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CN100336774C - Process for synthesizing heat-stable aluminium titanate - Google Patents

Process for synthesizing heat-stable aluminium titanate Download PDF

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CN100336774C
CN100336774C CNB2004100408568A CN200410040856A CN100336774C CN 100336774 C CN100336774 C CN 100336774C CN B2004100408568 A CNB2004100408568 A CN B2004100408568A CN 200410040856 A CN200410040856 A CN 200410040856A CN 100336774 C CN100336774 C CN 100336774C
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sosoloid
mgo
sol
aluminium titanates
aluminium
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CN1762900A (en
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张其春
叶巧明
林金辉
常嗣和
刘菁
宋继芳
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Chengdu Univeristy of Technology
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Abstract

The present invention relates to a technological process for synthesizing aluminium titanate which has good thermal stability, which aims at improving the thermal stability of aluminium titanate containing single MgO additive. The method comprises the following technological steps: synthesizing sol containing three components, such as titanium, aluminum and magnesium, by taking titanium alkoxide, aluminum sol and magnesium salts as raw materials; converting the sol into gel; solvating wet gel; calcining gel to be dry; obtaining a precursor containing mixed titanium oxide, aluminum oxide and magnesium oxide; preparing the aluminium titanate stabilized by MgO by calcining the precursor, namely that the aluminium titanate stabilized by MgO is an Al<2 (1-x)>Mg<x>Ti<1+x>O<5> sosoloid. The present invention arrives at a conclusion that the thermal decomposition rate of the technology of the present invention for synthesizing the aluminium titanate containing single MgO additive is 0 within a lower MgO content range, namely that the composition parameter x of the sosoloid is between 0.06 to 0.08, wherein the raw materials are proportioned according to the composition of the Al<2 (1-x)>Mg<x>Ti<1+x>O<5>.

Description

A kind of technology of synthetic thermostability aluminium titanates
Technical field
The present invention relates to the technology of synthetic aluminium titanates, particularly with the synthetic technology of improved sol-gel method, the thermostability that is intended to obviously improve aluminium titanates with low MgO addition with the stable aluminium titanates of single MgO additive.The invention belongs to the stupalith field.
Background technology
Aluminium titanates (is represented as Al 2TiO 5) be a kind of high temperature resistant, type material that thermal expansivity is little.The main inherent defect of pure aluminium titanates is that it can be decomposed into α-Al in 750～1300 ℃ of temperature ranges 2O 3And rutile TiO 2, particularly in its rate of decomposition maximum of 1100 ℃ of left and right sides, the half point in this temperature range is separated the time (being that rate of decomposition reaches for 50% time), according to sintering temperature, density, grain size, changes between 2～25 hours.This Decomposition can cause the thermal expansivity of aluminium titanates to increase, thereby loses its low-thermal-expansion rate characteristic, the use properties of deterioration aluminium titanates goods.The solution that adopts in order to overcome this inherent defect is that some special additives of introducing to suppress the thermolysis of aluminium titanates, improve its thermostability and improve its physical strength in aluminium titanates.The more additive of research is MgO at present, Fe 2O 3, ZrO 2, SiO 2, ZrSiO 4, mullite etc.
Check introduce additive to the thermostability of aluminium titanates improve effect the time, the thermolytic rate of using aluminium titanates usually is as measurement index.The measuring method of this thermolytic rate is: the thermolysis test temperature is 1100 ℃, and aluminium titanates is heated certain hour under this temperature, with the sample after the X ray powder crystal diffraction measurement experience thermolysis test, determines the rutile TiO by thermolysis generated then 2The diffraction peak area of particular crystal plane (be represented as I T), and the undecomposed Al that remains 2TiO 5The diffraction peak area of particular crystal plane (be represented as I AT), calculate Al with these two parameters 2TiO 5Rate of decomposition, the definition that is used to calculate is: the rate of decomposition of aluminium titanates=[I T/ (I T+ I AT)] * 100%.After the experience thermolysis test, the numerical value of the rate of decomposition of aluminium titanates is more little, reflects that the thermostability of aluminium titanates is good more.In actual the use, exist two classes to be used to calculate the crystal face selection system of the rate of decomposition of aluminium titanates, use the numerical value difference of the rate of decomposition of the aluminium titanates that this two classes crystal face selection system calculated.First kind selective system is by M Ishitsuka[Journalof American Ceramic Society, 1987,70:69-71] propose, he selects rutile TiO for use 2The diffraction peak area of (101) crystal face as I T, Al 2TiO 5The diffraction peak area of (023) crystal face as I ATThe second class selective system proposes by opening alliance [silicate journal, 2002,30 (4): 451-455], the Al that uses MgO as single additive 2TiO 5Be expressed as Al 2 (1-x)Mg xTi 1+xO 5(being abbreviated as AMT) sosoloid adopts rutile TiO 2The diffraction peak area of (110) crystal face as I T, the Al after the thermolysis 2TiO 5The diffraction peak area of (110) crystal face be labeled as I AMT, replace I with it AT, be used for Al 2TiO 5The rate of decomposition calculation formula in.To after the same experience thermolysis rutile TiO being arranged 2The aluminum titanate sample that occurs if use this two classes crystal face selection system to calculate rate of decomposition respectively, when then calculating with the crystal face selection system of opening alliance, can draw the high de-agglomeration rate score.Therefore, the rate of decomposition result of the crystal face selection system computing of a usefulness alliance reflects the thermostability of aluminium titanates, is comparatively strict mode.When investigating the thermostability of using present technique institute synthetic aluminium titanates product, we adopt the crystal face selection system computing thermolytic rate of opening alliance.
The researchist in present technique field knows that magnesium oxide (being represented as MgO) is a kind of additive commonly used in the aluminium titanates preparation, and MgO is mixed in the aluminium titanates, calcines, and can generate MgTi under proper temperature 2O 5, it can and Al 2TiO 5Form sosoloid, improve aluminium titanates opposing pyrolysated stability; In addition, an amount of introducing MgO can also improve the mechanical property of aluminium titanates porcelain body, and is also little to other excellent thermal characteristics influence of porcelain body.Relevant prior art comprises:
Jiang Weihui etc. [Journal of Inorganic Materials, 1999,14 (5): 801-805] are with ready-made Al 2TiO 5Powder is a raw material, and after mixing with additives such as MgO, the aluminium titanates that contains additive is prepared in process ball milling-drying-sample preparation-burn till.This synthetic technology should be classified as the china-clay method synthetic technology.They are with prepared 1100 ℃, 30 hours thermolysis of aluminium titanates experience test, definite rate of decomposition that does not add the stable pure aluminium titanates of any additives is 100%, using MgO is 38.2% (rate of decomposition numerical value system adopts the crystal face selection system computing of MIshitsuka) as the rate of decomposition of the stable aluminium titanates of single additive, uses Fe 2O 3Rate of decomposition as the stable aluminium titanates of single additive is 11.5%; In aluminium titanates, introduce simultaneously and remove Fe 2O 3Behind second kind of additive in addition, may improve the thermostability of aluminium titanates.Wherein, introduce Fe when simultaneously 2O 3And the MgO additive, when forming the continuous solid solution of iron content, magnesium with aluminium titanates, the rate of decomposition that can make aluminium titanates is 0.They record and narrate [Jiang Weihui etc., Journal of Inorganic Materials, 2000,15 (1): 163-168], and behind the introducing additive, if the unit cell parameters c of aluminium titanates does not change, then the stability of aluminium titanates can not improve in aluminium titanates; If introduce additive the c value of aluminium titanates is obviously increased, then the stability of aluminium titanates will significantly be improved, and the amplification of unit cell parameters c is big more, and aluminium titanates is just stable more.
Open [silicate journal, 2002,30 (4): 451-455] usefulness α-Al such as alliance 2O 3, rutile TiO 2Reaching the MgO powder is raw material, according to Al 2 (1-x)Mg xTi 1+xO 5The molar ratio ingredient of sosoloid (x is respectively 0,0.01,0.05,0.1,0.3) respectively through behind 12 hours batch mixings, adopts solid reaction process to synthesize Al in 2 hours 1450 ℃ of insulations 2 (1-x)Mg xTi 1+xO 5Sosoloid.Their synthetic method also belongs to china-clay method.They record and narrate, Al 2 (1-x)Mg xTi 1+xO 5The thermostability of sosoloid is than pure aluminium titanates height; Al 2 (1-x)Mg xTi 1+xO 5The thermostability of sosoloid increases with the x value and improves; When x=0.05, Al 2 (1-x)Mg xTi 1+xO 51100 ℃ of insulations 10 hours, its rate of decomposition was 9%.This rate of decomposition of 9% is the minimum rate of decomposition of their aluminium titanates that contains single additive MgO reported, also is the minimum rate of decomposition of the aluminium titanates that contains single additive MgO of existing documents and materials report.Under the equal conditions, pure aluminium titanates almost completely decomposes.For they the synthetic x of institute the Al of other value of non-0.05 2 (1-x)Mg xTi 1+xO 5Sosoloid, they do not provide corresponding rate of decomposition numerical value in report.
From these above-mentioned prior aries as can be seen, the existing independent synthetic technology of using MgO to stablize aluminium titanates as additive only is reduced to 9% with the thermolytic rate of aluminium titanates at most.Should illustrate, in aluminium titanates, introduce MgO, Fe when speaking of 2O 3Deng additive, make the unit cell parameters value generation considerable change of aluminium titanates, when stablizing aluminium titanates, the aluminium titanates of being talked comes down to a kind of by MgTi 2O 5, Fe 2TiO 5Same Al 2TiO 5Formed sosoloid.The regularity cognition that these above-mentioned prior aries are stablized aluminium titanates to additive can be reduced: (1) introduces additive in aluminium titanates after, if the unit cell parameters c value of aluminium titanates does not change, then the stability of aluminium titanates can not improve; If introduce additive in aluminium titanates the c value of aluminium titanates is obviously increased, then the stability of aluminium titanates will significantly be improved, and the amplification of unit cell parameters c is big more, and aluminium titanates is just stable more; (2) MgO can suppress the decomposition of aluminium titanates, the Al of formation effectively as additive 2 (1-x)Mg xTi 1+xO 5The thermostability of sosoloid is better than pure aluminium titanates; (3) Al 2 (1-x)Mg xTi 1+xO 5The thermostability of sosoloid improves with the increase of the composition parameter x value of sosoloid.Because Al 2 (1-x)Mg xTi 1+xO 5Have positive correlation between the composition parameter x of intravital MgO addition of solid solution and sosoloid, therefore, above-mentioned understanding (3) can be expressed as again: Al 2 (1-x)Mg xTi 1+xO 5The thermostability of sosoloid increases with the MgO addition and improves.The back can see that result of the present invention shows that there are some problems in regularity cognition (1) and understanding (3) that these above-mentioned prior aries are stablized aluminium titanates to additive, and these agnoeas reflect practical situation all sidedly.
The heat resistanceheat resistant of adopting composite additive to improve aluminium titanates decompose stable aspect, outside the technology except above-mentioned Jiang Weihui etc., can also enumerate: [East China University of Science's journal such as Xue Mingjun, 2001,27 (1): 76-79] adopt mullite and ferric oxide as composite additive, 20 hours thermolytic rates of institute's synthetic aluminium titanates can be dropped to 17%; Five kinds of basal component synthetic of ZL 88108143.4 usefulness ceramic body reaches the purpose of stablizing aluminium titanates, and these five kinds of components are Al 2O 3, TiO 2, SiO 2, RE 2O 3And Fe 2O 3, the ceramic body that is generated is made up of aluminium titanates and two kinds of crystalline phases of mullite basically.
In addition, Xue Mingjun etc. [East China University of Science's journal, 2000,26 (1): 66-69] synthesize the whole gel of titaniferous, aluminium with sol-gel method in pure medium, obtain pure Al after 1400 ℃ of calcinings 2TiO 5Powder, this work does not relate to Al 2TiO 5The thermal decomposition performance of powder.
The synthetic technology of stablizing aluminium titanates as additive in view of existing independent use MgO only is reduced to 9% with the thermolytic rate of aluminium titanates at most, the object of the present invention is to provide a kind of technology of synthetic aluminium titanates, have the thermostability of the aluminium titanates of low MgO addition with obvious raising.
Summary of the invention
The synthetic technology that contains the magnesian aluminium titanates of single additive of the present invention, used improved sol-gel method, that is: be initiator with titanium alkoxide, aluminium colloidal sol, magnesium salts, according to Ti: Al: Mg=(1+x): the molar ratio batching of 2 (1-x): x, just according to Al 2 (1-x)Mg xTi 1+xO 5The composition batching of sosoloid is that gel-wet gel precipitation thinner-roasting xerogel obtains TiO through the colloidal sol-conversion colloidal sol that synthesizes titanium, aluminium, magnesium three components 2-Al 2O 3The step of-MgO mixed oxide presoma-calcining presoma is prepared the stable Al with MgO 2TiO 5, Al just 2 (1-x)Mg xTi 1+xO 5The step of sosoloid and realize its purpose.
The synthetic method that contains the magnesian aluminium titanates of single additive of the present invention has following processing step:
(1) according to Ti: Al: Mg=(1+x): the molar ratio of 2 (1-x): x is got titanium alkoxide, aluminium colloidal sol, magnesium salts batching, just according to Al 2 (1-x)Mg xTi 1+xO 5The composition batching of sosoloid in conjunction with hyperacoustic dissemination, is reacted in the presence of sequestrant, obtains three limpid component stable sols;
(2) the three component colloidal sols that step (1) is obtained place 40 ℃ of-50 ℃ of water-baths to be incubated, and make colloidal sol generation gelation;
(3) make the whole quick freezing of wet gel that step (2) obtained with liquid nitrogen, then with the vacuum lyophilization mode from freezing to remove solvent in the body, make it change xerogel into;
(4) xerogel that step (3) is obtained changes roasting in 400 ℃ of-1000 ℃ of retort furnaces over to, obtains mixed with titanium, aluminium, magnesium oxide presoma;
(5) mixed with titanium, aluminium, the magnesium oxide presoma that is obtained at 1250 ℃ of-1650 ℃ of following calcining steps (4) obtains by the stable aluminium titanates product of single MgO additive.
Titanium alkoxide in the above-mentioned steps (1) is that butyl (tetra) titanate (is represented as Ti (OC 4H 9) 4).For the facility of analyzing titanium content and quantitatively pipetting synthetic required titanium amount, before the batching that is used for step (1), earlier butyl (tetra) titanate is made the aqueous isopropanol of butyl (tetra) titanate, measure the titanium content of the aqueous isopropanol of butyl (tetra) titanate with the diantipyrylmethane spectrophotometer method, amount accurately pipettes this solution and uses on demand then.
Aluminium colloidal sol in the above-mentioned steps (1) is boehmite sol (being represented as AlOOH).It is to use Al (NO at the scene 3) 39H 2O that is: adds NaOH solution earlier with Al (NO as the initiator synthetic 3) 3Solution changes Al (OH) into 3Precipitation continues to add NaOH solution and makes resolution of precipitate, changes NaAlO into 2Solution adds in rare nitric acid and NaAlO again 2, generate the AlOOH precipitation, after the AlOOH precipitation suction filtration that generated, washing, filter cake obtains AlOOH colloidal sol with rare nitric acid peptization; With the aluminium content of this boehmite sol of EDTA volumetric determination, then on demand the amount accurately pipette this colloidal sol be used for the batching.After this boehmite sol is at room temperature placed half a year, still both do not had precipitation and separated out, do not occurred jelly yet, shown having good stability of this colloidal sol.
Magnesium salts in the above-mentioned steps (1) is magnesium nitrate (Mg (NO 3) 26H 2O).
Sequestrant in the above-mentioned steps (1) is methyl ethyl diketone and Glacial acetic acid.
In the inventive method, step (1) is introduced component aluminium, is stablized titanium alkoxide butyl (tetra) titanate, step (3) with methyl ethyl diketone as main sequestering agent and make the whole quick freezing of wet gel with liquid nitrogen with the boehmite sol mode, in the wet gel that freezes, remove solvent with the vacuum lyophilization mode then, making it change xerogel into is crucial mode, and three components are according to Al in the step (1) 2 (1-x)Mg xTi 1+xO 5The molar ratio of sosoloid is formed batching, and selected parameter x is a key parameter.Wherein, introduce component aluminium with the boehmite sol mode, rather than directly use inorganic aluminates such as aluminum nitrate, the polycondensation product generation copolycondensation of the small molecular weight that the boehmite sol particle becomes with the hydrolysate of butyl (tetra) titanate and by hydrolysate low-shrinkage combinate form be can help in step (1), to make, titanium, aluminium, the even colloidal sol of magnesium three components generated.Because boehmite sol is a kind of water-sol, when in butyl (tetra) titanate, introducing component aluminium in the boehmite sol mode, also just in butyl (tetra) titanate, introduce a large amount of water simultaneously, this has just improved the molar ratio of the water/titanium alkoxide of this reaction system greatly, reached molar ratio 〉=200, and existing knowledge shows, the molar ratio of water/titanium alkoxide was above 1.5 o'clock, precipitation can be generated, colloidal sol can't be generated.This processing method is introduced methyl ethyl diketone and is stablized titanium alkoxide butyl (tetra) titanate as main sequestering agent, under the booster action of acetic acid, under the situation of molar ratio 〉=200 of water/titanium alkoxide, still can make the titanium alkoxide keep stable, slow hydrolysis, the polycondensation of hydrolysate and the copolycondensation of hydrolysis, polycondensation product and boehmite sol particle through the titanium alkoxide, be used in combination hyperacoustic dissemination, guaranteed the final even colloidal sol that generates clear and stable.When step (3) adopts the vacuum lyophilization mode to remove solvent in the wet gel, at first use the liquid nitrogen freezing wet gel, rather than it is freezing or directly freezing with freeze drier with refrigerator, the low temperature of liquid nitrogen makes all kinds of SOLVENTS that comprises in the wet gel frozen in moment, to freeze gel subsequently transfers to and removes solvent in the vacuum freeze drier, obtain loose porous xerogel, thereby the differentiation trend that has suppressed different components effectively continues to keep titanium, aluminium, the uniform distribution of three kinds of components of magnesium on miniature scale in the xerogel of gained.If it is freezing or during with refrigerator with the direct freezing wet gel of freeze drier in step (3), it is from gel surface that the cooling of wet gel is freezed, pass to nuclear portion gradually, when the freezing chamber of for example wet gel directly being put into the freeze drier about-50 ℃ freezes, the freeze all of wet gel needs 8-10 hour, under this environment, water contained in the wet gel top layer preferentially condenses, the isopropanol content of the inner water-aqueous isopropanol that does not freeze is increased gradually, in successively freezing part titanium appears consequently, aluminium, magnesium three components contents differences, i.e. differentiation phenomenon.
Compared with the prior art the present invention has following advantage and unusual effect:
One, the present invention relates to the synthesis technique of aluminium titanates, is purpose with the synthetic aluminium titanates that contains single MgO additive, good thermal stability.In order to solve the still not satisfied particular problem of thermostability of the aluminium titanates that prior art obtained when using single MgO additive, the present invention is by selecting suitable MgO addition for use, in strict accordance with Al 2 (1-x)Mg xTi 1+xO 5The stoicheiometry of sosoloid quantitatively uses the initiator of titanium, aluminium, three kinds of components of magnesium, and used improved sol-gel method, the special-effect of single MgO additive to the stabilizing power of aluminium titanates is improved, under the situation of single interpolation MgO, the low MgO addition of use, having obtained thermolytic rate is zero Al 2 (1-x)M GxTi 1+xO 5Sosoloid.The present invention obtains on the basis of the understanding of some given having a prejudice property of the aluminium titanates technology of preparing that overcomes the single MgO additive of existing use, and the understanding of these having a prejudice property is at Al 2 (1-x)Mg xTi 1+xO 5The regularity that the size of the unit cell parameters c of the addition of MgO and sosoloid provides the influence relation of the thermostability of sosoloid in the sosoloid is warned, and they can be reduced: the amplification of the unit cell parameters c of aluminium titanates is big more, and aluminium titanates is just stable more; Can make Al owing to improve MgO content 2 (1-x)Mg xTi 1+xO 5The unit cell parameters c value of sosoloid increases, and therefore increases with the MgO addition also will make Al 2 (1-x)Mg xTi 1+xO 5The thermostability of sosoloid improves.The present invention has broken through these regular warnings of above-mentioned prior art, does not follow from improving the MgO addition and improves Al 2 (1-x)Mg xTi 1+xO 5The relevant thinking of the thermostability of sosoloid, and be to use processing method of the present invention, synthesizing thermolytic rate under lower MgO addition is zero Al 2 (1-x)Mg xTi 1+xO 5Sosoloid.
Two, with the synthetic Al of technology of the present invention 2 (1-x)Mg xTi 1+xO 5The sosoloid product, when the composition parameter x of sosoloid equals 0.04,0.06,0.07,0.08,0.135 respectively, pairing Al 2 (1-x)Mg xTi 1+xO 5The thermostability of synthetic product is all far above pure aluminium titanates, and still, wherein thermolytic rate is minimum is composition parameter x=0.06,0.07,0.08 Al 2 (1-x)Mg xTi 1+xO 5Sosoloid, their thermolytic rate are zero, show these Al 2 (1-x)Mg xTi 1+xO 5The thermostability of synthetic product has obtained obvious improvement.Existing documents and materials show, consider Al from the possibility that forms sosoloid 2 (1-x)Mg xTi 1+xO 5The x of sosoloid can get the arbitrary value between 0 to 1; When x＞0, formed is Al 2TiO 5With MgTi 2O 5Sosoloid; Because pure MgTi 2O 5Each unit cell parameters all greater than pure Al 2TiO 5Respective value, therefore, with the increase of MgO addition in the sosoloid, Al 2 (1-x)Mg xTi 1+xO 5The unit cell parameters of sosoloid can increase, gradually to MgTi 2O 5Analog value close.In actual applications, the significant application value of alumina titanate ceramics is based on Al 2TiO 5Low, the resistant to elevated temperatures characteristic of thermal expansivity, rather than based on MgTi 2O 5Character.Therefore, above-mentioned prior art is improved Al by the addition that improves single MgO additive 2 (1-x)Mg xTi 1+xO 5The thermostability of sosoloid outside the still not satisfied problem of the thermostability that has formed aluminium titanates, with the increase again and again of MgO addition in the sosoloid, will make the synthetic Al of institute 2 (1-x)Mg xTi 1+xO 5The character of sosoloid departs from Al 2TiO 5, and to MgTi 2O 5Character close, this will lose low, the resistant to elevated temperatures excellent characteristic of thermal expansivity of aluminium titanates, the application performance of deterioration aluminium titanates porcelain body to a certain extent.
The Al that synthesizes with technology of the present invention 2 (1-x)Mg xTi 1+xO 5Sosoloid, when the composition parameter x of sosoloid was 0.06,0.07,0.08, the addition of MgO was lower, and the thermolytic rate of sosoloid is 0, thereby can keep Al preferably with the stable aluminium titanates porcelain body that this material preparation goes out 2TiO 5Application characteristic.
Three, aspect preparation technology, the china-clay method synthetic technology adopts two or more powder by the synthetic Al of solid-solid state reaction 2 (1-x)Mg xTi 1+xO 5Sosoloid, this class reaction system relies on grinding to increase the surface-area of powder and the contact area between the different powder, if the synthetic product with this class reaction system is compared with the synthetic product of sol-gel method, then the former is relatively poor relatively in the homogeneity between different components on the micro-scale, and this will reduce the Al that final calcining generates 2 (1-x)Mg xTi 1+xO 5The composition homogeneity of sosoloid on micro-scale makes the thermostability of sosoloid relatively poor relatively.The present invention uses that improved sol-gel technique is synthetic forms uniform three component gels, because the present invention accurately measures Ti, the Al content of initiator in preparation technology's step (1), in strict accordance with Al 2 (1-x)Mg xTi 1+xO 5The stoicheiometry of sosoloid uses titanium, aluminium, the initiator of three kinds of components of magnesium, in the presence of sequestrant methyl ethyl diketone and Glacial acetic acid, from mixing solutions, synthesize titanium, aluminium, the even colloidal sol of magnesium three components, at the further polycondensation generating structure of step (2) by sol particles, form uniform wet gel, the wet gel that is generated with the rapid freezing step of liquid nitrogen (2) in step (3), freeze from wet gel with the vacuum lyophilization mode then and remove solvent the piece, change it into xerogel, make titanium, aluminium, the composition homogeneity of three kinds of components of magnesium in mixing solutions can remain to mixed with titanium always, aluminium, in the magnesium oxide presoma, thereby can reduce the differentiation trend between the different components of nature difference in the preparation process effectively, improve the Al that is generated through final calcining 2 (1-x)Mg xTi 1+xO 5The composition homogeneity of sosoloid on micro-scale improved the thermostability of gained sosoloid product.
Embodiment
To help to understand the present invention by following embodiment, but following embodiment does not limit content of the present invention.
Embodiment 1
A kind of synthetic technology that contains the magnesian aluminium titanates powder of single additive of the present invention, its processing step is as follows:
At first use the isopropanol butyl (tetra) titanate, make the aqueous isopropanol of butyl (tetra) titanate, accurately measure the titanium concentration of the aqueous isopropanol of butyl (tetra) titanate with the diantipyrylmethane spectrophotometer method; Use Al (NO at the scene 3) 39H 2O synthesizes the boehmite sol that has good stability as initiator, accurately measures the aluminum concentration of this boehmite sol with the EDTA volumetry.According to sosoloid Al 2 (1-x)Mg xTi 1+xO 5Chemical constitution formula, selected sosoloid composition parameter x equals 0.04,0.07,0.135 respectively, to synthesize with the corresponding three kinds of Al of these three composition parameters 2 (1-x)Mg xTi 1+xO 5Sosoloid, that is: Al 1.92Mg 0.04Ti 1.04O 5(mass fraction of MgO is W in this sosoloid MgO/ W Sosoloid=0.89%) Al, 1.86Mg 0.07Ti 1.07O 5(W MgO/ W Sosoloid=1.56%) Al, 1.73Mg 0.135Ti 1.135O 5(W MgO/ W Sosoloid=3.00%).
(1) the aqueous isopropanol 40ml that pipettes butyl (tetra) titanate adds methyl ethyl diketone 4ml and Glacial acetic acid 10ml subsequently in the dry combustion method cup, stirs.According to Al 2 (1-x)Mg xTi 1+xO 5The composition parameter x of sosoloid product quantitatively pipettes the boehmite sol that contains required aluminium amount, takes by weighing the required amount of magnesium corresponding M g (NO with institute 3) 26H 2O is dissolved in the boehmite sol.Under violent stirring, will contain Mg (NO 3) 2Boehmite sol splash in the aqueous isopropanol of butyl (tetra) titanate, after adding, the pH value of solution is about 4.To this solution ultra-sonic dispersion 10 minutes, under violent stirring, slowly drip dehydrated alcohol in this solution then: the solution 20ml of water=1: 1, after adding, ultra-sonic dispersion 5 minutes obtains three transparent component colloidal sols.
(2) the three component colloidal sols that step (1) is obtained place 40 ℃ of-50 ℃ of water-baths to be incubated, and up to colloidal sol generation gelation, form the whole gel of even structure, this process 0.5-5 consuming time hour.
(3) the wet gel liquid nitrogen freezing that step (2) is obtained, lyophilize is 72 hours in vacuum freeze drier, to remove the interior solvent of wet gel that step (2) is obtained, makes it change xerogel into; The xerogel sample that takes out in the freeze drier is kept the volume of original wet gel, but loose porous.
(4) the xerogel sample is put into 120 ℃ of baking oven insulations after 1 hour, changed over to again in the retort furnace,, obtain mixed with titanium, aluminium, magnesium oxide presoma 500 ℃ of roastings 1 hour.
(5) mixed with titanium, aluminium, magnesium oxide presoma are placed retort furnace,, obtain by the stable aluminium titanates powder product of single MgO additive 1450 ℃ of calcinings 3 hours.
Measure through X ray powder crystal diffraction approach, be pure aluminium titanates phase with three products of above-mentioned technology institute's synthetic, inclusion-free is detected mutually.Table 1 provides these three Al of institute's synthetic 2 (1-x)Mg xTi 1+xO 5The nature parameters of sosoloid product.
Table 1Al 2 (1-x)Mg xTi 1+xO 5The nature parameters of sosoloid
Sample number The chemical constitution formula of sosoloid x Mass fraction/wt.% of MgO Unit cell parameters/the  of sosoloid Thermolytic rate/%
a b c
1 2 3 Al 1.92Mg 0.04Ti 1.04O 5 Al 1.86Mg 0.07Ti 1.07O 5 Al 1.73Mg 0.135Ti 1.135O 5 0.04 0.07 0.135 0.89 1.56 3.00 9.447 9.461 9.486 9.650 9.668 9.689 3.597 3.600 3.607 16.7 0.0 6.5
In order to contrast, table 2 provides the pure Al of the above-mentioned processing method of same use institute's synthetic 2TiO 5Nature parameters.
The pure Al of table 2 2TiO 5Nature parameters
Sample number Chemical constitution formula Al 2TiO 5Unit cell parameters/A Thermolytic rate/%
a b c
4 Al 2TiO 5 9.434 9.641 3.591 100
Following as can be known result from present embodiment:
Shown in sample 1, it is according to Al 2 (1-x)Mg xTi 1+xO 5The composition parameter x=0.04 batching of sosoloid uses technology of the present invention synthetic, and the mass fraction of its MgO is 0.89%.It has part A l after 1100 ℃ of thermolysiss of calcining down 10 hours of experience are tested 1.92Mg 0.04Ti 1.04O 5Sosoloid decomposes, and the thermolytic rate numerical value that adopts the crystal face selection system computing of above-mentioned alliance to go out this sosoloid is 16.7%.
Shown in sample 3, it is according to Al 2 (1-x)Mg xTi 1+xO 5The composition parameter x=0.135 batching of sosoloid uses technology of the present invention synthetic, and the mass fraction of its MgO is 3.00%.It has part A l after 1100 ℃ of thermolysiss of calcining down 10 hours of experience are tested 1.73Mg 0.135Ti 1.135O 5Sosoloid decomposes, and the thermolytic rate numerical value that calculates this sosoloid is 6.5%, and the mass fraction that the thermostability of this sample is better than MgO is 0.89% sample 1.
Shown in sample 2, it is according to Al 2 (1-x)Mg xTi 1+xO 5The composition parameter x=0.07 batching of sosoloid uses technology of the present invention synthetic, and the mass fraction of its MgO is 1.56%.It still is pure Al after 1100 ℃ of thermolysiss of calcining down 10 hours of experience are tested 1.86Mg 0.07Ti 1.07O 5Sosoloid is detected without any the sosoloid degradation production, and promptly the thermolytic rate of this sosoloid is 0.Under transmission electron microscope, as seen, experience the forward and backward Al of thermolysis 1.86Mg 0.07Ti 1.07O 5The particle diameter of sosoloid sample and form all do not change.
Shown in sample 4, it is according to pure Al 2TiO 5Batching (the special Al that also this sample can be regarded as a composition parameter x=0 2 (1-x)Mg xTi 1+xO 5Sosoloid), the mass fraction of its MgO is 0%, uses technology of the present invention synthetic equally.Synthetic product is pure Al 2TiO 5After 1100 ℃ of thermolysiss of calcining down 10 hours of experience were tested, synthetic product was decomposed into α-Al fully 2O 3And rutile, that is: its thermolytic rate numerical value is 100%.
As can be seen, use synthesis technique of the present invention, according to Al 2 (1-x)Mg xTi 1+xO 5The composition parameter x of sosoloid is respectively 0.04,0.07,0.135 and prepares burden, and prepares three Al respectively 2 (1-x)Mg xTi 1+xO 5Sosoloid product, their thermostability are all far above pure aluminium titanates.After experiencing 1100 ℃ of thermolysis tests, three samples are principal crystalline phase with the aluminium titanates still all, that is: their thermolytic rate is all little, and that wherein thermolytic rate is minimum is Al 1.86Mg 0.07Ti 1.07O 5(composition parameter x=0.07), its thermolytic rate are zero.In bibliographical information before this, the thermolytic rate of the aluminum titanate sample of single interpolation MgO never reaches this level, only just makes the thermolytic rate of aluminium titanates drop to zero with MgO and second kind of compound use of additive the time.
As can be seen from Table 1, three Al 2 (1-x)Mg xTi 1+xO 5The unit cell parameters a of sosoloid product, b, c are bordering on linearly with the increase of the composition parameter x of sosoloid respectively and increase, that is: be bordering on linearly with the increase of the addition of MgO to increase.This and existing document match to the report of this correlationship.But the present invention finds, at Al 2 (1-x)Mg xTi 1+xO 5The size of the unit cell parameters c of the addition of MgO and sosoloid is to the restricting relation aspect of the thermostability of sosoloid in the sosoloid, and the certain law warning that existing document provides is not exclusively to be suitable for.The regularity about these restricting relations that existing document provides is warned and was mentioned in front, and they are: the amplification of the unit cell parameters c of aluminium titanates is big more, and aluminium titanates is just stable more; Al 2 (1-x)Mg xTi 1+xO 5The thermostability of sosoloid increases with the x value and improves.
Result with present embodiment illustrates Al below 2 (1-x)Mg xTi 1+xO 5The addition of MgO and the unit cell parameters c value and the Al of sosoloid in the sosoloid 2 (1-x)Mg xTi 1+xO 5Relation between the thermostability of sosoloid.When only comparing with sample 1 with the sample 3 of present embodiment, the addition of the MgO of sample 3 and its unit cell parameters c value are all greater than the respective value of sample 1, and the thermolytic rate of sample 3 is starkly lower than sample 1, the thermostability that is sample 3 is better than sample 1, therefore, for these two samples of present embodiment, the size of the unit cell parameters c value of the addition of MgO and sosoloid is above-mentioned regular warning of deferring to prior art with the correlationship between the thermostability of sosoloid.But, when comparing with sample 3 and sample 2, or sample 1, sample 2, sample 3 counted when considering in the lump, it is just no longer suitable that prior art above-mentioned regular warned: the MgO addition of sample 2 be approximately sample 3 the MgO addition 1/2, its unit cell parameters c value is less than the unit cell parameters c value of sample 3, but its thermolytic rate is zero, is starkly lower than sample 3, and promptly the thermostability of sample 2 is better than sample 3.Therefore, from the result of present embodiment as can be seen, in order to improve Al 2 (1-x)Mg xTi 1+xO 5The thermostability of sosoloid not necessarily will rely on the addition that improves MgO greatly, also not necessarily requires the synthetic Al of institute 2 (1-x)Mg xTi 1+xO 5Sosoloid has high unit cell parameters c value.Using Al 2 (1-x)Mg xTi 1+xO 5In the following scope of the adding proportion of the interior MgO of the sosoloid that the composition parameter x of sosoloid expresses, promptly in the scope of 0.04≤x≤0.135, form parameter value according to the centre and fill a prescription, promptly adopt composition parameter x=0.07 to fill a prescription, use synthesis technique of the present invention, the Al that synthesizes 1.86Mg 0.07Ti 1.07O 5The unit cell parameters c value of sosoloid (being sample 2) occupy between the c value of two end member things, but after 10 hours thermolysis of 1100 ℃ of insulations of experience test, this sample still is pure aluminium titanates crystalline phase, α-Al do not occur 2O 3And rutile TiO 2, the thermolytic rate that shows this sample is zero, obviously is better than two end member things, shows good thermostability.The presentation of results of present embodiment, technology of the present invention have reached the purpose of thermostability of the aluminium titanates of the single interpolation of obvious raising MgO at the x=0.07 place.Therefore, the present invention embodies certain uniqueness.
The test-results of present embodiment shows, in the building-up process of sample 2, be made up of uniform spheres mixed with titanium, aluminium, magnesium oxide presoma that step (4) obtains, the granularity of spherolite is 0.1-0.2 μ m, and the X ray diffracting spectrum of this mixed oxide presoma is the amorphousness feature.Sampling is respectively calcined under differing temps from this mixed oxide presoma, and calcination time is fixed as 2h, and the production rate of AMT sosoloid awards table 3 in the calcinate of each temperature.From tabular data as seen, for mixed with titanium, aluminium, the magnesium oxide presoma with this composition, behind calcining 2h under 1250 ℃, it is the product of principal crystalline phase that this presoma has changed into AMT.
The relation of the production rate of table 3 calcining temperature and AMT sosoloid
Calcining temperature/℃ 1150 1200 1250
Production rate/% of AMT 8.3 30.6 87.0
In conjunction with present embodiment, for whether in strict accordance with Al 2 (1-x)Mg xTi 1+xO 5The stoicheiometry of sosoloid quantitatively uses the initiator of titanium, aluminium, three kinds of components of magnesium, may produce which kind of influence to the character of institute's synthetic aluminium titanates product and test, and found that, departs from Al 2 (1-x)Mg xTi 1+xO 5The stoicheiometry of sosoloid has significant adverse the sosoloid of good thermal stability in acquisition.This test is based on the sample 3 (Al of this sample of present embodiment 2 (1-x)Mg xTi 1+xO 5The x value of sosoloid is 0.135, and the MgO add-on is 3.00wt%), contrasted at the same 3.00wt%MgO of adding, but adopted different TiO 2: Al 2O 3: MgO stoichiometric ratio batching, when using processing step of the present invention to synthesize equally, the thermostability of the different aluminum titanate sample that obtained.Wherein, the amount that sample 5 equates according to the mole number with the magnesium that adds is reduced the consumption of aluminium colloidal sol, makes synthetics have Al (2-0.135)Mg 0.135TiO (5-0.135/2)Composition; Sample 6 is according to Al 2TiO 5Composition batching, and the MgO of 3wt% is additionally added to wherein.Table 4 provides the result of this simultaneous test.As can be seen from Table 4, in the sample of related three MgO that contain 3.00wt% equally, with in strict accordance with Al 2 (1-x)Mg xTi 1+xO 5The thermostability of the sample 3 of the chemical constitution batching of sosoloid is best; Sample 5 is according to having reduced the consumption of aluminium with the mode of the mole numbers such as magnesium that added, and its stoicheiometry has departed from Al 2 (1-x)Mg xTi 1+xO 5The stoichiometric relation of sosoloid makes its thermostability be worse than sample 3; Sample 6 is equivalent to additionally add MgO to Al 2TiO 5In, its stoicheiometry has departed from Al relatively more seriously 2 (1-x)Mg xTi 1+xO 5The stoichiometric relation of sosoloid, its thermostability is poorer.This comparative test result explanation, the present invention is in strict accordance with Al 2 (1-x)Mg xTi 1+xO 5The stoicheiometry of sosoloid quantitatively uses the initiator of titanium, aluminium, three kinds of components of magnesium, and to finish the synthetic of sosoloid, this treatment process has positive effect for the thermally-stabilised ability that improves synthetics.Aspect the stoicheiometry of sample, what sample 6 herein coexisted that " technical background " part quoted from uses ready-made Al 2TiO 5Powder mixes with additives such as MgO, and the aluminium titanates that contains additive [Jiang Weihui etc., Journal of Inorganic Materials, 1999,14 (5): 801-805] for preparing through ball milling-drying-sample preparation-burn till is equal to.Therefore, the data of table 4 contrasts shows, from the stoicheiometry aspect, to synthetic Al 2TiO 5Extra mode of adding MgO should be to be unfavorable for synthesizing the aluminium titanates product with high stability in the powder.
Table 4 has different Ti O 2: Al 2O 3: the thermolytic rate of the synthetic aluminium titanates product of MgO stoichiometric ratio
Sample number TiO 2∶Al 2O 3: the proportioning foundation of MgO I AT (101) I T (110) Thermolytic rate/%
3 5 6 Al 2(1-0.135)Mg 0.135Ti 1.135O 5Al (2-0.135)Mg 0.135TiO (5-0.135/2)0.135MgO+Al 2TiO 5 100 100 100 7 33 52 6.5 24.8 34.2
Embodiment 2
A kind of preparation of the present invention contains the technology of the magnesian aluminium titanates powder of single additive, its raw material and processing step are similar to embodiment 1, but, the composition parameter x of selected sosoloid is 0.06, step (4) was calcined 2 hours down at 1650 ℃ by mixed with titanium, aluminium, magnesium oxide presoma that the roasting xerogel obtained, obtain by the stable aluminium titanates powder product of single MgO additive.After making 1100 ℃ of this aluminium titanates powder experience calcine 10 hours thermolysis test down, its thermolytic rate is 0.
Embodiment 3
A kind of preparation of the present invention contains the technology of the magnesian aluminium titanates powder of single additive, its raw material and processing step are similar to embodiment 1, but, the composition parameter x of selected sosoloid is 0.08, step (4) was calcined 3 hours down at 1350 ℃ by mixed with titanium, aluminium, magnesium oxide presoma that the roasting xerogel obtained, obtain by the stable aluminium titanates powder product of single MgO additive.After making 1100 ℃ of this aluminium titanates powder experience calcine 10 hours thermolysis test down, its thermolytic rate is 0.
Embodiment 4
A kind of preparation of the present invention contains the technology of the magnesian aluminium titanates block of single additive, its raw material and processing step are similar to embodiment 1, but, fixedly sosoloid composition parameter x is 0.07, the temperature of step (4) roasting xerogel is 1000 ℃, the resulting mixed with titanium of roasting xerogel, aluminium, magnesium oxide presoma are ground, then the gained pressed by powder is become piece, this block is placed retort furnace, 1450 ℃ of calcinings 2 hours, obtain by the stable aluminium titanates porcelain piece of single MgO additive.After making 1100 ℃ of this aluminium titanates porcelain piece experience calcine 10 hours thermolysis test down, the thermolytic rate of sample is 0.

Claims (6)

1、一种用溶胶-凝胶法合成具有良好热稳定性的钛酸铝的工艺，其特征在于有如下工艺步骤：1. A process for synthesizing aluminum titanate with good thermal stability by a sol-gel method, characterized in that it has the following process steps: (1)按照TiO2∶Al2O3∶MgO＝(1+x)∶(1-x)∶x的摩尔比例配料，式中，0.04＜x＜0.135，也就是将钛酸丁酯的异丙醇溶液、勃姆石溶胶、Mg(NO3)2·6H2O按照Al2(1-x)MgxTi1+xO5固溶体的组成配料，结合超声波的分散作用，在螯合剂的存在下进行反应，得到三组分溶胶；(1) Dosing according to the molar ratio of TiO 2 : Al 2 O 3 : MgO=(1+x):(1-x):x, where 0.04<x<0.135, that is, the isobutyl titanate Propanol solution, boehmite sol, Mg(NO 3 ) 2 6H 2 O are formulated according to the composition of Al 2(1-x) Mg x Ti 1+x O 5 solid solution, combined with the dispersion of ultrasonic waves, the chelating agent Reaction is carried out under the existence, obtains three-component sol; (2)将步骤(1)所获的三组分溶胶置于水浴中保温，使溶胶发生凝胶化，转变为湿凝胶；(2) placing the three-component sol obtained in step (1) in a water bath for heat preservation, so that the sol is gelled and transformed into a wet gel; (3)从步骤(2)所获的湿凝胶中脱除溶剂，将其转变为干凝胶；(3) removing the solvent from the wet gel obtained in step (2), converting it into a dry gel; (4)在400℃-1000℃下焙烧由步骤(3)所获的干凝胶，得到混合钛、铝、镁氧化物前驱体；(4) Calcining the xerogel obtained in step (3) at 400°C-1000°C to obtain a mixed titanium, aluminum, and magnesium oxide precursor; (5)在1250℃-1650℃下煅烧步骤(4)所获的混合钛、铝、镁氧化物前驱体，得到由单一MgO添加剂稳定的钛酸铝粉体，即Al2(1-x)MgxTi1+xO5固溶体粉体。(5) Calcining the mixed titanium, aluminum, and magnesium oxide precursors obtained in step (4) at 1250°C-1650°C to obtain aluminum titanate powder stabilized by a single MgO additive, that is, Al 2(1-x) Mg x Ti 1+x O 5 solid solution powder. 2、根据权利要求1所述的合成具有良好热稳定性的钛酸铝的工艺，其特征在于所说的钛酸铝的热稳定性不是单调地随组成参数x的增大而提高，所说的具有如下组成的钛酸铝在1100℃保温10小时后的分解率为0：2. The process for synthesizing aluminum titanate with good thermal stability according to claim 1, characterized in that the thermal stability of said aluminum titanate does not increase monotonously with the increase of the composition parameter x, said The decomposition rate of aluminum titanate with the following composition is 0 after being kept at 1100°C for 10 hours: Al2(1-x)MgxTi1+xO5 Al 2(1-x) Mg x Ti 1+x O 5 式中，组成参数x为0.06-0.08。In the formula, the composition parameter x is 0.06-0.08. 3、根据权利要求1或2所述的合成工艺，对步骤(5)作如下的改变：研磨由步骤(4)所获的混合钛、铝、镁氧化物前驱体，将磨细后的粉体压制成块，在1250℃-1650℃下煅烧，得到由单一MgO添加剂稳定的钛酸铝瓷块。3. According to the synthesis process described in claim 1 or 2, step (5) is changed as follows: grind the mixed titanium, aluminum, and magnesium oxide precursors obtained in step (4), and grind the powder The body is pressed into a block and calcined at 1250°C-1650°C to obtain an aluminum titanate ceramic block stabilized by a single MgO additive. 4、根据权利要求1或2所述的合成工艺，其特征在于所说的步骤(1)在合成钛、铝、镁三组分溶胶时，加入乙酰丙酮和冰醋酸作为螯合剂，合成过程在10℃-30℃的室温下进行，所形成的溶胶的pH值为3.5-4.5，不对溶胶的pH值作任何调整。4, according to claim 1 or 2 described synthetic techniques, it is characterized in that said step (1) when synthesizing titanium, aluminum, magnesium three-component sol, add acetylacetone and glacial acetic acid as chelating agent, synthetic process is in It is carried out at room temperature of 10°C-30°C, and the pH value of the formed sol is 3.5-4.5, and the pH value of the sol is not adjusted in any way. 5、根据权利要求1或2所述的合成工艺，其特征在于所说的步骤(2)的保温水浴的温度为40℃-50℃，保温后得到的湿凝胶为完整块状。5. The synthesis process according to claim 1 or 2, characterized in that the temperature of the heat preservation water bath in the step (2) is 40°C-50°C, and the wet gel obtained after heat preservation is a complete block. 6、根据权利要求1或2所述的合成工艺，其特征在于所说的步骤(3)从湿凝胶中脱除溶剂、将湿凝胶转变为干凝胶时，先用液氮使湿凝胶整体快速冻结，然后使用真空冷冻干燥方式从湿凝胶冻块中脱除溶剂。6. The synthesis process according to claim 1 or 2, characterized in that said step (3) removes the solvent from the wet gel, and when the wet gel is converted into a dry gel, the wet gel is first made wet with liquid nitrogen. The gel mass is flash-frozen, and the solvent is removed from the wet gel block using vacuum freeze-drying.
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