CN104003697A - Preparation method of BSAS composite ceramic powder - Google Patents
Preparation method of BSAS composite ceramic powder Download PDFInfo
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- CN104003697A CN104003697A CN201410253549.1A CN201410253549A CN104003697A CN 104003697 A CN104003697 A CN 104003697A CN 201410253549 A CN201410253549 A CN 201410253549A CN 104003697 A CN104003697 A CN 104003697A
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Abstract
The invention discloses a preparation method of a composite ceramic powder material used for an environmental barrier coating. The composite ceramic powder is composed of single phase BSAS (1-xBaO-xSrO-Al2O3-2SiO2, x is more than 0 and less than 1). The obtained BSAS composite ceramic powder has the advantages of easiness for ingredient control, high purity, high crystallinity and low synthesis temperature. The composite ceramic powder can be used for plasma spraying after being subjected to ball milling, agglomeration, pelletizing and high-temperature heat treatment, so that the environmental barrier coating is prepared on the surface of a C/C-SiC composite material, the coating can be used for effectively improving high-temperature water oxygen corrosion resistance performance of a C/C-SiC matrix, is applicable to surface high-temperature protection of other silicon substrate materials, can be used for solving the problem of high-temperature water oxygen corrosion of a silicon substrate composite material and has an important application value.
Description
Technical field
The present invention relates to the preparation method of composite ceramic powder for a kind of environment barrier coating, particularly a kind of preparation method of BSAS composite ceramic powder; Belong to oxide ceramic material preparing technical field.
Technical background
Charcoal/carbon-silicon carbide (C/C-SiC) matrix material is to take the ceramic matric composite that charcoal fiber is wild phase, combine the superior mechanical property of fibre reinforcement and good chemistry and the thermostability of pottery, have high than strong, Gao Bimo, the outstanding advantages such as density is low, antioxidant property good, corrosion-resistant, excellent mechanical property and heat physical properties, be high thrust-weight ratio aircraft engine, rocket engine and the empty day desirable high-temperature structural material of the contour warm end pieces of aircraft.Adopt chemical vapour deposition (CVD) technology can significantly improve antioxidant property in C/C-SiC surface preparation SiC coating, but high-temperature water oxygen coupling environment have stronger corrosive nature to SiC coating.Due to the existence of a large amount of water vapors, the SiO that SiC coating oxidation generates
2film can generate the volatile Si of gaseous state (OH) with steam reaction
4, the loss of Si causes composite property to decline rapidly.For SiC coating Quick Oxidation and the problem that cannot work is lastingly comparatively desirable measure at its surface deposition environment barrier coating (EBCs) under high-temperature water oxygen environment.The EBCs system that extensively adopts plasma spraying technology to prepare at CMC-SiC material surface at present.
With celsian-felspar (BaAl
2si
2o
8) be the BaOAl of principal crystalline phase
2o
3siO
2(BAS) microcrystalline glass in series pottery is the EBCs material that has application prospect.The main crystal formation of celsian-felspar has monocline celsian-felspar, six side's celsian-felspars and quadrature celsian-felspar, and from thermodynamics, monocline celsian-felspar is 1590 ℃ of following stable phases, and six side's celsian-felspars are the stable phase higher than 1590 ℃.Monocline celsian-felspar has that chemical stability is good, stablizing mutually (within the scope of 0-1590 ℃, keep monoclinic phase constant), thermal expansivity, little (monoclinic phase BSA is 2.29 * 10 at the thermal expansivity of 20-1000 ℃
-6/ ℃), good thermal shock, resistance of oxidation and acid-alkali-corrosive-resisting ability is strong, with SiC, Si
3n
4and mullite etc. has the good premium propertiess such as chemical compatibility, preferably as EBCs system high-temperature structured material, this is also the how controls by composition and technique and improve the major cause that obtains monocline celsian-felspar of numerous scholar's primary studies.Six side's celsian-felspar structural symmetries are high, simple in structure, and forming core resistance is little, so during BAS devitrified glass crystallization, six metastable side's celsian-felspar ordinary priority forming cores are grown up, then monocline celsian-felspar is grown up at the surface nucleation of six side's celsian-felspars, and this process is very difficult.Research finds that the key that promotes six side's celsian-felspars to change to monocline celsian-felspar is promote the forming core of monocline celsian-felspar or promote the movement of ion in six side's celsian-felspar structures or promote SiO
2diffusion.But under solid conditions, realize SiO
2solid-state diffusion, be difficult to.Along with further going deep into of research, find BaAl
2si
2o
8with SrAl
2si
2o
8forming sosoloid, is one of effective measure that promote celsian-felspar phase transformation.Strontium feldspar (SrAl
2si
2o
8) identical with celsian-felspar structure, comprise equally three kinds of monocline strontium feldspar, quadrature strontium feldspar and six side's strontium feldspars, wherein, the over-all properties of monocline strontium feldspar is good.Preparation SAS also often first obtains six side's strontium feldspars during devitrified glass, and then six side's strontium feldspars change monocline strontium feldspar into, different from celsian-felspar, SrAl
2si
2o
8six side's strontium feldspars occur to be easier to the transformation ratio of monocline strontium feldspar.Therefore, when preparation BAS microcrystalline glass in series pottery, add SrO, SrO and SiO
2, Al
2o
3generate six side's strontium feldspars, six side's strontium feldspars change monocline strontium feldspar into when sintering, the epitaxy that the similar monocline strontium feldspar of crystalline structure is monocline celsian-felspar provides core position, monocline strontium feldspar also can be used as the core of the heterogeneous forming core of monocline celsian-felspar simultaneously, promote the forming core of monocline celsian-felspar, thereby promote six side's celsian-felspars to the transformation of monocline celsian-felspar.
At present typical EBCs composing system is 3Al
2o
32SiO
2/ 3Al
2o
32SiO
2+ BSAS/BSAS (1-xBaO-xSrO-Al
2o
3-2SiO
2, 0<x<1).The method of synthetic BSAS system powder mainly contains conventional sintering method, solid phase method, sol-gel method and hydrolytic precipitation method.Conventional sintering legal system, for BSA microcrystalline glass in series, adopts BaCO mostly
3, Al
2o
3and SiO
2for raw material, smelting temperature is higher than 2000 ℃; Solid phase method is conventionally with SiO
2, Al
2o
3, BaO, SrO or SiO
2, Al (OH)
3, Ba (OH)
2, Sr (OH)
2, or SiO
2, Al
2o
3, BaCO
3, SrCO
3, or SiO
2, Al
2o
3, Ba (Ac)
2, Sr (Ac)
2for raw material, after batch mixing, high temperature sintering obtains oxide composite end, and sintering temperature is generally more than 1700 ℃, even if take hot pressed sintering, sintering temperature is also higher than 1500 ℃.The synthesis temperature of these two kinds of methods is higher, long reaction time, and energy consumption is high, and cost is large; In addition, aluminium silicon ion diffusion difficulty in this system, lattice dislocation skid resistance is large, makes this combined oxidation objects system compared with hard-to-sinter, conventionally contains the segregation phase of aluminum oxide and silicon oxide, the BSAS powdered material that more difficult acquisition purity is high, phase structure is single.In the synthetic BSAS powder of solid phase method, there are a large amount of unreacted SiO
2, when these powder are used for coating, these unreacted SiO
2, be easy to just generate the volatile Si of gaseous state (OH)
4, so water vapour holds by original SiO very much
2occupied space enters, and reacts with SiC, thereby causes the performance of charcoal/carbon-silicon carbide (C/C-SiC) matrix material to decline rapidly.Sol-gel method is prepared powder, and mostly adopting ester class and metal alcoholate is raw material, and this process costs is high, complex process, synthesis cycle long, it is in enormous quantities synthetic to be difficult to realize.Hydrolytic precipitation method is in settled solution, to use precipitation agent, then throw out calcining is obtained to required powder, and research finds that the soluble inorganic salt of take containing Ba, Al is raw material, with the same one-step hydrolysis of tetraethoxy, is difficult to obtain the BaO-Al of stable and uniform
2o
3-SiO
2gel.
In a word, yet there are no with Al in the prior art
2o
32SiO
2powder, BaCO
3powder, SrCO
3powder is the report that raw material is prepared BSAS composite powder.
Summary of the invention
The present invention is directed to the shortcoming existing in above-mentioned prior art, a kind of preparation method of BSAS composite ceramic powder is provided; The present invention is synthetic by single silicoaluminate barium (strontium) BSAS composite ceramic powder phase composite, that purity is high, phase structure is stable lower than 1400 ℃.
The preparation method of composite ceramic powder for a kind of environment barrier coating of the present invention, comprises the steps:
Step 1
Al:Si=1:1, adds water-soluble aluminum salts solution in silicon ester solution in molar ratio, stirs and obtains mixed solution, then mixed solution being joined to pH value is in the ammoniacal liquor in 8～9, stirs reaction, filter, filter residue 600～900 ℃ of calcinings at least 2 hours, obtains Al after washing, being dried
2o
32SiO
2composite ceramic powder; When described mixed solution joins in ammoniacal liquor, the pH value of controlling reaction system is 8～9;
Step 2
With the prepared Al of step 1
2o
32SiO
2ceramic composite powder, barium salt or barium oxide, strontium salt or strontium oxide are raw material, the ratio of (Ba+Sr)/Al=1:2 is joined and is got raw material in molar ratio, by join the raw material of getting mix after 1250～1400 ℃ of calcinings at least 4 hours, obtain monoclinic BSAS composite ceramic powder; The chemical formula of described BSAS composite ceramic powder is (1-x) BaO-xSrO-Al
2o
3-2SiO
2, wherein x is greater than 0 and be less than 1.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, in step 1, described water-soluble aluminum salt is selected from the Al (NO of purity>=99%
3)
3, AlCl
3, a kind of in Burow Solution; In described water-soluble aluminum salts solution, the concentration of aluminium element is 0.3-1.5mol/l.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, in step 1, described silicon ester solution is by silicon ester and alcohol silicon ester in mass ratio: alcohol=1:3-1:1 forms; Described silicon ester is selected from a kind of in the methyl silicate, tetraethoxy of purity >=99%, positive silicic acid propyl ester; Described alcohol is selected from least one in methyl alcohol, ethanol, propyl alcohol.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, in step 1, described mixed solution adds in ammoniacal liquor with the speed of 0.1-0.5l/min; When described mixed solution joins pH value completely, be in the ammoniacal liquor in 8～9, after stopping stirring, standing 24～48h.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, in step 1, filter residue with deionized water wash to the pH of washing lotion be 6.5～7.5.In actual mechanical process, generally use deionized water wash 4～5 times; Volume ratio >=3 of each washing deionized water used and filter residue, are preferably 3-6 doubly, and the pH that just can realize washing lotion is 6.5～7.5.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, in step 1, by washing after filter residue at 100～110 ℃ of dry 24h～48h; Then 600～900 ℃ of calcinings 2～4 hours; Obtaining granularity is that 0.1 μ m-2 μ m, purity are more than or equal to 99% Al
2o
32SiO
2ceramic composite powder.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, in step 2, the purity of described barium salt, barium oxide, strontium salt, strontium oxide is all more than or equal to 99%; Described barium salt is barium carbonate or barium acetate; Described strontium salt is Strontium carbonate powder or strontium acetate.In actual mechanical process, when the granularity of barium salt, barium oxide, strontium salt, strontium oxide is larger, need by break process, making its granularity is 0.1 μ m-2 μ m.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, in step 2, join the raw material of getting and mix by ball milling, ball milling parameter is that mass ratio 5-1:1-1, the Material quality of grinding balls of rotating speed 220～250r/min, time 2～4h, abrading-ball and raw material are: ZrO
2or Al
2o
3, ball-milling medium is the mass ratio of dehydrated alcohol, ball-milling medium and raw material: 1:1-3:1.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, in step 2, the mixing rear dress alumina crucible and send in process furnace of raw material, process furnace is preferably Si-Mo rod stove, at 1100～1400 ℃, be preferably 1250～1400 ℃ of calcining 4～10h and be preferably 8～10h, make carbonate, acetate change oxide compound completely into, obtain monoclinic (1-x) BaO-xSrO-Al
2o
3-2SiO
2composite ceramic powder; Described (1-x) BaO-xSrO-Al
2o
3-2SiO
2composite ceramic powder granularity is that 0.1-2 μ m, purity are more than or equal to 99%.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, the monoclinic BSAS composite ceramic powder of step 2 gained, after ball milling, granulation, at 1050～1250 ℃ of thermal treatment 2～4h, obtaining granularity is the environment barrier coating composite ceramic powder material of 45-100 μ m.The monoclinic BSAS composite ceramic powder of gained is carried out to ball milling, granulation and thermal treatment, is mainly in order to facilitate follow-up spraying coating process.By ball milling, caking agent is mixed with ceramic powder, be convenient to follow-up granulation, so the time of this section of ball milling of general control is 8-10h in actual mechanical process; By 1050～1250 ℃ of thermal treatment 2～4h, both removed granulation caking agent used, increased again the mobility of powder, follow-up spraying coating process can be carried out smoothly.
Principle and advantage
Principle
First the present invention adopts hydrolytic precipitation method to synthesize Al
2o
3-SiO
2aqueous precursor gel, aqueous precursor gel calcining obtains Al
2o
32SiO
2composite powder, then with Al
2o
32SiO
2for raw material powder has just been avoided rich SiO
2or rich Al
2o
3appearance, thereby be easy to get to, meet the product of stoichiometric ratio, this raw materials technology is relatively inexpensive, technique is simply controlled, be easy to realize preparation in batches.
Adopt the present invention at the synthetic Al of lesser temps (600～900 ℃)
2o
32SiO
2powder.With Al
2o
32SiO
2, BaCO
3, SrCO
3for raw material, during high temperature sintering, first form the sosoloid of strontium feldspar and celsian-felspar, when sintering temperature is 1250 ℃, six side's strontium feldspars change monocline strontium feldspar completely into, and the epitaxy that the similar monocline strontium feldspar of crystalline structure is monocline celsian-felspar provides core position, monocline strontium feldspar also can be used as the core of the heterogeneous forming core of monocline celsian-felspar simultaneously, promote the forming core of monocline celsian-felspar, promote six side's celsian-felspars to the transformation of monocline celsian-felspar, reduce the transformation temperature of celsian-felspar.Therefore, when sintering temperature is 1300～1400 ℃, can synthesize the monoclinic phase BSAS composite powder of single structure, be environment barrier coating composite ceramic powder.
It is raw material that water-soluble aluminum salt and silicon ester are take in the present invention, by strict control aluminium silicon mol ratio and Al
2o
32SiO
2pH value in preparation process, under this pH condition, Al
3+ion forms Y (OH)
3speed and silicon ester hydrolysis generate (Si (OH)
4) speed be almost infinitely close to 1:1,, this has just guaranteed that Al, Si evenly mix in the ratio in 1:1 of atomic level, thereby has avoided local SiO in Al-Si ceramic composite powder
2the difficult problem of content distribution inequality, for preparing high-quality BSAS composite ceramic powder, provide prerequisite.This has also just guaranteed that the chemical formula of prepared Al-Si ceramic composite powder is Al
2o
32SiO
2.Simultaneously due to single Al
2o
32SiO
2particle is done as a whole participation reaction, this guaranteed to a great extent (Ba+Sr) and Al and Si by the ratio key of (Ba+Sr): Al:Si=1:2:1 and, this provides precondition for acquisition high purity, BSAS powdered material that phase structure is single.
Advantage
(1) the method for the invention adopts chemical coprecipitation-solid phase method phase compounding technology, can realize environment barrier coating synthetic with the low temperature of BSAS composite ceramic powder, and synthesis temperature is lower than 1400 ℃.Compare with conventional sintering method and solid phase method, its energy consumption obviously reduces;
(2) the synthetic environment barrier coating of technical solution of the present invention is with BSAS composite ceramic powder purity high (being more than or equal to 99%), single silicoaluminate barium (strontium) phase (oblique system), consist of, the feature of this thing phase is that fusing point is high, thermal expansivity is little, anti-oxidant and acid-alkali-corrosive-resisting performance is good, phase structure stable, has good chemical compatibility with SiC.Compare with conventional sintering method and solid phase method, the purity of the product that the present invention obtains is high, phase structure is single, is more suitable for for environment barrier coating.
(3) simultaneously owing to adopting chemical coprecipitation, preparation efficiency is improved greatly, in the container of 100L, prepare 10 kilograms of Al
2o
32SiO
2reaction times is less than or equal to 60min, is generally 20-60min, and time of repose is 12-24h; Compare with existing sol-gel method, its working efficiency obviously increases, simultaneously because sol-gel is in preparation process, how impurity being washed out is also a difficult problem, and the present invention utilizes water-soluble aluminum salt and silicon ester cleverly, it is raw material, by hydrolytic precipitation method, avoided cleverly this difficult problem, this is further for large-scale industrial production provides strong guarantee.Compare with existing hydrolytic precipitation method, owing to having designed cleverly, in hydrolytic precipitation process, only prepare Al
2o
32SiO
2composite powder, has avoided unstable the brought a series of deficiencies due to system.
(4) composite ceramic powder material of the present invention, adopt plasma spraying technology to prepare environment barrier coating, test result shows that this coating keeps single monoclinic phase structure in 1500 ℃ of thermal treatment 100h cool to room temperature processes, phase structure is stable, can meet the long-time high temperature protection of SiC material.
Accompanying drawing explanation
Preparation technology's flow process of composite ceramic powder for accompanying drawing 1 environment barrier coating.
Accompanying drawing 2 is the 0.5BaO-0.5SrO-Al of the embodiment of the present invention one preparation
2o
3-2SiO
2(BSAS) X-ray diffractogram of composite ceramic powder is general.
Accompanying drawing 3 is the 0.75BaO-0.25SrO-Al of the embodiment of the present invention two preparations
2o
3-2SiO
2(BSAS) X ray diffracting spectrum of composite ceramic powder.
Accompanying drawing 4 is the 0.75BaO-0.25SrO-Al of the embodiment of the present invention two preparations
2o
3-2SiO
2(BSAS) the SEM photo of composite ceramic powder.
Accompanying drawing 5 is the X ray diffracting spectrum of the BSAS composite ceramic powder of comparative example 1 preparation.
As can be seen from Figure 2 with Al
2o
32SiO
2, BaCO
3, SrCO
3for raw material, at 1350 ℃ of synthetic single 0.5BaO-0.5SrO-Al
2o
3-2SiO
2(BSAS) composite powder, powder crystallization degree is high, without single oxide powder, occurs; And products therefrom is single oblique system.
As can be seen from Figure 3 with Al
2o
32SiO
2, BaCO
3, SrCO
3for raw material, at 1350 ℃ of synthetic single 0.75BaO-0.25SrO-Al
2o
3-2SiO
2(BSAS) composite powder, powder crystallization degree is high, without single oxide powder, occurs; And products therefrom is single oblique system.
From Fig. 4 (a), find out prepared 0.75BaO-0.25SrO-Al
2o
3-2SiO
2(BSAS) composite powder is reunion state, large agglomerating particles (3～20 μ m); From finding out that from Fig. 4 (b) large agglomerating particles is to be reunited and formed by the nano particle (10-50nm) of size uniform.
As can be seen from Figure 5, BaCO
3, SrCO
3, Al
2o
3and SiO
2raw material powder, after mixing and ball milling, dry, 1500 ℃ of calcining 20h, still has a large amount of SiO in product
2and Al
2o
3exist, silicon-dioxide diffraction peak is the strongest, and aluminum oxide diffraction peak is taken second place, and a large amount of silicon-dioxide and aluminum oxide be reaction not, has part Ba
0.5sr
0.5al
2si
2o
8synthetic, almost without the Ba that meets stoichiometric ratio
0.75sr
0.25al
2si
2o
8(BSAS) composite powder is synthetic.Comparison diagram 2 and Fig. 3 are known, and simple solid phase method is difficult to that synthetic purity is high, crystalline structure is single, meets the BSAS composite powder of stoichiometric ratio, and its synthesis temperature is higher.
Embodiment
Embodiment mono-
With preparation 0.5BaO-0.5SrO-Al
2o
3-2SiO
2(BSAS) 10 kilograms of composite ceramic powders are example, and being scaled mole number is 28.52mol, Al in composition
2o
3mole number is 28.52mol, raw material A l (NO
3)
39H
2the mole number of O is 57.04mol, and being scaled quality is 21.4 kilograms.Take 21.4 kilograms of solid nitric acid al dissolutions in deionized water to forming transparent aluminum nitrate solution.SiO in 10 kilograms of BSAS powder
2mole number be 57.04mol, being scaled quality is 3.43 kilograms, tetraethoxy ((C used
2h
5)
4siO
4) middle SiO
2content is 28%, and density is 0.929g/cm
3, need 12.25 kilograms of tetraethoxy quality, being scaled tetraethoxy volume is 13.2L.Measure 13.2L tetraethoxy, measure 15.4 kilograms of ethanol, the tetraethoxy measuring, ethanol are added in aluminum nitrate solution after mixing, stirring fully mixes it in 30 minutes, then the speed of 0.2l/min of mixed solution being take joins in the ammoniacal liquor of pH value in 8～9, during reaction, by filling into ammoniacal liquor, to make the pH value perseverance of reaction system be 8～9, stir reaction.React complete continuation and stir 30 minutes, then standing 24h, guarantees that aluminum ion precipitates completely, tetraethoxy complete hydrolysis.Deionized water repetitive scrubbing and filtering-depositing 4 times for the method for adopt to hang filtering, remove NH
4+ion, in 110 ℃ of dry 24h, obtains precursor powder by the gelatinous precipitate through washing and filtering, and precursor powder is obtained to Al at 800 ℃ of calcining 3h
2o
3-2SiO
2(AS) composite ceramic powder.Take 2.8 kilograms of barium carbonates and 2.1 kilograms of Strontium carbonate powders, with AS powder mixing and ball milling 2h, ball milling disposed slurry is dry after in 1350 ℃ of thermal treatment 10h, obtain 0.5BaO-0.5SrO-Al after cooling
2o
3-2SiO
2(BSAS) composite ceramic powder material.Adopt XRD to detect products therefrom, as shown in Figure 2, as can be seen from Figure 2 prepared 0.5BaO-0.5SrO-Al
2o
3-2SiO
2(BSAS) composite powder degree of crystallinity is high, without single oxide powder, occurs; And products therefrom is single oblique system.Adopt XRF technology for detection to detect gained 0.75BaO-0.25SrO-Al
2o
3-2SiO
2purity, obtain the purity > 99% of products therefrom.
By this superfine composite ceramic powder mechanical ball milling 10h, mist projection granulating then, the 1150 ℃ of thermal treatment 2.5h of powder particle after granulation obtain 0.5BaO-0.5SrO-Al
2o
3-2SiO
2(BSAS) composite ceramic powder material is 10 kilograms.This composite powder can be used for plasma spraying and prepares environment barrier coating, realizes the high temperature water resistant oxygen protection to C/C-SiC matrix material, and its working temperature can reach 1500 ℃.
Embodiment bis-
With preparation 0.75BaO-0.25SrO-Al
2o
3-2SiO
2(BSAS) 10 kilograms of composite ceramic powders are example, and being scaled mole number is 27.55mol, Al in composition
2o
3mole number is 27.55mol, raw material A l (NO
3)
39H
2the mole number of O is 55.1mol, and being scaled quality is 20.7 kilograms.Take 20.7 kilograms of solid nitric acid al dissolutions in deionized water to forming transparent aluminum nitrate solution.SiO in 10 kilograms of BSA powder
2mole number be 55.1mol, being scaled quality is 3.31 kilograms, tetraethoxy ((C used
2h
5)
4siO
4) middle SiO
2content is 28%, and density is 0.929g/cm
3, need 11.82 kilograms of tetraethoxy quality, being scaled tetraethoxy volume is 12.7L.Measure 12.7L tetraethoxy, measure 14.8 kilograms of ethanol, the tetraethoxy measuring, ethanol are added in aluminum nitrate solution after mixing, stirring fully mixes it in 30 minutes, then the speed of 0.2l/min of mixed solution being take joins in the ammoniacal liquor of pH value in 8～9, during reaction, by filling into ammoniacal liquor, to make the pH value perseverance of reaction system be 8～9, stir reaction; React complete continuation and stir 30 minutes, then standing 24h, guarantees that aluminum ion precipitates completely, tetraethoxy complete hydrolysis.Deionized water repetitive scrubbing and filtering-depositing 4 times for the method for adopt to hang filtering, remove NH
4+ion, in 110 ℃ of dry 24h, obtains precursor powder by the gelatinous precipitate through washing and filtering, and precursor powder is obtained to Al at 800 ℃ of calcining 3h
2o
3-2SiO
2(AS) composite ceramic powder.Take 4.1 kilograms of barium carbonates and 1.02 kilograms of Strontium carbonate powders, with AS powder mixing and ball milling 2h, ball milling disposed slurry is dry after in 1350 ℃ of thermal treatment 10h, obtain 0.75BaO-0.25SrO-Al after cooling
2o
3-2SiO
2(BSAS) composite ceramic powder material.Adopt XRD to detect products therefrom, as shown in Figure 3, as can be seen from Figure 3 prepared 0.75BaO-0.25SrO-Al
2o
3-2SiO
2(BSAS) composite ceramic powder degree of crystallinity is high, without single oxide powder, occurs; And products therefrom is single oblique system.Adopt scanning electron microscope (SEM) to observe this powder, as shown in Figure 4, from Fig. 4 (a), find out prepared 0.75BaO-0.25SrO-Al
2o
3-2SiO
2(BSAS) composite powder is reunion state, large agglomerating particles (3～20 μ m); From finding out that from Fig. 4 (b) large agglomerating particles is to be reunited and formed by the nano particle (10-50nm) of size uniform.Adopt XRF technology for detection to detect gained 0.75BaO-0.25SrO-Al
2o
3-2SiO
2purity, the purity that obtains products therefrom is 99.09% (> 99%).
By this superfine composite ceramic powder mechanical ball milling 10h, mist projection granulating then, the 1150 ℃ of thermal treatment 2.5h of powder particle after granulation obtain 0.75BaO-0.25SrO-Al
2o
3-2SiO
2(BSAS) composite ceramic powder material is 10 kilograms.This composite powder can be used for plasma spraying and prepares environment barrier coating, realizes the high temperature water resistant oxygen protection to C/C-SiC matrix material, and its working temperature can reach 1500 ℃.
Comparative example 1
Predetermined product is 0.75BaO-0.25SrO-Al
2o
3-2SiO
2(BSAS) composite ceramic powder;
By preparation 0.75BaO-0.25SrO-Al
2o
3-2SiO
2(BSAS) 1 kilogram of composite ceramic powder is joined and is got each raw material, with BaCO
3, SrCO
3, Al
2o
3and SiO
2powder is raw material, adopts the synthetic BSAS composite powder of solid phase method.Take respectively 316.8gBaO, 71.3gSrO, 280.9gAl
2o
3and 331gSiO
2, Material quality of grinding balls is Al
2o
3, material, dehydrated alcohol, abrading-ball be take to mass ratio and add in ball grinder as 1:2:5.Then by ball grinder rotating speed ball milling 12h with 200rpm on planetary ball mill.After ball milling, slurry is placed in to loft drier, at 120 ℃ of dry 12h, obtains dry mixed powder.Use Si-Mo rod High Temperature Furnaces Heating Apparatus to calcine mixed powder, calcining temperature is 1500 ℃, and soaking time is 20h, and heat-up rate is 10 ℃/min, and the type of cooling is furnace cooling.Powder after adopting XRD to high-temperature calcination carries out material phase analysis, as shown in Fig. 5 institute, as can be seen from Figure 5, BaCO
3, SrCO
3, Al
2o
3and SiO
2raw material powder, after mixing and ball milling, dry, 1500 ℃ of calcining 20h, still has a large amount of SiO in product
2and Al
2o
3exist, silicon-dioxide diffraction peak is the strongest, and aluminum oxide diffraction peak is taken second place, and a large amount of silicon-dioxide and aluminum oxide be reaction not, has part Ba
0.5sr
0.5al
2si
2o
8synthetic, almost without the Ba that meets stoichiometric ratio
0.75sr
0.25al
2si
2o
8(BSAS) composite powder is synthetic.
Claims (10)
1. a preparation method for BSAS composite ceramic powder, is characterized in that comprising the steps:
Step 1
Al:Si=1:1 in molar ratio, water-soluble aluminum salts solution is added in silicon ester solution, stir and obtain mixed solution, then mixed solution is joined to pH value and be in 8～9 ammoniacal liquor, stir, reaction, the pH value of controlling reaction system is 8～9, after having reacted, filters, filter residue 600～900 ℃ of calcinings at least 2 hours, obtains Al after washing, being dried
2o
32SiO
2composite ceramic powder;
Step 2
With the prepared Al of step 1
2o
32SiO
2ceramic composite powder, barium salt or barium oxide, strontium salt or strontium oxide are raw material, the ratio of (Ba+Sr)/Al=1:2 is joined and is got raw material in molar ratio, by join the raw material of getting mix after 1250～1400 ℃ of calcinings at least 4 hours, obtain monoclinic BSAS composite ceramic powder; The chemical formula of described BSAS composite ceramic powder is (1-x) BaO-xSrO-Al
2o
3-2SiO
2, wherein x is greater than 0 and be less than 1.
2. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, is characterized in that: in step 1, described water-soluble aluminum salt is selected from the Al (NO of purity>=99%
3)
3, AlCl
3, a kind of in Burow Solution; In described water-soluble aluminum salts solution, the concentration of aluminium element is 0.3-1.5mol/l.
3. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, is characterized in that: in step 1, described silicon ester solution is by silicon ester and alcohol silicon ester in mass ratio: alcohol=1:3-1:1 forms; Described silicon ester is selected from a kind of in the methyl silicate, tetraethoxy of purity >=99%, positive silicic acid propyl ester; Described alcohol is selected from least one in methyl alcohol, ethanol, propyl alcohol.
4. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, is characterized in that: in step 1, described mixed solution adds in ammoniacal liquor with the speed of 0.1-0.5l/min; After having reacted, stop stirring standing 24～48h.
5. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, is characterized in that: in step 1, filter residue with deionized water wash to the pH of washing lotion be 6.5～7.5.
6. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, is characterized in that: in step 1, by the filter residue after washing at 100～110 ℃ of dry 24h～48h; Then 600～900 ℃ of calcinings 2～4 hours; Obtaining granularity is that 0.1 μ m-2 μ m, purity are more than or equal to 99% Al
2o
32SiO
2ceramic composite powder.
7. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, is characterized in that: in step, the purity of described barium salt, barium oxide, strontium salt, strontium oxide is all more than or equal to 99%; Described barium salt is barium carbonate or barium acetate; Described strontium salt is Strontium carbonate powder or strontium acetate.
8. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, it is characterized in that: in step 2, join the raw material of getting and mix by ball milling, ball milling parameter is that mass ratio 5-1:1-1, the Material quality of grinding balls of rotating speed 220～250r/min, time 2～4h, abrading-ball and raw material are: ZrO
2or Al
2o
3, ball-milling medium is the mass ratio of dehydrated alcohol, ball-milling medium and raw material: 1:1-3:1.
9. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, it is characterized in that: in step 2, after raw material mixes, pack alumina crucible into and send in process furnace, at 1250～1400 ℃ of calcining 4～10h, obtaining monoclinic (1-x) BaO-xSrO-Al
2o
3-2SiO
2composite ceramic powder; Described (1-x) BaO-xSrO-Al
2o
3-2SiO
2composite ceramic powder granularity is that 0.1-2 μ m, purity are more than or equal to 99%.
10. according to the preparation method of a kind of BSAS composite ceramic powder described in claim 1-9 any one, it is characterized in that: monoclinic BSAS composite ceramic powder by ball milling, granulation after, at 1050～1250 ℃ of thermal treatment 2～4h, obtaining granularity is the environment barrier coating composite ceramic powder material of 45-100 μ m.
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| CN105503272A (en) * | 2015-12-22 | 2016-04-20 | 中南大学 | Preparation method of composite material of barium strontium aluminum containing silicate/mullite/SiC three-layer composite structural coating |
| CN107746267A (en) * | 2017-10-11 | 2018-03-02 | 中国航发北京航空材料研究院 | A kind of Ba used for plasma sprayingxSr1‑xAl2Si2O8Raw powder's production technology |
| CN108275989A (en) * | 2017-12-27 | 2018-07-13 | 佛山科学技术学院 | A kind of preparation method and application method of nano modification BSAS ceramic coatings |
| CN109485387A (en) * | 2017-12-29 | 2019-03-19 | 西安航天复合材料研究所 | A kind of preparation method of Environmental Barrier Coatings on Si-based Ceramics hollow ball shape BSAS powder |
| CN109485396A (en) * | 2017-12-29 | 2019-03-19 | 西安航天复合材料研究所 | A kind of preparation method of Environmental Barrier Coatings on Si-based Ceramics BSAS ceramic powders |
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| CN112225569A (en) * | 2020-10-16 | 2021-01-15 | 中国航发北京航空材料研究院 | BSAS powder solid-phase synthesis method for environmental barrier coating |
| CN112521150A (en) * | 2020-11-02 | 2021-03-19 | 广西科技大学 | Preparation method of perovskite-like structure ceramic coating |
| CN113121214A (en) * | 2021-04-22 | 2021-07-16 | 苏州中材非金属矿工业设计研究院有限公司 | Graphite tailing-based microwave dielectric ceramic material and preparation method thereof |
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| CN105503272A (en) * | 2015-12-22 | 2016-04-20 | 中南大学 | Preparation method of composite material of barium strontium aluminum containing silicate/mullite/SiC three-layer composite structural coating |
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