CN104140537B - Hybridization liquid precursor, and method for preparing ZrC-SiC superhigh temperature ceramics and composite materials of ZrC-SiC superhigh temperature ceramics through hybridization liquid precursor - Google Patents
Hybridization liquid precursor, and method for preparing ZrC-SiC superhigh temperature ceramics and composite materials of ZrC-SiC superhigh temperature ceramics through hybridization liquid precursor Download PDFInfo
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Abstract
The invention relates to hybridization liquid precursor, and a method for preparing ZrC-SiC superhigh temperature ceramics and composite materials of the ZrC-SiC superhigh temperature ceramics through the hybridization liquid precursor. Solid PZC precursor and carbon-rich vinyl adopted to replace liquid polycarbosilane (LPCS) precursor serve as raw materials for the first time and are processed in a hybridization mode to synthesize the brand new hybridization liquid precursor which is low in viscosity, adjustable in component, low in solidifying temperature, good in dipping performance, free of toxicity, harmless and high in productivity, organic solvent does not need to be added to the hybridization liquid precursor, the hybridization liquid precursor can be used for preparing the ZrC-SiC superhigh temperature ceramics and the composite materials of the ZrC-SiC superhigh temperature ceramics, and according to the thermogravimetric analysis, the ceramic productivity of the hybridization liquid LPCS-PZC ceramic precursor is more than 69 percent. The percent conversion of the ZrC-SiC superhigh temperature ceramics or the percent conversion of the fiber-reinforced ZrC-SiC superhigh temperature ceramic composite material ceramic is high, the technology is simple, and the high-temperature oxidation resistance of the obtained materials is good.
Description
Technical field
The present invention relates to a kind of hydridization liquid precursor, ZrC-SiC superhigh temperature ceramics and its multiple be prepared using the presoma
The method of condensation material, belongs to superhigh temperature ceramics field.
Background technology
The boride and carbide superhigh temperature ceramics of transition metal and its composite are hypersonic aircraft, super burn punching
The important thermally protective materials of hydraulic motor, are also solar absorption, the critical material of nuclear reactor application.ZrC is due to height
Fusing point, high heat conductance, room temperature to fusing point becomes space industry and nuclear industry field most without phase transformation, thermo-chemical stability the advantages of good
There are one of superhigh temperature ceramics of application potential.But, it is undesirable in the antioxygenic property of high temperature and superhigh temperature ZrC ceramics, need
Introduce SiC second and mutually improve its high-temperature oxidation resistance.[the Key.Eng.Mater.512-515 of document 1:715-718 (2012) passes through
The method of solid phase mechanical mixture is prepared for ZrC-SiC composite powders, this process is simple, but ensures that ZrC-SiC composite powders are mixed
Conjunction is uniformly a scabrous problem.Additionally, need in ultra-temperature ceramic-based composite material preparation process by ZrC-SiC with
The form of liquid precursor is incorporated in fabric, and the reaction of Jing Pintsch process generates ZrC-SiC matrixes.Therefore, ZrC-SiC liquid
State presoma is all extremely important for preparation ZrC-SiC superhigh temperature ceramics and fiber reinforcement ZrC-SiC based composites.Liquid is made pottery
The major advantage of porcelain presoma include (1) can control composition uniformity on a molecular scale, (2) need not add extra to be had
Machine solvent, the process equipment required for (3) is simple, and (4) can both prepare ZrC-SiC superhigh temperature ceramics and can also prepare fiber increasing
Strong ZrC-SiC based composites or superhigh temperature ceramics coating.
However, at present still without ZrC-SiC liquid superhigh temperature ceramics presomas.The presoma of generally ZrC ceramics is acetyl
Acetone zirconium (PZC), room temperature is solid, prepares fiber reinforcement ultra-temperature ceramic-based composite material or prepares ZrC-SiC superhigh temperature pottery
Need to add organic solvent during porcelain (see (Ceram.Inter.37 of document 2:2089-2093(2011))).Due in technical process
Add organic solvent so that the conversion ratio of ceramics is reduced to less than 40%.And the presoma of SiC ceramic is the Polycarbosilane of solid phase
(PCS), prepare fiber reinforcement ultra-temperature ceramic-based composite material or need addition organic molten when preparing ZrC-SiC superhigh temperature ceramics
Agent.Similarly, since adding organic solvent in technical process so that the conversion ratio of ceramics is reduced to.Existing method is by solid phase
Polycarbosilane (PCS) and solid phase acetylacetone,2,4-pentanedione zirconium (PZC) mixing, adding organic solvent, to be prepared into hybrid ceramic presoma molten
Liquid, then directly prepares ZrC-SiC superhigh temperature ceramics or after being impregnated in fabric repeatedly, solidifies, is cracked into fiber
Strengthen the ceramic matric composite ((Ceram.Inter.38 of document 4:3419-3425(2012))).The shortcoming of the method is ceramics
Low yield, the volatilization of organic matter in dipping process causes the viscosity of presoma to change, and organic solvent has to human body and environment
Certain injury.
The content of the invention
It is an object of the invention to overcome the above-mentioned deficiency of prior art, there is provided a kind of hydridization liquid precursor and its preparation
Method, the hydridization liquid precursor is miscellaneous by the way that the acetylacetone,2,4-pentanedione zirconium (PZC) of solid phase is dissolved in into Jing in liquid Polycarbosilane (LPCS)
Change to process and generate, the viscosity of the hydridization liquid precursor is low, composition is adjustable, curing process temperature is relatively low, using the forerunner figure
Prepare the high conversion rate of ZrC-SiC superhigh temperature ceramics or fiber reinforcement ZrC-SiC ultra-temperature ceramic-based composite materials ceramics, technique
Simply, the high-temperature oxidation resistance of the material for being obtained is good.
Another object of the present invention be provide using above-mentioned hydridization presoma prepare ZrC-SiC superhigh temperature ceramics and
The method of its composite.
What the above-mentioned purpose of the present invention was mainly achieved by following technical solution：
A kind of hydridization liquid precursor, it is characterised in that：Its structural formula is as follows：
Wherein：R=CH3Or H.
In above-mentioned hydridization liquid precursor, the viscosity of hydridization liquid ceramic presoma is 1.8-20Pa.s.
The preparation method of above-mentioned hydridization liquid precursor, by the vinyl of rich carbon liquid Polycarbosilane presoma LPCS is replaced
With solid-state acetylacetone,2,4-pentanedione zirconium precursor body PZC according to 1：0.5-1：After 4 mass ratio mixing, carry out hydridization process and obtain, at hydridization
Manage bar part is：Hydridization treatment temperature 10-40 DEG C, 90-280 rev/min of magnetic agitation rotating speed, process time 2-10 hour；
The vinyl of wherein rich carbon replaces the structural formula of liquid Polycarbosilane presoma LPCS as follows：
Wherein：R=CH3Or H；
The structural formula of solid-state acetylacetone,2,4-pentanedione zirconium precursor body PZC is as follows：
Wherein：R=CH3Or H.
In the preparation method of above-mentioned hydridization liquid precursor, the vinyl of rich carbon replaces liquid Polycarbosilane presoma
The molecular weight M of LPCSwFor 1449, the molecular weight M of solid-state acetylacetone,2,4-pentanedione zirconium precursor body PZCwFor 64870.
The method for preparing ZrC-SiC superhigh temperature ceramics using above-mentioned hydridization liquid precursor, comprises the steps：
(1), hydridization liquid ceramic presoma is carried out into curing process, solidification temperature is 150 DEG C -220 DEG C, hardening time is
1-5 hours；
(2), the hydridization liquid ceramic presoma after solidification is carried out into Pintsch process under the protection of inert gas or hydrogen
Process, or Pintsch process process is carried out in vacuum environment, obtain ZrC-SiC superhigh temperature ceramics.
Prepare in the method for ZrC-SiC superhigh temperature ceramics in above-mentioned employing hydridization liquid precursor, step (2) high temperature is split
The temperature that solution is processed is 1100-1600 DEG C, and process time is 1-8 hours.
The method that ZrC-SiC ultra-temperature ceramic-based composite materials are prepared using above-mentioned hydridization liquid precursor, including it is as follows
Step：
(1) in, hydridization liquid ceramic presoma being impregnated into into fabric or foraminous die plate, dipping environment is vacuum, is soaked
Stain temperature is 25-50 DEG C, and dip time is 2-10 hours；
(2), the fabric after impregnation process is carried out into curing process, solidification temperature is 150 DEG C -220 DEG C, hardening time
For 1-5 hours；
(3), by the fabric or foraminous die plate of the presoma of liquid ceramic containing hydridization after solidification in inert gas or hydrogen
Protection under carry out Pintsch process process, or Pintsch process process is carried out in vacuum environment, obtain fiber reinforcement ZrC-SiC
Ultra-temperature ceramic-based composite material.
Prepare in the method for ZrC-SiC ultra-temperature ceramic-based composite materials in above-mentioned employing hydridization liquid precursor, step
(3) temperature that high temperature cracking is processed is 1100-1600 DEG C, and process time is 1-8 hours.
Prepare in the method for ZrC-SiC ultra-temperature ceramic-based composite materials in above-mentioned employing hydridization liquid precursor, fiber
Fabric is carbon fibre fabric or silicon carbide fibre；Foraminous die plate is carbon template.
The present invention has the advantages that compared with prior art：
(1), the present invention replaces liquid Polycarbosilane presoma (LPCS) and solid-state acetyl using the vinyl of rich carbon first
Acetone zirconium precursor body (PZC) is raw material, and the process of Jing hydridization has synthesized a kind of brand-new hydridization liquid precursor, and the presoma is in liquid
State, viscosity is low, immersion good, nontoxic, harmless, and yield is high, need not add organic solvent, can be used to prepare ZrC-SiC superelevation
Warm ceramic composite materials, Jing thermogravimetric analysis show hydridization liquid LPCS-PZC ceramic forerunner ceramic yield be 69% with
On；
(2), the solidification temperature of the hydridization liquid LPCS-PZC ceramic forerunner that the present invention is prepared is relatively low, curing process
Simply；Simultaneously hydridization liquid LPCS-PZC ceramic forerunner impregnation technology is simple, and dipping temperature is low, without the need for high-tension apparatus；
(3), the direct product of the hydridization liquid LPCS-PZC ceramic forerunner Pintsch process that the present invention is prepared is
ZrC-SiC, the content of the two can as needed adjust material rate and obtain during hydridization presoma is prepared, and make
Obtain preparation process more flexibly controllable；
(4) the ZrC-SiC superhigh temperature ceramics and the non-oxidizability of composite that, present invention is prepared are good, 400-
1400 DEG C of long-time oxidation kinetics meet parabola rule, the ZrO of Surface Creation2And SiO2To matrix and carbon fibre fabric tool
There is good protectiveness；
(5), the present invention passes through lot of experiments to ZrC-SiC superhigh temperature ceramics and the process conditions of composite preparation process
It is optimized, especially the composition of hydridization liquid ceramic presoma, viscosity, the process conditions of dipping, solidification and cracking enter one
Step improves the intensity and high-temperature oxidation resistance of ZrC-SiC superhigh temperature ceramics and composite；
(6), the preparation method process is simple of ZrC-SiC superhigh temperature ceramics of the present invention and composite, be easily achieved, have
Stronger practicality.
Description of the drawings
Fig. 1 is rich carbon liquid state Polycarbosilane (LPCS) used by the present invention, solid-state acetylacetone,2,4-pentanedione zirconium precursor body (PZC) and miscellaneous
Change processes the infrared spectrogram of the hydridization liquid LPCS-PZC ceramic forerunner for obtaining；Wherein a is rich carbon liquid state Polycarbosilane
(LPCS) infrared spectrum, b is the infrared spectrum of solid-state acetylacetone,2,4-pentanedione zirconium precursor body (PZC), and c is hydridization liquid LPCS-PZC pottery
The infrared spectrum of porcelain presoma；
Fig. 2 is the viscosity and liquid Polycarbosilane (LPCS) and solid-state of hydridization liquid LPCS-PZC ceramic forerunner of the present invention
The relation of acetylacetone,2,4-pentanedione zirconium (PZC) ratio；Illustration dissolves in liquid Polycarbosilane for solid-state acetylacetone,2,4-pentanedione zirconium (PZC) of different content
(LPCS) the minimum time needed in；
Fig. 3 is the different liquid Polycarbosilanes (LPCS) and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) ratio that the present invention is prepared
Hydridization liquid LPCS-PZC ceramic forerunner solidification after ceramic conversion rate；
Fig. 4 is liquid Polycarbosilane (LPCS) of the present invention and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) ratio is 1：Hydridization liquid when 1
The high-temperature oxydation kinetic curve of the ZrC-SiC ceramics obtained after LPCS-PZC ceramic forerunner Pintsch process；
Fig. 5 is liquid Polycarbosilane (LPCS) of the present invention and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) ratio is 1：Hydridization liquid when 1
600 DEG C, 800 DEG C, 1000 DEG C and 1300 of the ZrC-SiC superhigh temperature ceramics Jing obtained after LPCS-PZC ceramic forerunner Pintsch process
Pattern after DEG C high-temperature oxydation；It is 600 DEG C wherein to scheme a, and figure b is 800 DEG C, and figure c is 1000 DEG C, and figure d is 1300 DEG C；
Fig. 6 is impregnated in carbon fibre fabric for hydridization liquid LPCS-PZC ceramic forerunner of the present invention, cured, high anneal crack
The microstructure photograph of the fiber reinforcement ZrC-SiC ultra-temperature ceramic-based composite materials obtained after solution；
Fig. 7 is that liquid Polycarbosilane and solid-state acetylacetone,2,4-pentanedione zirconium precursor body mass ratio are 1 in the embodiment of the present invention：When 0.7
The stereoscan photograph and composition analysis result figure of the ZrC-SiC superhigh temperature ceramics for obtaining, wherein figure a is stereoscan photograph,
Figure b is energy spectrum composition analysis result.
Specific embodiment
Below in conjunction with the accompanying drawings the present invention is further detailed explanation with specific embodiment：
The liquid Polycarbosilane (LPCS) of rich carbon in example 1 below -7, is that vinyl replaces, its molecular weight MwFor
1449, solid-state acetylacetone,2,4-pentanedione zirconium precursor body (PZC), molecular weight MwFor 64870.
Embodiment 1
Rich carbon liquid state Polycarbosilane (LPCS) and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) presoma are pressed into 1：The mixing of 1 mass ratio is equal
Even, hydridization processes 3 hours hydridization and processes under the conditions of 30 DEG C of temperature and 200 revs/min of magnetic agitations, the hydridization liquid for obtaining
The molecular structural formula of LPCS-PZC ceramic forerunners is as follows：
Wherein：R=CH3Or H.
The vinyl of wherein rich carbon replaces the structural formula of liquid Polycarbosilane presoma LPCS as follows：
Wherein：R=CH3Or H；
The structural formula of solid-state acetylacetone,2,4-pentanedione zirconium precursor body PZC is as follows：
Wherein：R=CH3Or H.
The present invention is illustrated in figure 1 using rich carbon liquid state Polycarbosilane (LPCS), solid-state acetylacetone,2,4-pentanedione zirconium precursor body (PZC)
The infrared spectrogram of the hydridization liquid LPCS-PZC ceramic forerunner obtained with hydridization process；Wherein a is the poly- carbon silicon of rich carbon liquid state
The infrared spectrum of alkane (LPCS), b is the infrared spectrum of solid-state acetylacetone,2,4-pentanedione zirconium precursor body (PZC), and c is hydridization liquid LPCS-PZC
The infrared spectrum of ceramic forerunner；
Jing infrared spectrum analysis can be seen that 2920,2135,1356,1047,926 and 765cm in Fig. 1 (c)-1Place has by force
The increase of degree and the skew of peak position, it was demonstrated that liquid Polycarbosilane (LPCS) and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) presoma there occurs
Hydridization.Hydridization liquid LPCS-PZC ceramic forerunner combines liquid Polycarbosilane (LPCS) and solid-state acetylacetone,2,4-pentanedione zirconium (PZC)
The Common advantages of presoma.
Embodiment 2
Rich carbon liquid state Polycarbosilane (LPCS) and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) presoma are pressed into 1：1,1：1.5,1：2,1：
2.5,1：3,1：3.5,1：4 mass ratio is well mixed, and hydridization processes 5 under the conditions of 25 DEG C of temperature and 250 revs/min of magnetic agitations
Hour hydridization is processed, the hydridization liquid LPCS-PZC ceramic forerunner for obtaining.Before the liquid LPCS-PZC ceramics of the hydridization for obtaining
Drive liquid flowability good, be suitable for ultra-temperature ceramic-based multiple using dipping-solidification-cracking technology preparation fiber reinforcement ZrC-SiC
Condensation material.
It is illustrated in figure 2 the viscosity and liquid Polycarbosilane (LPCS) of hydridization liquid LPCS-PZC ceramic forerunner of the present invention
With the relation of solid-state acetylacetone,2,4-pentanedione zirconium (PZC) ratio；Illustration dissolves in liquid and gathers for solid-state acetylacetone,2,4-pentanedione zirconium (PZC) of different content
The minimum time needed in carbon silane (LPCS).As seen from Figure 2 under this process conditions before hydridization liquid LPCS-PZC ceramics
The spread of viscosity for driving body is 2-19Pa.s.
Embodiment 3
Rich carbon liquid state Polycarbosilane (LPCS) and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) presoma are pressed into 1：1,1：2,1：3,1：4
Mass ratio be well mixed, hydridization processes 8 hours hydridization and processes under the conditions of 35 DEG C of temperature and 180 revs/min of magnetic agitations, obtains
Hydridization liquid LPCS-PZC ceramic forerunner.The good fluidity of hydridization liquid LPCS-PZC ceramic forerunner.By hydridization liquid
State LPCS-PZC ceramic forerunner solidifies 4 hours at 195 DEG C, and Jing thermogravimetric analysis shows hydridization liquid LPCS-PZC ceramic forerunner
Ceramic yield when ratio be 1：It is 77%, 1 when 1:It is 75%, 1 when 2：It is 74%, 1 when 3：It is 69% when 4.It is illustrated in figure 3
Different liquid Polycarbosilanes (LPCS) and the hydridization liquid of solid-state acetylacetone,2,4-pentanedione zirconium (PZC) ratio that the present invention is prepared
Ceramic conversion rate after the solidification of LPCS-PZC ceramic forerunners.
Embodiment 4
Rich carbon liquid state Polycarbosilane (LPCS) and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) presoma are pressed into 1：The mixing of 1 mass ratio is equal
Even, hydridization processes 3 hours hydridization and processes under the conditions of 30 DEG C of temperature and 200 revs/min of magnetic agitations, the hydridization liquid for obtaining
LPCS-PZC ceramic forerunners.200 DEG C of solidifications of Jing obtain the hydridization LPCS-PZC ceramic forerunner for solidifying, Ran Hou for 2 hours
1500 DEG C, the lower cracking of argon gas protection obtain ZrC-SiC superhigh temperature ceramics within 1 hour.400-1300 DEG C of oxidation experiment shows：ZrC-
SiC superhigh temperature ceramics high-temperature oxidation resistance is good, is diffusion control, and oxidation kinetics follows all the time parabola rule, such as Fig. 4 institutes
It is 1 to be shown as liquid Polycarbosilane (LPCS) of the present invention and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) ratio：Hydridization liquid LPCS-PZC when 1
The high-temperature oxydation kinetic curve of the ZrC-SiC ceramics obtained after ceramic forerunner Pintsch process.
The ZrO generated after high-temperature oxydation2And SiO2ZrC-SiC superhigh temperature ceramics are played a protective role, is prevented further
Oxidation, it is 1 to be illustrated in figure 5 liquid Polycarbosilane (LPCS) of the present invention and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) ratio：Hydridization when 1
600 DEG C of the ZrC-SiC superhigh temperature ceramics Jing obtained after liquid LPCS-PZC ceramic forerunner Pintsch process, 800 DEG C, 1000 DEG C and
Pattern after 1300 DEG C of high-temperature oxydations；It is 600 DEG C wherein to scheme a, and figure b is 800 DEG C, and figure c is 1000 DEG C, and figure d is 1300 DEG C.
Embodiment 5
Rich carbon liquid state Polycarbosilane (LPCS) and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) presoma are pressed into 1：3 mass ratio mixing
Uniformly, hydridization processes hydridization process in 2 hours, the hydridization liquid for obtaining under the conditions of 35 DEG C of temperature and 150 revs/min of magnetic agitations
LPCS-PZC ceramic forerunners.180 DEG C of solidifications of Jing obtain the hydridization LPCS-PZC ceramic forerunner for solidifying, Ran Hou for 3 hours
1400 DEG C, the lower cracking of argon gas protection obtain ZrC-SiC superhigh temperature ceramics within 3 hours.400-1300 DEG C of oxidation experiment shows：ZrC-
SiC superhigh temperature ceramics high-temperature oxidation resistance is good, is diffusion control, and oxidation kinetics follows all the time parabola rule.
Embodiment 6
Rich carbon liquid state Polycarbosilane (LPCS) and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) presoma are pressed into 1：The mixing of 1 mass ratio is equal
Even, hydridization processes 3 hours hydridization and processes under the conditions of 30 DEG C of temperature and 200 revs/min of magnetic agitations, the hydridization liquid for obtaining
LPCS-PZC ceramic forerunners.Hydridization liquid LPCS-PZC ceramic forerunner is impregnated into under vacuum conditions two-dimentional needled carbon fine
In dimensional fabric, dipping temperature is 35 DEG C, and dip time is 10 hours, after 180 DEG C of Jing solidification obtain within 3 hours solidifying containing hydridization
Cracking under the fiber preform of LPCS-PZC ceramic forerunners, then the protection of 1500 DEG C of Jing, argon gas obtains fibre reinforced in 2 hours
ZrC-SiC based ultra-high temperature ceramic composites, are illustrated in figure 6 hydridization liquid LPCS-PZC ceramic forerunner of the present invention and are impregnated into
The fiber reinforcement ZrC-SiC ultra-temperature ceramic-based composite materials obtained in carbon fibre fabric, after cured, Pintsch process it is micro-
Structure photo.The density of the composite for obtaining is 2.1g/cm3, intensity is 145MPa, and 1300 DEG C of static state are tied after aoxidizing 2 hours
Structure is complete, the oxide-film of surface existence white.
Embodiment 7
Rich carbon liquid state Polycarbosilane (LPCS) and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) presoma are pressed into 1：The mixing of 4 mass ratioes is equal
Even, hydridization processes 5 hours hydridization and processes under the conditions of 40 DEG C of temperature and 200 revs/min of magnetic agitations, the hydridization liquid for obtaining
LPCS-PZC ceramic forerunners.Hydridization liquid LPCS-PZC ceramic forerunner is impregnated into under vacuum conditions two-dimentional acupuncture carbonization
In silica fibre fabric, dipping temperature is 40 DEG C, and dip time is 8 hours, after 200 DEG C of Jing solidification containing of obtaining for 5 hours solidifying
Cracking under the fiber preform of hydridization LPCS-PZC ceramic forerunner, then the protection of 1400 DEG C of Jing, argon gas obtains carborundum fibre for 5 hours
Dimension strengthens ZrC-SiC based ultra-high temperature ceramic composites.The density of the composite for obtaining is 2.8g/cm3, intensity is
130MPa, 1800 DEG C of ablation tests show that anti-yaw damper is functional.
Embodiment 8
Rich carbon liquid state Polycarbosilane (LPCS) and solid-state acetylacetone,2,4-pentanedione zirconium (PZC) presoma are pressed into 1：0.7 mass ratio mixes
Uniformly, hydridization processes hydridization process in 3 hours, the hydridization liquid for obtaining under the conditions of 30 DEG C of temperature and 200 revs/min of magnetic agitations
LPCS-PZC ceramic forerunners.200 DEG C of solidifications of Jing obtain the hydridization LPCS-PZC ceramic forerunner for solidifying, Ran Hou for 2 hours
1300 DEG C, the lower cracking of argon gas protection obtain ZrC-SiC superhigh temperature ceramics within 1 hour.
It is 1 to be illustrated in figure 7 liquid Polycarbosilane and solid-state acetylacetone,2,4-pentanedione zirconium precursor body mass ratio in the embodiment of the present invention：
The stereoscan photograph and composition analysis result figure of the ZrC-SiC superhigh temperature ceramics obtained when 0.7, wherein figure a is ESEM
Photo, figure b is energy spectrum composition analysis result.As seen from the figure ZrC and SiC two-phases are evenly distributed, the composition and raw material of ZrC and SiC
The ratio of middle LPCS and PZC is suitable.
The above, optimal specific embodiment only of the invention, but protection scope of the present invention is not limited thereto,
Any those familiar with the art the invention discloses technical scope in, the change or replacement that can be readily occurred in,
All should be included within the scope of the present invention.
The content not being described in detail in description of the invention belongs to the known technology of professional and technical personnel in the field.
Claims (8)
1. a kind of hydridization liquid precursor, it is characterised in that be prepared via a method which to obtain：
Liquid Polycarbosilane presoma LPCS and solid-state acetylacetone,2,4-pentanedione zirconium precursor body PZC is replaced according to 1 by the vinyl of rich carbon：
0.5-1：After 4 mass ratio mixing, carry out hydridization process and obtain, hydridization treatment conditions are：Hydridization treatment temperature 10-40 DEG C, magnetic
90-280 rev/min of power speed of agitator, process time 2-10 hour；
The vinyl of wherein rich carbon replaces the structural formula of liquid Polycarbosilane presoma LPCS as follows：
Wherein：R=CH3Or H, n, x are positive integer, and x<n；
The structural formula of solid-state acetylacetone,2,4-pentanedione zirconium precursor body PZC is as follows：
Wherein：N is positive integer.
2. a kind of hydridization liquid precursor according to claim 1, it is characterised in that：The vinyl of the rich carbon replaces liquid
The molecular weight M of state Polycarbosilane presoma LPCSwFor 1449, the molecular weight M of solid-state acetylacetone,2,4-pentanedione zirconium precursor body PZCwFor 64870.
3. the method for preparing ZrC-SiC superhigh temperature ceramics using the hydridization liquid precursor described in claim 1, its feature exists
In：Comprise the steps：
(1), hydridization liquid ceramic presoma is carried out into curing process, solidification temperature is 150 DEG C -220 DEG C, and hardening time is 1-5
Hour；
(2), the hydridization liquid ceramic presoma after solidification is carried out into Pintsch process process under the protection of inert gas or hydrogen,
Or Pintsch process process is carried out in vacuum environment, obtain ZrC-SiC superhigh temperature ceramics.
4. the method that employing hydridization liquid precursor according to claim 3 prepares ZrC-SiC superhigh temperature ceramics, its feature
It is：The temperature that step (2) the high temperature cracking is processed is 1100-1600 DEG C, and process time is 1-8 hours.
5. the method for ZrC-SiC ultra-temperature ceramic-based composite materials being prepared using the hydridization liquid precursor described in claim 1,
It is characterized in that：Comprise the steps：
(1) in, hydridization liquid ceramic presoma being impregnated into into fabric or foraminous die plate, dipping environment is vacuum, and dipping is warm
Spend for 25-50 DEG C, dip time is 2-10 hours；
(2), the fabric after impregnation process is carried out into curing process, solidification temperature is 150 DEG C -220 DEG C, and hardening time is 1-
5 hours；
(3), by the fabric or foraminous die plate of the presoma of liquid ceramic containing hydridization after solidification in inert gas or the guarantor of hydrogen
Pintsch process process is carried out under shield, or Pintsch process process is carried out in vacuum environment, obtain fiber reinforcement ZrC-SiC superelevation
Warm ceramic matric composite.
6. employing hydridization liquid precursor according to claim 5 prepares ZrC-SiC ultra-temperature ceramic-based composite materials
Method, it is characterised in that：The temperature that step (3) the high temperature cracking is processed is 1100-1600 DEG C, and process time is that 1-8 is little
When.
7. the employing hydridization liquid precursor according to claim 5 or 6 prepares ZrC-SiC ultra-temperature ceramic-based composite materials
Method, it is characterised in that：The fabric is carbon fibre fabric or silicon carbide fibre；The foraminous die plate is carbon template.
8. a kind of hydridization liquid precursor according to claim 1, it is characterised in that：The hydridization liquid ceramic presoma
Viscosity be 1.8-20Pa.s.
Priority Applications (1)
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| CN106083114A (en) * | 2016-06-03 | 2016-11-09 | 苏州赛力菲陶纤有限公司 | A kind of C/C ZrC SiC ceramic based composites brake disc and preparation method thereof |
| CN107188590B (en) * | 2017-05-19 | 2021-07-16 | 中国航空工业集团公司基础技术研究院 | Forming method of fiber reinforced SiC-based composite material |
| CN107244917A (en) * | 2017-05-25 | 2017-10-13 | 中国科学院上海硅酸盐研究所 | A kind of low viscosity liquid ZrC SiC presomas and its preparation method and application |
| CN110066186B (en) * | 2018-01-23 | 2021-11-30 | 航天特种材料及工艺技术研究所 | C/SiC composite material and preparation method thereof |
| CN111018533A (en) * | 2019-12-25 | 2020-04-17 | 南方科技大学 | Porous silicon carbide-based composite ceramic material and preparation method and application thereof |
| CN116063102B (en) * | 2022-12-04 | 2024-04-05 | 航天材料及工艺研究所 | High-temperature-resistant coating capable of being repaired online and preparation method thereof |
| CN115849910A (en) * | 2022-12-04 | 2023-03-28 | 航天材料及工艺研究所 | HfC-SiC complex phase ceramic matrix composite material and preparation method thereof |
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