CN104003697B - A kind of preparation method of BSAS composite ceramic powder - Google Patents

A kind of preparation method of BSAS composite ceramic powder Download PDF

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CN104003697B
CN104003697B CN201410253549.1A CN201410253549A CN104003697B CN 104003697 B CN104003697 B CN 104003697B CN 201410253549 A CN201410253549 A CN 201410253549A CN 104003697 B CN104003697 B CN 104003697B
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ceramic powder
bsas
composite ceramic
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strontium
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CN104003697A (en
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刘怀菲
熊翔
王雅雷
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Central South University
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Abstract

The invention discloses a kind of preparation method of environment barrier coating composite ceramic powder material.This composite ceramic powder is by single-phase BSAS (1-xBaO-xSrO-Al 2o 3-2SiO 2, 0 < x < 1) and composition, adopt liquid phase method-solid phase method compounding technology to prepare.This invention obtains, and BSAS composite ceramic powder composition is easily controlled, purity is high, degree of crystallinity is high, synthesis temperature is low.This composite ceramic powder can be used for plasma spray and is coated in C/C-SiC composite material surface and prepares environment barrier coating after ball milling, agglomeration granulation and high-temperature heat treatment, the application of this coating effectively can improve the high temperature resistance water oxygen corrosion performance of C/C-SiC matrix, be applicable to the surface high-temp protection of other silica-based body materials simultaneously, the high-temperature water oxygen corrosion problem of silicon based composite material can be solved, there is important using value.

Description

A kind of preparation method of BSAS composite ceramic powder
Technical field
The present invention relates to a kind of preparation method of environment barrier coating composite ceramic powder, 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 take Carbon fibe as the ceramic matric composite of wild phase, combine the superior mechanical property of fibre reinforcement and pottery good chemistry and thermostability, 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 the desirable high-temperature structural material of the high-temperature hot end pieces such as high thrust-weight ratio aircraft engine, rocket engine and re-entry space vehicle.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 vapor, the SiO that SiC coating oxidation generates 2film can generate the Si (OH) of gaseous volatile with steam reaction 4, the loss of Si causes composite property to decline rapidly.For SiC coating Quick Oxidation and problem that cannot work lastingly under high-temperature water oxygen environment, be ideal measure at its surface deposition environment barrier coating (EBCs).Extensively adopt the EBCs system that plasma spraying technology is prepared 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 having application prospect.The main crystal formation of celsian-felspar has monocline celsian-felspar, six side's celsian-felspars and orthogonal celsian-felspar, and from thermodynamics, monocline celsian-felspar is the stable phase of less than 1590 DEG C, and six side's celsian-felspars are the stable phase higher than 1590 DEG C.Monocline celsian-felspar has that chemical stability is good, stablizing (keep within the scope of 0-1590 DEG C monoclinic phase constant), thermal expansivity mutually, little (monoclinic phase BSA is 2.29 × 10 at the thermal expansivity of 20-1000 DEG C -6/ DEG C), good thermal shock, resistance of oxidation and acid-alkali-corrosive-resisting ability be strong, with SiC, Si 3n 4and mullite etc. has the premium propertiess such as good chemical compatibility, preferably as EBCs system high-temperature structured material, this is also that numerous scholar's primary study is how by the control of composition and technique with improve the major cause obtaining monocline celsian-felspar.Six side's celsian-felspar structural symmetries are high, and structure is simple, 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, and 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 promotion six side 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 to the key that monocline celsian-felspar changes 2diffusion.But under solid conditions, SiO be realized 2solid-state diffusion, be very difficult.Along with going deep into further of research, find BaAl 2si 2o 8with SrAl 2si 2o 8forming sosoloid, is one of effective measure promoting celsian-felspar phase transformation.Strontium feldspar (SrAl 2si 2o 8) identical with celsian-felspar structure, comprise monocline strontium feldspar, orthogonal strontium feldspar and six side's strontium feldspars three kinds equally, wherein, the over-all properties of monocline strontium feldspar is good.Also often first obtain six side's strontium feldspars during preparation SAS devitrified glass, then six side's strontium feldspars change monocline strontium feldspar into, with celsian-felspar unlike, SrAl 2si 2o 8there are six side's strontium feldspars to be easier to the transformation ratio of monocline strontium feldspar.Therefore, SrO is added, SrO and SiO when preparing BAS microcrystalline glass in series pottery 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, thus promote that six side's celsian-felspars are to the transformation of monocline celsian-felspar.
Typical EBCs system consists of 3Al at present 2o 32SiO 2/ 3Al 2o 32SiO 2+ BSAS/BSAS (1-xBaO-xSrO-Al 2o 3-2SiO 2, 0<x<1).The method of synthesis BSAS system powder mainly contains conventional sintering method, solid phase method, sol-gel method and hydrolysis methods.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 DEG C; Solid phase method is usually 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 DEG C, even if take hot pressed sintering, sintering temperature is also higher than 1500 DEG C.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 system composite oxide comparatively hard-to-sinter, usually 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.A large amount of unreacted SiO is there is in the BSAS powder of Solid phase synthesis 2, when these powder are used for coating, these unreacted SiO 2, be easy to the Si (OH) just generating gaseous volatile 4, so water vapour holds by original SiO very much 2occupied space enters, and reacts with SiC, thus causes the performance of charcoal/carbon-silicon carbide (C/C-SiC) matrix material to decline rapidly.Sol-gel method prepares powder, mostly adopts ester class and metal alcoholate to be raw material, this process costs is high, complex process, synthesis cycle are long, is difficult to realize synthesis in enormous quantities.Hydrolysis methods uses precipitation agent in settled solution, then throw out calcining obtained required powder, and research discovery for raw material, with tetraethoxy synchronous hydrolysis, is difficult to the BaO-Al obtaining stable and uniform with the soluble inorganic salt containing Ba, Al 2o 3-SiO 2gel.
In a word, yet there are no in the prior art with Al 2o 32SiO 2powder, BaCO 3powder, SrCO 3powder is the report that BSAS composite powder prepared by raw material.
Summary of the invention
The present invention is directed to the shortcoming existed in above-mentioned prior art, a kind of preparation method of BSAS composite ceramic powder is provided; The present invention lower than 1400 DEG C of synthesis by the phase composite of single silicoaluminate barium (strontium), purity is high, phase structure is stable BSAS composite ceramic powder.
The preparation method of a kind of environment barrier coating composite ceramic powder of the present invention, comprises the steps:
Step one
Al:Si=1:1 in molar ratio, adds aqueous aluminum salt solution in silicon ester solution, stirs and obtain mixed solution, then mixed solution being joined pH value is in the ammoniacal liquor in 8 ~ 9, stirs, reaction, filter, filter residue 600 ~ 900 DEG C of calcinings at least 2 hours, obtains Al after washing, drying 2o 32SiO 2composite ceramic powder; When described mixed solution joins in ammoniacal liquor, the pH value controlling reaction system is 8 ~ 9;
Step 2
With the Al prepared by step one 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 got mix after 1250 ~ 1400 DEG C calcining 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 is less than 1.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, in step one, described water-soluble aluminum salt is selected from the Al (NO of purity>=99% 3) 3, AlCl 3, one in Burow Solution; In described aqueous aluminum salt 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 one, 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 the one in the methyl silicate of purity >=99%, tetraethoxy, 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 one, described mixed solution adds in ammoniacal liquor with the speed of 0.1-0.5l/min; Be in the ammoniacal liquor in 8 ~ 9 when described mixed solution joins pH value completely, after stopping stirring, leave standstill 24 ~ 48h.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, in step one, filter residue deionized water wash is 6.5 ~ 7.5 to the pH of washing lotion.Generally deionized water wash 4 ~ 5 times are used in actual mechanical process; Volume ratio >=3 of each washing deionized water used and filter residue, be preferably 3-6 doubly, 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 one, by the filter residue after washing at 100 ~ 110 DEG C of dry 24h ~ 48h; Then 600 ~ 900 DEG C of calcinings 2 ~ 4 hours; Obtain that granularity is 0.1 μm-2 μm, purity be 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, its granularity be made to be 0.1 μm-2 μm.
The preparation method of a kind of BSAS composite ceramic powder of the present invention, in step 2, join the raw material got and mixed by ball milling, ball milling parameter is, 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, be preferably 1250 ~ 1400 DEG C of calcining 4 ~ 10h at 1100 ~ 1400 DEG C and be preferably 8 ~ 10h, make carbonate, acetate changes oxide compound into completely, 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 0.1-2 μm, purity is 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 DEG C of thermal treatment 2 ~ 4h, obtain the environment barrier coating composite ceramic powder material that granularity is 45-100 μm.Ball milling, granulation and thermal treatment are carried out, mainly conveniently follow-up spraying coating process to the monoclinic BSAS composite ceramic powder of gained.By ball milling, caking agent is mixed with ceramic powder, is convenient to follow-up granulation, thus in actual mechanical process the time of general control this section of ball milling be 8-10h; By 1050 ~ 1250 DEG C of thermal treatment 2 ~ 4h, both eliminated granulation caking agent used, turn increased the mobility of powder, follow-up spraying coating process can be carried out smoothly.
Principle and advantage
Principle
First the present invention adopts hydrolysis methods 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 just avoids rich SiO 2or rich Al 2o 3appearance, thus be easy to get to and meet the product of stoichiometric ratio, this raw materials technology is relatively inexpensive, technique is simply controlled, be easy to realize batch preparation.
Adopt the present invention at lesser temps (600 ~ 900 DEG C) synthesis Al 2o 32SiO 2powder.With Al 2o 32SiO 2, BaCO 3, SrCO 3for raw material, during high temperature sintering, first the sosoloid of strontium feldspar and celsian-felspar is formed, when sintering temperature is 1250 DEG C, 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 that six side's celsian-felspars are to the transformation of monocline celsian-felspar, reduce the transformation temperature of celsian-felspar.Therefore, when sintering temperature is 1300 ~ 1400 DEG C, the monoclinic phase BSAS composite powder of single structure can be synthesized, be environment barrier coating composite ceramic powder.
The present invention with water-soluble aluminum salt and silicon ester for raw material, by strictly controlling 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 be hydrolyzed and generate (Si (OH) 4) speed be almost infinitely close to 1:1, guarantee Al, Si and mix at the ratio uniform by 1:1 of atomic level, thus to avoid in Al-Si ceramic composite powder local SiO 2the difficult problem of content distribution inequality, provide prerequisite for preparing high-quality BSAS composite ceramic powder.This also just ensure that the chemical formula of prepared Al-Si ceramic composite powder is Al 2o 32SiO 2.Simultaneously due to single Al 2o 32SiO 2particle integrally participates in reaction, this ensure that to a great extent (Ba+Sr) with Al and Si by the ratio key of (Ba+Sr): Al:Si=1:2:1 and, this is acquisition high purity, BSAS powdered material that phase structure is single provides precondition.
Advantage
(1) the method for the invention adopts chemical coprecipitation-solid phase method phase compounding technology, and can realize the low temperature synthesis of environment barrier coating BSAS composite ceramic powder, synthesis temperature is lower than 1400 DEG C.Compared with conventional sintering method and solid phase method, its energy consumption obviously reduces;
(2) the environment barrier coating BSAS composite ceramic powder purity high (being more than or equal to 99%) of technical solution of the present invention synthesis, be made up of single silicoaluminate barium (strontium) phase (oblique system), 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.Compared 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; Compared with existing sol-gel method, its working efficiency obviously increases, simultaneously because sol-gel is in preparation process, how to be washed out by impurity is also a difficult problem, and the present invention utilizes water-soluble aluminum salt and silicon ester to be raw material cleverly, avoid this difficult problem cleverly by hydrolysis methods, this is further for large-scale industrial production provides strong guarantee.Compared with existing hydrolysis methods, in hydrolytic precipitation process, only prepare Al due to devising cleverly 2o 32SiO 2composite powder, avoids a series of deficiencies that the instability due to system is brought.
(4) composite ceramic powder material of the present invention, plasma spraying technology is adopted to prepare environment barrier coating, test result shows that this coating keeps single monoclinic phase structure in 1500 DEG C of thermal treatment 100h cool to room temperature processes, phase structure is stablized, and can meet the long-time high temperature protection of SiC material.
Accompanying drawing explanation
Preparation technology's flow process of accompanying drawing 1 environment barrier coating composite ceramic powder.
Accompanying drawing 2 is 0.5BaO-0.5SrO-Al prepared by the embodiment of the present invention one 2o 3-2SiO 2(BSAS) X-ray diffractogram of composite ceramic powder is general.
Accompanying drawing 3 is 0.75BaO-0.25SrO-Al prepared by the embodiment of the present invention two 2o 3-2SiO 2(BSAS) X ray diffracting spectrum of composite ceramic powder.
Accompanying drawing 4 is 0.75BaO-0.25SrO-Al prepared by the embodiment of the present invention two 2o 3-2SiO 2(BSAS) the SEM photo of composite ceramic powder.
Accompanying drawing 5 is the X ray diffracting spectrum of BSAS composite ceramic powder prepared by comparative example 1.
As can be seen from Figure 2 with Al 2o 32SiO 2, BaCO 3, SrCO 3for raw material, at 1350 DEG C of single 0.5BaO-0.5SrO-Al of synthesis 2o 3-2SiO 2(BSAS) composite powder, powder crystallinity is high, occurs without single oxide powder; 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 DEG C of single 0.75BaO-0.25SrO-Al of synthesis 2o 3-2SiO 2(BSAS) composite powder, powder crystallinity is high, occurs without single oxide powder; And products therefrom is single oblique system.
Find out from Fig. 4 (a), prepared 0.75BaO-0.25SrO-Al 2o 3-2SiO 2(BSAS) composite powder is reunion state, large agglomerating particles (3 ~ 20 μm); From finding out that from Fig. 4 (b) large agglomerating particles is reunited by the nano particle of size uniform (10-50nm) with forming.
As can be seen from Figure 5, BaCO 3, SrCO 3, Al 2o 3and SiO 2raw material powder, after mixing and ball milling, drying, 1500 DEG C 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 do not react, and has part Ba 0.5sr 0.5al 2si 2o 8synthesis, almost without the Ba meeting stoichiometric ratio 0.75sr 0.25al 2si 2o 8(BSAS) composite powder synthesis.Comparison diagram 2 and Fig. 3 known, simple solid phase method is difficult to that synthesis purity is high, crystalline structure is single, meet the BSAS composite powder of stoichiometric ratio, and its synthesis temperature is higher.
Embodiment
Embodiment one
To prepare 0.5BaO-0.5SrO-Al 2o 3-2SiO 2(BSAS) composite ceramic powder 10 kilograms is example, and being scaled mole number is 28.52mol, Al in composition 2o 3mole number is 28.52mol, then 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, then need tetraethoxy quality 12.25 kilograms, being scaled tetraethoxy volume is 13.2L.Measure 13.2L tetraethoxy, measure 15.4 kilograms of ethanol, to add in aluminum nitrate solution after the tetraethoxy measured, ethanol mixing, stirring makes it fully mix in 30 minutes, then mixed solution being joined pH value with the speed of 0.2l/min is in the ammoniacal liquor in 8 ~ 9, the pH value perseverance of reaction system is made to be 8 ~ 9 by filling into ammoniacal liquor during reaction, stir, reaction.React complete continuation stirring 30 minutes, then leave standstill 24h, ensure that aluminum ion precipitates completely, tetraethoxy complete hydrolysis.Adopt the method deionized water repetitive scrubbing and filtering-depositing 4 times that hang and filter, remove NH 4+ion, by through wash and the gelatinous precipitate filtered in 110 DEG C of dry 24h, obtain precursor powder, by precursor powder 800 DEG C calcine 3h obtain Al 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, by after the drying of ball milling disposed slurry in 1350 DEG C of thermal treatment 10h, obtain 0.5BaO-0.5SrO-Al after cooling 2o 3-2SiO 2(BSAS) composite ceramic powder material.XRD is adopted 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, occurs without single oxide powder; And products therefrom is single oblique system.XRF technology for detection is adopted 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, then mist projection granulating, namely the 1150 DEG C of thermal treatment 2.5h of the powder particle after granulation obtain 0.5BaO-0.5SrO-Al 2o 3-2SiO 2(BSAS) composite ceramic powder material 10 kilograms.This composite powder can be used for plasma spraying and prepares environment barrier coating, realizes protecting the high temperature water resistant oxygen of C/C-SiC matrix material, and its working temperature can reach 1500 DEG C.
Embodiment two
To prepare 0.75BaO-0.25SrO-Al 2o 3-2SiO 2(BSAS) composite ceramic powder 10 kilograms is example, and being scaled mole number is 27.55mol, Al in composition 2o 3mole number is 27.55mol, then 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, then need tetraethoxy quality 11.82 kilograms, being scaled tetraethoxy volume is 12.7L.Measure 12.7L tetraethoxy, measure 14.8 kilograms of ethanol, to add in aluminum nitrate solution after the tetraethoxy measured, ethanol mixing, stirring makes it fully mix in 30 minutes, then mixed solution being joined pH value with the speed of 0.2l/min is in the ammoniacal liquor in 8 ~ 9, the pH value perseverance of reaction system is made to be 8 ~ 9 by filling into ammoniacal liquor during reaction, stir, reaction; React complete continuation stirring 30 minutes, then leave standstill 24h, ensure that aluminum ion precipitates completely, tetraethoxy complete hydrolysis.Adopt the method deionized water repetitive scrubbing and filtering-depositing 4 times that hang and filter, remove NH 4+ion, by through wash and the gelatinous precipitate filtered in 110 DEG C of dry 24h, obtain precursor powder, by precursor powder 800 DEG C calcine 3h obtain Al 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, by after the drying of ball milling disposed slurry in 1350 DEG C of thermal treatment 10h, obtain 0.75BaO-0.25SrO-Al after cooling 2o 3-2SiO 2(BSAS) composite ceramic powder material.XRD is adopted 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, occurs without single oxide powder; And products therefrom is single oblique system.Adopt scanning electron microscope (SEM) to observe this powder, as shown in Figure 4, find out from Fig. 4 (a), prepared 0.75BaO-0.25SrO-Al 2o 3-2SiO 2(BSAS) composite powder is reunion state, large agglomerating particles (3 ~ 20 μm); From finding out that from Fig. 4 (b) large agglomerating particles is reunited by the nano particle of size uniform (10-50nm) with forming.XRF technology for detection is adopted to detect gained 0.75BaO-0.25SrO-Al 2o 3-2SiO 2purity, the purity obtaining products therefrom is 99.09% (> 99%).
By this superfine composite ceramic powder mechanical ball milling 10h, then mist projection granulating, namely the 1150 DEG C of thermal treatment 2.5h of the powder particle after granulation obtain 0.75BaO-0.25SrO-Al 2o 3-2SiO 2(BSAS) composite ceramic powder material 10 kilograms.This composite powder can be used for plasma spraying and prepares environment barrier coating, realizes protecting the high temperature water resistant oxygen of C/C-SiC matrix material, and its working temperature can reach 1500 DEG C.
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) composite ceramic powder 1 kilogram is joined and is got each raw material, with BaCO 3, SrCO 3, Al 2o 3and SiO 2powder is raw material, adopts Solid phase synthesis BSAS composite powder.Take 316.8gBaO, 71.3gSrO, 280.9gAl respectively 2o 3and 331gSiO 2, Material quality of grinding balls is Al 2o 3, be that 1:2:5 adds in ball grinder with mass ratio by material, dehydrated alcohol, abrading-ball.Then by ball grinder on planetary ball mill with the rotating speed ball milling 12h of 200rpm.After ball milling, slurry is placed in loft drier, at 120 DEG C of dry 12h, obtains dry mixed powder.Use Si-Mo rod High Temperature Furnaces Heating Apparatus to calcine mixed powder, calcining temperature is 1500 DEG C, and soaking time is 20h, and heat-up rate is 10 DEG C/min, and the type of cooling is furnace cooling.XRD is adopted to carry out material phase analysis to the powder after high-temperature calcination, 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, drying, 1500 DEG C 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 do not react, and has part Ba 0.5sr 0.5al 2si 2o 8synthesis, almost without the Ba meeting stoichiometric ratio 0.75sr 0.25al 2si 2o 8(BSAS) composite powder synthesis.

Claims (6)

1. a preparation method for BSAS composite ceramic powder, is characterized in that comprising the steps:
Step one
Al:Si=1:1 in molar ratio, aqueous aluminum salt solution is added in silicon ester solution, stir and obtain mixed solution, then mixed solution being joined pH value is in the ammoniacal liquor of 8 ~ 9, stirs, reaction, the pH value controlling reaction system is 8 ~ 9, after having reacted, and filters, filter residue through washing after, at 100 ~ 110 DEG C of dry 24h ~ 48h; Then 600 ~ 900 DEG C of calcinings 2 ~ 4 hours; Obtain that granularity is 0.1 μm-2 μm, purity be more than or equal to 99% Al 2o 32SiO 2composite ceramic powder; Described water-soluble aluminum salt is selected from the Al (NO of purity>=99% 3) 3, AlCl 3, one in Burow Solution; In described aqueous aluminum salt solution, the concentration of aluminium element is 0.3-1.5mol/L;
Step 2
With the Al prepared by step one 2o 32SiO 2composite ceramic 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 got and mix rear loading alumina crucible and send in process furnace, at 1250 ~ 1400 DEG C of calcining 4 ~ 10h, 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 is less than 1; The granularity of described BSAS composite ceramic powder is 0.1-2 μm, purity is more than or equal to 99%.
2. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, is characterized in that: in step one, and 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 the one in the methyl silicate of purity >=99%, tetraethoxy, positive silicic acid propyl ester; Described alcohol is selected from least one in methyl alcohol, ethanol, propyl alcohol.
3. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, it is characterized in that: in step one, described mixed solution adds in ammoniacal liquor with the speed of 0.1-0.5L/min; After having reacted, stop stirring, leave standstill 24 ~ 48h.
4. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, is characterized in that: in step one, and filter residue deionized water wash is 6.5 ~ 7.5 to the pH of washing lotion.
5. the preparation method of a kind of BSAS composite ceramic powder according to claim 1, is characterized in that: in step 2, and 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.
6. 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 got and mixed by ball milling, ball milling parameter is, 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.
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