction, into
Row hydrolytie polycondensation, wherein the molar ratio of zirconium alkoxide, complexing agent, water and monohydric alcohol is 1:0.5:0.5:20；
(2) 20mol n-hexane is added in the solution in step (1) after hydrolytie polycondensation, heating makes it at a temperature of 120 DEG C
Pre-polymerization 1.5h obtains the poly- zirconium oxygen alkane of nonpolarity；
(3) by nonpolarity office zirconium oxygen alkane made from step (2) and etherificate rate be 99% propargyl phenolic aldehyde with zr element with
The mass ratio of carbon is 1:1.8 mixing, and reacts 0.5h at 80 DEG C, obtains ZrC presoma；
(4) Polycarbosilane is dissolved in dimethylbenzene, stirring 3.5h obtains SiC presoma；
(5) ZrC presoma made from step (3) and (4) and SiC presoma are pressed to the molar ratio 1 of zr element and element silicon:
Stirring 4h mixing after 6 mixing, and complex phase presoma is obtained after reacting 0.5h at 80 DEG C；
(6) complex phase presoma made from step (5) is solidified at 120 DEG C 1h, solidifies 1h at 140 DEG C later, later
Solidify 2h at 160 DEG C, solidify 2h at 180 DEG C later, solidify 2h at 200 DEG C later, solidifies 2h at 220 DEG C later,
Finally solidify 4h at 250 DEG C, be subsequently placed in graphite furnace, inert atmosphere is heated to 1500 DEG C, obtains ZrC/SiC complex phase pottery
Porcelain.
Embodiment 6
In the present embodiment, ZrC/SiC complex phase ceramic presoma is prepared with the following method:
(1) 95 DEG C at a temperature of, 2mol complexing agent ethyl acetoacetate is added to containing 1mol zirconium alkoxide and 5mol
In the zirconium alkoxide ethylene glycol ethyl ethers ethereal solution of ethylene glycol ethyl ether, 1h is reacted；Later 100 DEG C at a temperature of, by the solution after reaction
In add 2mol water and 1mol ethylene glycol ethyl ether, polycondensation is hydrolyzed, wherein zirconium alkoxide, complexing agent, water and monohydric alcohol rub
You are than being 1:2:2:6；
(2) 6mol normal heptane is added in the solution in step (1) after hydrolytie polycondensation, heating makes it at a temperature of 150 DEG C
Pre-polymerization 2h obtains the poly- zirconium oxygen alkane of nonpolarity；
(3) by nonpolarity office zirconium oxygen alkane made from step (2) and etherificate rate be 95% propargyl phenolic aldehyde with zr element with
The mass ratio of carbon is 1:2 mixing, and reacts 0.8h at 100 DEG C, obtains ZrC presoma；
(4) Polycarbosilane is dissolved in dimethylbenzene, stirring 2h obtains SiC presoma；
(5) ZrC presoma made from step (3) and (4) and SiC presoma are pressed to the molar ratio 1 of zr element and element silicon:
Stirring 2h mixing after 0.3 mixing, and complex phase presoma is obtained after reacting 0.8h at 100 DEG C；
(6) complex phase presoma made from step (5) is solidified at 120 DEG C 2h, solidifies 2h at 160 DEG C later, later
Solidify 2h at 180 DEG C, solidify 2h at 220 DEG C later, finally solidifies 2h at 250 DEG C, be subsequently placed in graphite furnace, inertia
Atmosphere is heated to 1800 DEG C, obtains ZrC/SiC complex phase ceramic.
Embodiment 7
In the present embodiment, ZrC/SiC complex phase ceramic presoma is prepared with the following method:
(1) 60 DEG C at a temperature of, 3mol complexing agent ethyl acetoacetate and 3mol complexing agent acetylacetone,2,4-pentanedione are added to
In zirconium alkoxide aqueous isopropanol containing 1mol zirconium alkoxide and 5mol isopropanol, 2h is reacted；Later 60 DEG C at a temperature of, will be anti-
1.5mol water and 5mol isopropanol are added in solution after answering, polycondensation is hydrolyzed, wherein zirconium alkoxide, complexing agent, water and one
The molar ratio of first alcohol is 1:6:1.5:10；
(2) 10mol toluene is added in the solution in step (1) after hydrolytie polycondensation, heating keeps it pre- at a temperature of 100 DEG C
Poly- 5h obtains the poly- zirconium oxygen alkane of nonpolarity；
(3) by nonpolarity office zirconium oxygen alkane made from step (2) and etherificate rate be 85% propargyl phenolic aldehyde with zr element with
The mass ratio of carbon is 1:2.5 mixing, and reacts 4h at 30 DEG C, obtains ZrC presoma；
(4) Polycarbosilane is dissolved in dimethylbenzene, stirring 4h obtains SiC presoma；
(5) ZrC presoma made from step (3) and (4) and SiC presoma are pressed to the molar ratio 1 of zr element and element silicon:
Stirring 1h mixing after 0.1 mixing, and complex phase presoma is obtained after reacting 4h at 30 DEG C；
(6) complex phase presoma made from step (5) is solidified at 120 DEG C 3h, solidifies 3h at 160 DEG C later, later
Solidify 3h at 180 DEG C, solidify 3h at 220 DEG C later, finally solidifies 2h at 250 DEG C, be subsequently placed in graphite furnace, inertia
Atmosphere is heated to 1700 DEG C, obtains ZrC/SiC complex phase ceramic.
Embodiment 8
In the present embodiment, ZrC/SiC complex phase ceramic presoma is prepared with the following method:
(1) 75 DEG C at a temperature of, 3mol complexing agent ethyl acetoacetate is added to containing 1mol zirconium alkoxide and 5mol
In the zirconium alkoxide ethylene glycol monomethyl ether solution of ethylene glycol monomethyl ether, 3h is reacted；Later 75 DEG C at a temperature of, will be in the solution after reaction
1.5mol water and 10mol ethylene glycol monomethyl ether are added, polycondensation is hydrolyzed, wherein zirconium alkoxide, complexing agent, water and monohydric alcohol
Molar ratio is 1:3:1.5:15；
(2) 10mol n-hexane and 5mol normal heptane are added in the solution in step (1) after hydrolytie polycondensation, heating makes it
Pre-polymerization 0.5h at a temperature of 180 DEG C obtains the poly- zirconium oxygen alkane of nonpolarity；
(3) by nonpolarity office zirconium oxygen alkane made from step (2) and etherificate rate be 80% propargyl phenolic aldehyde with zr element with
The mass ratio of carbon is 1:3 mixing, and reacts 5h at 130 DEG C, obtains ZrC presoma；
(4) Polycarbosilane is dissolved in dimethylbenzene, stirring 6h obtains SiC presoma；
(5) ZrC presoma made from step (3) and (4) and SiC presoma are pressed to the molar ratio 1 of zr element and element silicon:
Stirring 6h mixing after 15 mixing, and complex phase presoma is obtained after reacting 5h at 130 DEG C；
(6) complex phase presoma made from step (5) is solidified at 120 DEG C 1h, solidifies 1h at 140 DEG C later, later
Solidify 1h at 160 DEG C, solidify 2h at 180 DEG C later, solidify 2h at 200 DEG C later, solidifies 2h at 220 DEG C later,
Finally solidify 3h at 250 DEG C, be subsequently placed in graphite furnace, inert atmosphere is heated to 1600 DEG C, obtains ZrC/SiC complex phase pottery
Porcelain.
Embodiment 9
In the present embodiment, ZrC/SiC complex phase ceramic presoma is prepared with the following method:
(1) 40 DEG C at a temperature of, 1mol complexing agent ethyl acetoacetate is added to containing 1mol zirconium alkoxide and 5mol
In the zirconium alkoxide butanol solution of n-butanol, 4h is reacted；Later 40 DEG C at a temperature of, will be added in the solution after reaction
1mol water and 7mol n-butanol, are hydrolyzed polycondensation, wherein the molar ratio of zirconium alkoxide, complexing agent, water and monohydric alcohol is 1:1:1:
12；
(2) 12mol dimethylbenzene is added in the solution in step (1) after hydrolytie polycondensation, heating makes it at a temperature of 125 DEG C
Pre-polymerization 2h obtains the poly- zirconium oxygen alkane of nonpolarity；
(3) by nonpolarity office zirconium oxygen alkane made from step (2) and etherificate rate be 88% propargyl phenolic aldehyde with zr element with
The mass ratio of carbon is 1:1.2 mixing, and reacts 1h at 70 DEG C, obtains ZrC presoma；
(4) Polycarbosilane is dissolved in dimethylbenzene, stirring 1h obtains SiC presoma；
(5) ZrC presoma made from step (3) and (4) and SiC presoma are pressed to the molar ratio 1 of zr element and element silicon:
Stirring 1.8h mixing after 3 mixing, and complex phase presoma is obtained after reacting 1h at 70 DEG C；
(6) complex phase presoma made from step (5) is solidified at 120 DEG C 2h, solidifies 2h at 160 DEG C later, later
Solidify 2h at 180 DEG C, solidify 2h at 220 DEG C later, finally solidifies 2h at 250 DEG C, be subsequently placed in graphite furnace, inertia
Atmosphere is heated to 1600 DEG C, obtains ZrC/SiC complex phase ceramic.
Embodiment 10
In the present embodiment, ZrC/SiC complex phase ceramic presoma is prepared with the following method:
(1) 25 DEG C at a temperature of, 0.8mol complexing agent ethyl acetoacetate is added to containing 1mol zirconium alkoxide and
In the zirconium alkoxide normal propyl alcohol solution of 5mol normal propyl alcohol, 5h is reacted；Later 25 DEG C at a temperature of, will in the solution after reaction again plus
Enter 1mol water and 2mol normal propyl alcohol, polycondensation be hydrolyzed, wherein the molar ratio of zirconium alkoxide, complexing agent, water and monohydric alcohol is 1:
0.8:1:7；
(2) be added 3mol toluene and 4mol dimethylbenzene in the solution in step (1) after hydrolytie polycondensation, heating make its
Pre-polymerization 3h at a temperature of 125 DEG C obtains the poly- zirconium oxygen alkane of nonpolarity；
(3) by nonpolarity office zirconium oxygen alkane made from step (2) and etherificate rate be 93% propargyl phenolic aldehyde with zr element with
The mass ratio of carbon is 1:1 mixing, and reacts 0.5h at 60 DEG C, obtains ZrC presoma；
(4) Polycarbosilane is dissolved in dimethylbenzene, stirring 0.5h obtains SiC presoma；
(5) ZrC presoma made from step (3) and (4) and SiC presoma are pressed to the molar ratio 1 of zr element and element silicon:
Stirring 1.4h mixing after 1 mixing, and complex phase presoma is obtained after reacting 0.5h at 60 DEG C；
(6) by complex phase presoma made from step (5) in 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 250
DEG C each heat preservation 2h is allowed to solidify, and is subsequently placed in graphite furnace, inert atmosphere is heated to 1600 DEG C, obtains ZrC/SiC complex phase ceramic.
Comparative example 1
On the basis of embodiment 1, select etherificate rate for 79% modified phenolic as carbon source, the same embodiment of other conditions
1, the preparation of complex phase phase ceramics presoma is carried out,
Comparative example 2
On the basis of embodiment 1, select etherificate rate for 100% modified phenolic as carbon source, other conditions are the same as implementing
Example 1 carries out the preparation of complex phase phase ceramics presoma.
Comparative example 3
On the basis of embodiment 1, remove step (2), other embodiments are the same as embodiment 1.
Comparative example 4
On the basis of embodiment 1, remove the poly- zirconium oxygen alkane of nonpolarity and modified phenolic in step (3) and react 2h at 50 DEG C
Process, other embodiments are the same as embodiment 1.
Experimental example 1
The survey of viscosity change is carried out to ZrC/SiC complex phase ceramic presoma made from Examples 1 to 10 and comparative example 1~4
Examination, result are as shown in the table:
As seen from the above table, according to an embodiment of the present application obtained ZrC/SiC complex phase ceramic presoma in room temperature storage
Viscosity change after 12 months is less than 10%, although and comparative example 1 and 2 also uses the method in embodiment, the change of its viscosity
Change exceed 10% range, analysis be due to the etherificate degree of hydroxyl in carbon source phenolic resin is too low or it is excessively high caused by, and it is right
Viscosity change is very big after placement for the presoma produced in ratio 3 and 4, then is poly- due to having lacked high temperature pre-polymerization and nonpolarity
The reaction step of zirconium oxygen alkane and carbon source.It can be seen that the application increases high temperature prepolymerization step during the preparation process and will be non-
The method that the poly- zirconium oxygen alkane of polarity is reacted with carbon source reduces the active group in presoma, significantly increases presoma
Storage stability.
Experimental example 2
The ceramic yield of ZrC/SiC complex phase ceramic presoma made from Examples 1 to 10 and comparative example 1~4 is surveyed
Examination, the result is as follows:
As seen from the above table, the ceramic yield of ZrC/SiC complex phase ceramic presoma made from the embodiment of the present invention is higher than
Comparative example, wherein the etherificate rate of modified phenolic hydroxyl is lower in comparative example 1, i.e., can hand over strand in poly- zirconium oxygen alkane in carbon source
The carbon carbon unsaturated group mass contg of connection is lower, and carbon source can not be prevented to be lost in subsequent high temperature processing, and changes in comparative example 2
Property phenolic aldehyde hydroxyl etherificate rate it is higher, make in carbon source there is no not etherified phenolic hydroxyl group, therefore can not be reacted with poly- zirconium oxygen alkane
Yield is affected to reduce stability further to remove the active group in poly- zirconium oxygen alkane.And comparative example 3 and 4 due to
The reaction step for having lacked high temperature pre-polymerization and nonpolarity poly- zirconium oxygen alkane and carbon source, can not effectively reduce the activity in precursor solution
Group, and carbon source can not also be formed with poly- zirconium oxygen alkane strand and is crosslinked, and be lost carbon source in subsequent high temperature treatment process, thus
Reduce ceramic green yield.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this patent
Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompt make it is a little change or be modified to
The equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, it is right according to the technical essence of the invention
Any simple modification, equivalent change and modification made by above embodiments, in the range of still falling within the present invention program.
Claims (10)
1. a kind of ZrC/SiC complex phase ceramic presoma, which is characterized in that the presoma using the poly- zirconium oxygen alkane of nonpolarity as zirconium source,
Modified phenolic is carbon source, and Polycarbosilane is that silicon source reaction is prepared；Part of hydroxyl in the modified phenolic is etherified, and is contained
There is carbon carbon unsaturated functional group.
2. ZrC/SiC complex phase ceramic presoma according to claim 1, which is characterized in that hydroxyl in the modified phenolic
Etherificate rate be 80~99%, preferably 85~95%.
3. ZrC/SiC complex phase ceramic presoma according to claim 1, which is characterized in that the complex phase ceramic presoma
In, the molar ratio of zr element and carbon is 1:1~3, preferably 1:1~2；The molar ratio of zr element and element silicon is 1:0.1
~15, preferably 1:0.3~6.
4. ZrC/SiC complex phase ceramic presoma according to any one of claims 1 to 3, which is characterized in that the non-pole
It is hydrogen-based and/or alkyl that the molar content of Zr-OR, which is 0~3%, R, in the poly- zirconium oxygen alkane of property.
5. ZrC/SiC complex phase ceramic presoma described in any one according to claim 1~4, which is characterized in that the complex phase
After ceramic forerunner is placed 12 months at 25 DEG C, the change rate of viscosity is not more than 10%.
6. a kind of preparation method of ZrC/SiC complex phase ceramic presoma as claimed in any one of claims 1 to 5, wherein, feature
It is, the preparation method carries out high temperature pre-polymerization and be made nonpolar poly- after carrying out coordination protection and hydrolytie polycondensation to zirconium alkoxide
Zirconium oxygen alkane；The poly- zirconium oxygen alkane of nonpolarity obtained is mixed with modified phenolic later, ZrC forerunner is made after reacting at a certain temperature
Body.
7. the preparation method of ZrC/SiC complex phase ceramic presoma according to claim 6, which is characterized in that preparation nonpolarity
Poly- zirconium oxygen alkane includes the following steps:
(1) coordination protection: 25~100 DEG C at a temperature of, a certain amount of complexing agent is added to the unitary alcoholic solution of zirconium alkoxide
In, react 0.5~5h；
(2) hydrolytie polycondensation: 25~100 DEG C at a temperature of, step (1) reaction after solution in add a certain amount of water and
The mixed liquor of monohydric alcohol, is hydrolyzed polycondensation；
(3) high temperature pre-polymerization: to after step (2) hydrolytie polycondensation solution heat, make its at a temperature of 100~180 DEG C pre-polymerization 0.5~
Nonpolar solvent is added later and obtains the poly- zirconium oxygen alkane of nonpolarity by 5h；
Wherein, the molar ratio of zirconium alkoxide, complexing agent, water and monohydric alcohol is 1:0.5~6:0.5~2:6~20；
Preferably, the reaction temperature in step (1) and (2) is 60~95 DEG C, and the pre-polymerization temperature in step (3) is 120~150
℃。
8. the preparation method of ZrC/SiC complex phase ceramic presoma according to claim 6, which is characterized in that preparation ZrC forerunner
Body includes being blended in the poly- zirconium oxygen alkane of nonpolarity at 30~130 DEG C with modified phenolic to react 0.5~5h；
Preferably, the poly- zirconium oxygen alkane of nonpolarity is blended at 50~80 DEG C with modified phenolic reacts 2~4h.
9. according to the preparation method of ZrC/SiC complex phase ceramic presoma described in claim 6~8 any one, which is characterized in that
The preparation method further includes Polycarbosilane being dissolved to and being stirred 0.5~6h SiC precursor solution is made in nonpolar solvent,
And it is laggard after being mixed in a certain ratio SiC precursor solution with the ZrC presoma to react 0.5~5h at 30~130 DEG C
Row solidification；
Preferably, 2~4h is reacted at 50~80 DEG C after SiC precursor solution is mixed in a certain ratio with the ZrC presoma.
10. the preparation method of ZrC/SiC complex phase ceramic presoma according to claim 9, which is characterized in that the solidification packet
It includes and carries out the solidification of 4~normal pressure for 24 hours under the conditions of 110~300 DEG C, crack system under 1500~1800 DEG C of inert atmosphere later
Obtain complex phase ceramic presoma；
The solidification process includes: 2~3h of solidification at 120 DEG C, solidifies 2~3h at 160 DEG C later, later at 180 DEG C
Solidify 2~3h, solidify 2~3h at 220 DEG C later, finally solidifies 2h at 250 DEG C and be made；
Alternatively, solidifying 1~2h at 120 DEG C, solidify 1~2h at 140 DEG C later, solidifies 1~2h at 160 DEG C later, it
Solidify 1~2h at 180 DEG C afterwards, solidify 1~2h at 200 DEG C later, solidifies 1~2h at 220 DEG C later, finally 250
Solidify 2~4h at DEG C to be made.
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| CN111187075A (en) * | 2020-02-18 | 2020-05-22 | 陕西科技大学 | Precursor conversion method preparation process of self-dispersion superfine ZrC-SiC ceramic composite powder |
| CN111592358A (en) * | 2020-04-09 | 2020-08-28 | 中国科学院化学研究所 | Carbide high-entropy ceramic fiber and preparation method thereof |
| CN112409020A (en) * | 2020-10-30 | 2021-02-26 | 江苏材睿科技有限公司 | High-temperature-resistant and antioxidant coating on surface of graphite material and preparation method thereof |
| CN112299871A (en) * | 2020-11-16 | 2021-02-02 | 哈尔滨科友半导体产业装备与技术研究院有限公司 | Preparation method of porous ceramic containing silicon carbide film |
| CN115385717A (en) * | 2022-08-23 | 2022-11-25 | 合肥学院 | Preparation method and application of silicon carbide film with sub-nanometer aperture |
| CN115385717B (en) * | 2022-08-23 | 2023-08-25 | 合肥学院 | Preparation method and application of silicon carbide film with sub-nanometer pore diameter |
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