CN101838153A - Molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material - Google Patents
Molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material Download PDFInfo
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Abstract
The invention relates to a ceramic matrix composite material, and provides a molding method of a mullite fiber reinforced magnesium silicate ceramic matrix composite material with complex shape, better uniformity, high density and strength and stronger toughness. The method comprises the following steps: calcining raw material MgO, drying SiO2, mixing MgO with SiO2, ball-milling, drying, screening, presintering and then obtaining magnesium silicate powder; mixing the obtained magnesium silicate powder with premixed liquid to prepare ceramic slurry, adding mullite fiber and a dispersing agent into the ceramic slurry, mixing, adding a catalyst and an initiator, and then injecting into a mold to obtain a molded green body; and demolding the molded green body, and then sintering to obtain the mullite fiber reinforced magnesium silicate ceramic matrix composite material.
Description
Technical field
The present invention relates to a kind of ceramic matric composite, especially relate to a kind of low-cost and high-performance molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material.
Background technology
Mg
2SiO
4(Forsterite) be the main component of ground in slow, often be called as forsterite, because its fusing point is higher, stable crystal form, goods can obtain the good high-temperature performance, therefore be widely used in industries such as iron and steel, nonferrous smelting and glass (appoint strong, Wu Xiulan. the progress of synthesis of dichroite stupalith. Chinese pottery, 2000, (6): 23-26), simultaneously, it has low specific inductivity, high Qf value is compared Al
2O
3Pottery, has low sintering temperature, abundant raw material is cheap, the also basic plate material in the Chang Zuowei electronic circuit, be focus (H.OhsatoT.Tsunooka, A.Kan, the Y.Ohishi in the present advanced low-k materials research, Y.Miyauehi.Mierowave Milliimeterwave Dielectric Materials.Key Eng.Mater, 2004; 269:195-198).
The synthetic magnesium silicate main component is MgO and SiO
2, its optimum burning temperature-forming is 1300～1400 ℃.The Magnesium Silicate q-agent light material that makes after burning till in this temperature range has higher void content, pore mean pore size＜10 μ m, and be evenly distributed, the compressive strength of material can reach 40～50MPa, be a kind of high-intensity lightweight refractory (Hu Limin, Li Nan. decomposition in situ prepares high-strength light forsterite material. refractory materials/NA IHUO CA ILIAO, 2005,39 (4): 283-285).Magnesium Silicate q-agent has lower dielectric loss, can be used as millimeter wavelength dielectric materials (Du Yonghui, Zhang Tiechen, Su Zuopeng. the High Temperature High Pressure of forsterite and enstatite is synthetic. Chinese Journal Of High Pressure Physics, 2006,20 (3): 281-28); Secondly, magnesium silicate ceramic has stronger flexural strength and high toughness, can be used as biological ceramics (Siyu N, i Lee Chou, JiangChang[J] .CeramicsInternational, 2007,33:83-88).
Though magnesium silicate ceramic class material has more excellent properties and very big development potentiality, deadly defect such as big and poor reliability hinders its practicability again as the fragility of stupalith itself.For improving ceramics toughness, in nearest 20 years, people are doing a lot of work aspect experiment and the theoretical investigation, in multiple toughness reinforcing approach, FRCMC is the most noticeable: on the one hand, it has overcome the shortcoming of single stupalith brittle rupture, has improved the anti-thermal shock impact capacity of material; On the other hand, it has kept that ceramic matrix is high temperature resistant, (Lee is special for the advantage of low bulk, low density, Heat stability is good, Xiao Peng, Xiong Xiang. the progress of Continuous Fiber Reinforced Ceramic Matrix Composites. Materials Science and Engineering of Powder Metallurgy, 2007 (2): 13-19).
The preparation method of FRCMC mainly contain following several (He Xinbo, Yang Hui, Zhang Changrui, all upstarts. Continuous Fiber Reinforced Ceramic Matrix Composites general introduction. Materials Science and Engineering, 2002 (2): 273-278):
(1) slurry dipping-pressure sintering in containing the slurry of matrix powder, is made no latitude cloth by twining the fiber that will be soaked with slurry with fiber impregnation then, makes matrix material behind section, stack, hot compression molding and hot pressed sintering.Slurry generally is made up of matrix powder, organic binder bond, organic solvent and sintering aid.Because the matrix softening temperature is lower, can make hot pressing temperature be near or below ceramic softening temperature, utilize the VISCOUS FLOW of some pottery (as glass) to obtain fine and close matrix material.This method is mainly used in glass and low melting point ceramic matric composite.
(2) chemical reaction method, in reactant gases infiltrated fiber precast body, reacting and being deposited on forms ceramic matrix between the fiber, makes finally that the space all is full of by the matrix pottery in the precast body, thereby forms fine and close matrix material.The weak point of this method mainly is: equipment is complicated, preparation cycle is long, be not suitable for preparing thick walled part, matrix material residual porosity rate is higher, thereby influences composite property.
(3) melt infiltration (dipping) method under the plus load effect, by fused ceramic matrix permeable fiber precast body and compound with it, thereby obtains composite product.The shortcoming of this method is that ceramic fusing point is higher, in soak process easily the damage fiber and cause fiber and matrix between surface reaction takes place; The viscosity of pottery melt is much larger than the viscosity of metal, and therefore ceramic melt is difficult to soak into.
(4) sol-gel method is to utilize sol impregnation to strengthen skeleton, and then the matrix material that makes through pyrolysis.Its main drawback is: because the transformation efficiency of alkoxide is lower and contraction is bigger, so the compactness of matrix material is relatively poor, is difficult to reach densification without repeatedly flooding; Owing to it is to utilize hydrolysis of alkoxide to make ceramic matrix, so this technology only limits to the oxide ceramics matrix.
(5) precursor conversion method is to utilize organic precursor method cracking at high temperature and a kind of method of being converted into the inorganic ceramic matrix.The main drawback of this method is: the fine and close cycle is longer, and the porosity of goods is higher; Matrix density differs greatly before and after cracking, causes the volumetric shrinkage of matrix very big (can reach 50%～70%); Because the skeleton of strongthener is pining down the volumetric shrinkage of matrix, therefore be easy to generate crackle and pore in matrix inside, destroy the globality of matrix material, and finally influenced performance of composites.
Summary of the invention
The object of the present invention is to provide a kind of complex-shapedly, homogeneity is better, and density, intensity are higher, the molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material that toughness is stronger.
The present invention includes following steps:
1) gets the calcination of MgO raw material, with SiO
2Oven dry is again with MgO and SiO
2Mix, ball milling, oven dry is sieved, and gets the Magnesium Silicate q-agent powder after the pre-burning;
2) Magnesium Silicate q-agent powder and premixed liquid are mixed with ceramic size, add mullite fiber and dispersion agent in ceramic size, add catalyzer and initiator after the mixing again, the mould that reinjects gets molding blank;
3), get mullite fiber reinforced magnesium silicate ceramic matrix composite material with sintering after the molding blank demoulding.
In step 1), described calcination temperature can be 500～800 ℃, and the calcination time can be 2～4h; Described SiO
2The temperature of oven dry can be 80～150 ℃, and the time of oven dry can be 12～24h; Described with MgO and SiO
2Mix, press mass ratio, can be MgO: SiO
2=1.375: 1, the drum's speed of rotation of described ball milling can be 200～400rpm/min, and the ball milling time can be 6～12h, and described sieving can be crossed 60～160 mesh sieves, and the temperature of described pre-burning can be 1050～1250 ℃, and the time of pre-burning can be 3～5h.
In step 2) in, described Magnesium Silicate q-agent powder and premixed liquid are mixed with the solid content of ceramic size, by mass percentage more preferably greater than 50%; Described mullite fiber and the dispersion agent of in ceramic size, adding, by mass percentage, the add-on of mullite fiber is preferably 5%～30% of Magnesium Silicate q-agent powder, and the add-on of dispersion agent is preferably 0%～5% of Magnesium Silicate q-agent powder; Described premixed liquid can be acrylamide and N, N, and it is 4%～30% solution by mass percentage that the mixing of-methylene-bisacrylamide is dissolved in the organic content of making in the distilled water; Described dispersion agent can be the TH-904 aqueous dispersant; It is 5% ammonium persulfate aqueous solution that described initiator is preferably concentration; It is 5wt%N that described catalyzer is preferably concentration, N, N, the N ,-Tetramethyl Ethylene Diamine aqueous solution.
In step 3), described agglomerating temperature is 1～2 ℃/min at temperature rise rate below 600 ℃ preferably, speed with 3～5 ℃/min rises to 1300～1400 ℃ then, and the agglomerating time can be 120～240min, reduce to 1000 ℃ with the speed of-5 ℃/min again after furnace cooling.
The present invention is a kind of low cost, dead size forming technique of preparation high-performance complicated shape FRCMC of novelty, its principle is earlier ceramic powder to be scattered in the aqueous solution of organic monomer, form stable and uniform, high solid loading, low viscosity slurry, again fiber is scattered in wherein equably, then under certain catalysis, temperature, pressure condition, the organic monomer polymerization crosslinking becomes tridimensional network, the slurry in-situ solidifying, with the fiber preform combined shaping, obtain the FRCMC base substrate.The forming technique that the present invention proposes is compared with existing FRCMC shaping technology of preparing, all has obvious superiority, molding time is controlled, the production efficiency height, mold temperature is low, ceramic species is adapted to extensively, can form complex-shaped FRCMC goods.The present invention combines and annotates the principle of coagulating, permeating, and complex-shaped in order to prepare, structural constituent density is even, and high-intensity ceramic matric composite base substrate carries out sintering again and obtains the high tenacity ceramic matrix composite articles.
Description of drawings
Fig. 1 is the bending strength and the fibre content graph of a relation of mullite fiber reinforced magnesium silicate ceramic matrix composite material.In Fig. 1, X-coordinate is fibre content x (wt%), and ordinate zou is flexural strength P (MPa).
Fig. 2 is the micro-structure diagram of mullite fiber reinforced magnesium silicate ceramic matrix composite material.In Fig. 2, scale is 10 μ m.
Embodiment
The present invention is further illustrated below in conjunction with embodiment and accompanying drawing.
From the bending strength of mullite fiber reinforced magnesium silicate pottery shown in Figure 1 and fibre content relation as can be seen, the flexural strength of mullite fiber reinforced magnesium silicate ceramic composite increases reduction then earlier with the increase of fibre content, the maximum deflection intensity of matrix material is the 15wt% place at fibre content, its value is bigger by 66.38% than the flexural strength that does not have the fiber reinforced magnesium silicate pottery behind sintering, and its performance is obviously strengthened.Fibre content is (less than 15wt%) more after a little while, and polycrystalline mullite fibre is evenly distributed in the magnesium silicate ceramic matrix.When matrix material is subjected to load, matrix at first ftractures under the effect of load, than the strength, fiber and matrix rupture under the breaking strain of matrix simultaneously in the combination of fiber interface, thereby the fracture of fiber will absorb part energy the flexural strength of matrix material are raise; At the fiber interface in conjunction with more weak place, when crackle when the matrix expansion reaches the interface, crackle deflects, the tensile stress that crackle is subjected to often reduces and the extensions path of crackle increases, and the flexural strength of matrix material is increased.A spot of decomposition can take place during sintering in polycrystalline mullite fibre under the effect of impurity in addition, produces liquid phase, and acceleration of sintering is made contributions to the raising of flexural strength.Along with increasing of fibre content, the strengthening action of fiber is obvious more, and the flexural strength of matrix material is just high more.As polycrystalline mullite fibre content (greater than 20wt%) more for a long time, reasons such as reunion owing to fiber, the skewness of polycrystalline mullite fibre in Magnesium Silicate q-agent, the strengthening action of fiber is not obvious, and can introduce more pore with increasing also of fibre content, the quantity of mullite increases gradually, and the quantity of Magnesium Silicate q-agent reduces gradually, just makes the matrix material flexural strength reduce rapidly.
From the matrix material micro-structure diagram of mullite fiber reinforced magnesium silicate pottery shown in Figure 2 as can be seen, adding mullite fiber can well-proportionedly be dispersed in the magnesium silicate ceramic matrix, fiber plays the skeleton supporting role, and the performance of composites for preparing is had certain influence.
Embodiment 1
Take by weighing the MgO powder, be placed on earlier in the retort furnace at 500 ℃ of following calcination 3h, to get rid of CO
2And moisture; Again with SiO
2Be placed in the loft drier at 100 ℃ of oven dry 24h, in order to avoid the stoichiometry ratio deviation that brings because of the moisture absorption.Raw material later be will handle with the precise electronic balance and MgO and SiO pressed
2Mass ratio be to prepare burden after the accurate weighing in 1.375: 1.The powder for preparing is put into alumina crucible be placed on 1200 ℃ of air atmosphere pre-burnings of retort furnace 3h, raw material powder is fully reacted.Preburning powdered material is through ball milling, the oven dry and the processing of sieving, Magnesium Silicate q-agent powder that obtains and premixed liquid are mixed with solid content greater than 50% ceramic size, in ceramic size, add according to being uniformly dispersed behind the mullite fiber of the ratio of Magnesium Silicate q-agent powder 5wt% and the dispersion agent, to inject mould fast behind initiator and catalyzer adding slurry and the uniform mixing again, mullite fiber reinforced magnesium silicate ceramic body pressureless sintering under air atmosphere of demoulding after drying, sintering temperature is 1360 ℃, insulation 180min burns till, make the ceramic matric composite finished product, its flexural strength is 142.719MPa.
Embodiment 2
Take by weighing the MgO powder, be placed on earlier in the retort furnace at 700 ℃ of following calcination 4h, to get rid of CO
2And moisture; Again with SiO
2Be placed in the loft drier at 150 ℃ of oven dry 12h, in order to avoid the stoichiometry ratio deviation that brings because of the moisture absorption.Raw material later be will handle with the precise electronic balance and MgO and SiO pressed
2Mass ratio be to prepare burden after the accurate weighing in 1.375: 1.The powder for preparing is put into alumina crucible be placed on 1050 ℃ of air atmosphere pre-burnings of retort furnace 3h, raw material powder is fully reacted.Preburning powdered material is through ball milling, the oven dry and the processing of sieving, Magnesium Silicate q-agent powder that obtains and premixed liquid are mixed with solid content greater than 50% ceramic size, in ceramic size, add according to being uniformly dispersed behind the mullite fiber of the ratio of Magnesium Silicate q-agent powder 10wt% and the dispersion agent, to inject mould fast behind initiator and catalyzer adding slurry and the uniform mixing again, mullite fiber reinforced magnesium silicate ceramic body pressureless sintering under air atmosphere of demoulding after drying, sintering temperature is 1340 ℃, insulation 120min burns till, make the ceramic matric composite finished product, its flexural strength is 166.441MPa.
Embodiment 3
Take by weighing the MgO powder, be placed on earlier in the retort furnace at 800 ℃ of following calcination 2h, to get rid of CO
2And moisture; Again with SiO
2Be placed in the loft drier at 80 ℃ of oven dry 24h, in order to avoid the stoichiometry ratio deviation that brings because of the moisture absorption.Raw material later be will handle with the precise electronic balance and MgO and SiO pressed
2Prepare burden after the mass ratio accurate weighing in 1.375: 1.The powder for preparing is put into alumina crucible be placed on 1100 ℃ of air atmosphere pre-burnings of retort furnace 4h, raw material powder is fully reacted.Preburning powdered material is through ball milling, the oven dry and the processing of sieving, Magnesium Silicate q-agent powder that obtains and premixed liquid are mixed with solid content greater than 50% ceramic size, in ceramic size, add according to being uniformly dispersed behind the mullite fiber of the ratio of Magnesium Silicate q-agent powder 15wt% and the dispersion agent, to inject mould fast behind initiator and catalyzer adding slurry and the uniform mixing again, mullite fiber reinforced magnesium silicate ceramic body pressureless sintering under air atmosphere of demoulding after drying, sintering temperature is 1300 ℃, insulation 240min burns till, make the ceramic matric composite finished product, its flexural strength is 207.755MPa.
Embodiment 4
Take by weighing the MgO powder, be placed on earlier in the retort furnace at 600 ℃ of following calcination 3h, to get rid of CO
2And moisture; Again with SiO
2Be placed in the loft drier at 120 ℃ of oven dry 18h, in order to avoid the stoichiometry ratio deviation that brings because of the moisture absorption.Raw material later be will handle with the precise electronic balance and MgO and SiO pressed
2Prepare burden after the mass ratio accurate weighing in 1.375: 1.The powder for preparing is put into alumina crucible be placed on 1250 ℃ of air atmosphere pre-burnings of retort furnace 3h, raw material powder is fully reacted.Preburning powdered material is through ball milling, the oven dry and the processing of sieving, Magnesium Silicate q-agent powder that obtains and premixed liquid are mixed with solid content greater than 50% ceramic size, in ceramic size, add according to being uniformly dispersed behind the mullite fiber of the ratio of Magnesium Silicate q-agent powder 20wt% and the dispersion agent, to inject mould fast behind initiator and catalyzer adding slurry and the uniform mixing again, mullite fiber reinforced magnesium silicate ceramic body pressureless sintering under air atmosphere of demoulding after drying, sintering temperature is 1320 ℃, insulation 180min burns till, make the ceramic matric composite finished product, its flexural strength is 180.185MPa.
Take by weighing the MgO powder, be placed on earlier in the retort furnace at 700 ℃ of following calcination 4h, to get rid of CO
2And moisture; Again with SiO
2Be placed in the loft drier at 120 ℃ of oven dry 18h, in order to avoid the stoichiometry ratio deviation that brings because of the moisture absorption.Raw material later be will handle with the precise electronic balance and MgO and SiO pressed
2Prepare burden after the mass ratio accurate weighing in 1.375: 1.The powder for preparing is put into alumina crucible be placed on 1150 ℃ of air atmosphere pre-burnings of retort furnace 3h, raw material powder is fully reacted.Preburning powdered material is through ball milling, the oven dry and the processing of sieving, Magnesium Silicate q-agent powder that obtains and premixed liquid are mixed with solid content greater than 50% ceramic size, in ceramic size, add according to being uniformly dispersed behind the mullite fiber of the ratio of Magnesium Silicate q-agent powder 25wt% and the dispersion agent, to inject mould fast behind initiator and catalyzer adding slurry and the uniform mixing again, mullite fiber reinforced magnesium silicate ceramic body pressureless sintering under air atmosphere of demoulding after drying, sintering temperature is 1320 ℃, insulation 240min burns till, make the ceramic matric composite finished product, its flexural strength is 109.663MPa.
Embodiment 6
Take by weighing the MgO powder, be placed on earlier in the retort furnace at 600 ℃ of following calcination 4h, to get rid of CO
2And moisture; Again with SiO
2Be placed in the loft drier at 100 ℃ of oven dry 24h, in order to avoid the stoichiometry ratio deviation that brings because of the moisture absorption.Raw material later be will handle with the precise electronic balance and MgO and SiO pressed
2Prepare burden after the mass ratio accurate weighing in 1.375: 1.The powder for preparing is put into alumina crucible be placed on 1200 ℃ of air atmosphere pre-burnings of retort furnace 3h, raw material powder is fully reacted.Preburning powdered material is through ball milling, the oven dry and the processing of sieving, Magnesium Silicate q-agent powder that obtains and premixed liquid are mixed with solid content greater than 50% ceramic size, in ceramic size, add according to being uniformly dispersed behind the mullite fiber of the ratio of Magnesium Silicate q-agent powder 30wt% and the dispersion agent, to inject mould fast behind initiator and catalyzer adding slurry and the uniform mixing again, mullite fiber reinforced magnesium silicate ceramic body pressureless sintering under air atmosphere of demoulding after drying, sintering temperature is 1400 ℃, insulation 120min burns till, make the ceramic matric composite finished product, its flexural strength is 90.465MPa.
Claims (10)
1. molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material is characterized in that may further comprise the steps:
1) gets the calcination of MgO raw material, with SiO
2Oven dry is again with MgO and SiO
2Mix, ball milling, oven dry is sieved, and gets the Magnesium Silicate q-agent powder after the pre-burning;
2) Magnesium Silicate q-agent powder and premixed liquid are mixed with ceramic size, add mullite fiber and dispersion agent in ceramic size, add catalyzer and initiator after the mixing again, the mould that reinjects gets molding blank;
3), get mullite fiber reinforced magnesium silicate ceramic matrix composite material with sintering after the molding blank demoulding.
2. molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material as claimed in claim 1 is characterized in that in step 1), and described calcination temperature is 500～800 ℃, and the calcination time is 2～4h; Described SiO
2The temperature of oven dry is 80～150 ℃, and the time of oven dry is 12～24h.
3. molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material as claimed in claim 1 is characterized in that in step 1), and is described with MgO and SiO
2Mix, press mass ratio, be MgO: SiO
2=1.375: 1.
4. molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material as claimed in claim 1 is characterized in that in step 1), and the drum's speed of rotation of described ball milling is 200～400rpm/min, and the ball milling time is 6～12h; Described sieving was 60～160 mesh sieves, and the temperature of described pre-burning is 1050～1250 ℃, and the time of pre-burning is 3～5h.
5. molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material as claimed in claim 1 is characterized in that in step 2) in, described Magnesium Silicate q-agent powder and premixed liquid are mixed with the solid content of ceramic size, by mass percentage greater than 50%.
6. molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material as claimed in claim 1, it is characterized in that in step 2) in, described mullite fiber and the dispersion agent of adding in ceramic size, by mass percentage, the add-on of mullite fiber is 5%～30% of a Magnesium Silicate q-agent powder.
7. molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material as claimed in claim 1 is characterized in that in step 2) in, the add-on of dispersion agent is 0%～5% of a Magnesium Silicate q-agent powder.
8. molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material as claimed in claim 1, it is characterized in that in step 2) in, described premixed liquid is acrylamide and N, N, it is 4%～30% solution by mass percentage that the mixing of-methylene-bisacrylamide is dissolved in the organic content of making in the distilled water.
9. molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material as claimed in claim 1 is characterized in that in step 2) in, described dispersion agent is the TH-904 aqueous dispersant; Described initiator is that concentration is 5% ammonium persulfate aqueous solution; Described catalyzer is that concentration is 5wt%N, N, N, the N ,-Tetramethyl Ethylene Diamine aqueous solution.
10. molding method of mullite fiber reinforced magnesium silicate ceramic matrix composite material as claimed in claim 1, it is characterized in that in step 3), described agglomerating temperature is to be 1～2 ℃/min at temperature rise rate below 600 ℃, speed with 3～5 ℃/min rises to 1300～1400 ℃ then, the agglomerating time is 120～240min, reduce to 1000 ℃ with the speed of-5 ℃/min again after furnace cooling.
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| CN102397986A (en) * | 2011-11-01 | 2012-04-04 | 昆明理工大学 | Method for preparing metal grinding ball die by using ceramic model |
| CN104529497A (en) * | 2014-11-28 | 2015-04-22 | 西安交通大学 | Method for improving ceramic mold precision with vacuum freeze-drying technology |
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| CN104529497A (en) * | 2014-11-28 | 2015-04-22 | 西安交通大学 | Method for improving ceramic mold precision with vacuum freeze-drying technology |
| CN105669229A (en) * | 2016-01-11 | 2016-06-15 | 杜桑·里斯蒂奇 | Method for producing ceramic material |
| CN106927847A (en) * | 2017-02-27 | 2017-07-07 | 西安交通大学 | A kind of FRCMC manufacturing process and device based on 3D printing technique |
| CN106927847B (en) * | 2017-02-27 | 2020-08-18 | 西安交通大学 | Method and device for forming fiber reinforced ceramic matrix composite based on 3D printing technology |
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| CN109133954B (en) * | 2018-11-14 | 2021-10-26 | 福建省德化龙辉陶瓷有限公司 | High-toughness refractory domestic ceramic and preparation method thereof |
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| CN113698226A (en) * | 2021-09-23 | 2021-11-26 | 景德镇陶瓷大学 | Preparation method of high-strength porous ceramic and product prepared by same |
| CN114507079A (en) * | 2022-03-09 | 2022-05-17 | 陕西科技大学 | Mullite fiber reinforced metal matrix composite ceramic sheet and preparation method thereof |
| CN114507079B (en) * | 2022-03-09 | 2022-12-30 | 陕西科技大学 | Mullite fiber reinforced metal-based composite ceramic sheet and preparation method thereof |
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Application publication date: 20100922 |