CN1762900A - Process for synthesizing heat-stable aluminium titanate - Google Patents

Process for synthesizing heat-stable aluminium titanate Download PDF

Info

Publication number
CN1762900A
CN1762900A CN 200410040856 CN200410040856A CN1762900A CN 1762900 A CN1762900 A CN 1762900A CN 200410040856 CN200410040856 CN 200410040856 CN 200410040856 A CN200410040856 A CN 200410040856A CN 1762900 A CN1762900 A CN 1762900A
Authority
CN
China
Prior art keywords
aluminium titanates
aluminium
sosoloid
mgo
additive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 200410040856
Other languages
Chinese (zh)
Other versions
CN100336774C (en
Inventor
张其春
叶巧明
林金辉
常嗣和
刘菁
宋继芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu Univeristy of Technology
Original Assignee
Chengdu Univeristy of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chengdu Univeristy of Technology filed Critical Chengdu Univeristy of Technology
Priority to CNB2004100408568A priority Critical patent/CN100336774C/en
Publication of CN1762900A publication Critical patent/CN1762900A/en
Application granted granted Critical
Publication of CN100336774C publication Critical patent/CN100336774C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The present invention relates to technological process of synthesizing aluminum titanate solid solution with high heat stability, and aims at improving the heat stability of aluminum titanate solid solution containing MgO as single additive. The technological process includes the following steps: synthesizing sol containing Ti, Al and Mg components with titanium alkoxide, aluminum sol and magnesium salt as material; converting the sol into gel; eliminating solvent from wet gel; roasting to obtain mixed Ti, Al and Mg oxide precursor, and calcining to obtain Al2(1-x)MgxTi1+xO5 solid solution as stable aluminum titanate solid solution containing MgO. It is determined that under the condition of lower MgO content or x value in 0.06-0.08, the Al2(1-x)MgxTi1+xO5 solid solution has zero thermal decomposition rate.

Description

A kind of processing method of synthetic thermostability aluminium titanates
Technical field
The present invention relates to the processing method of synthetic aluminium titanates, particularly synthesize processing method, be intended to improve the thermostability of the aluminium titanates that contains single MgO additive 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 specific 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 understanding (1) and understanding (3) that these above-mentioned prior aries are stablized the regularity of 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 processing method of synthetic aluminium titanates, contain the thermostability of the aluminium titanates of single additive MgO with improvement.
Summary of the invention
The synthetic processing method 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, the colloidal sol-conversion colloidal sol of process synthesizing titanium-containing, aluminium, magnesium three components are that gel-wet gel precipitation thinner-roasting xerogel obtains TiO 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, can help in step (1), to make 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, generate the even colloidal sol of titaniferous, aluminium, three kinds of components of magnesium.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 synthetic process 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, at single interpolation MgO, use under the situation of lower MgO addition, obtained thermolytic rate and be zero Al 2 (1-x)Mg xTi 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 processing method 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, for improving Al by the addition that improves single MgO additive 2 (1-x)Mg xTi 1+xO 5The above-mentioned prior art of the thermostability of sosoloid exists outside the still not satisfied problem except the thermostability of formed aluminium titanates, with the increase 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 0.06-0.08, 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, two or more powder of existing employing is by the synthetic Al of solid-solid state reaction 2 (1-x)Mg xTi 1+xO 5The china-clay method synthetic technology of sosoloid, because 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 titaniferous, aluminium, the even colloidal sol of three kinds of components of magnesium, 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.
EXAMPLE l
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 processing method 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 1 Al 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/ 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 preparing 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 preparing 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 preparing 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 preparing 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, processing method of the present invention have reached the purpose of the thermostability of the aluminium titanates that improves single interpolation MgO.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, and the influence of the character of institute's synthetic aluminium titanates product is tested, and finds to depart from Al 2 (1-x)Mg xTi 1+xO 5The stoicheiometry of sosoloid is a significant adverse to the thermostability of improving sosoloid.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 5 Al (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 (8)

1, a kind of synthetic processing method by the stable aluminium titanates of single MgO additive is characterized in that the composition expression formula of said aluminium titanates is:
Al 2(1-x)Mg xTi 1+xO 5
In the formula: 0.04＜x＜0.135.
2, synthetic processing method by the stable aluminium titanates of single MgO additive according to claim 1 is characterized in that the composition expression formula of said aluminium titanates is:
Al 2(1-x)Mg xTi 1+xO 5
In the formula, composition parameter x is 0.06-0.08.
3, synthetic processing method by the stable aluminium titanates of single MgO additive according to claim 1 is characterized in that following processing step is arranged:
(1) with butyl (tetra) titanate (the aqueous isopropanol form with butyl (tetra) titanate is used), aluminium colloidal sol, Mg (NO 3) 26H 2O is according to TiO 2: Al 2O 3: the molar ratio batching of MgO=(1+x): (1-x): x, 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 component colloidal sols;
(2) the three component colloidal sols that step (1) is obtained place water-bath to be incubated, and make colloidal sol generation gelation, change wet gel into;
(3) from the wet gel that step (2) is obtained, remove solvent, change it into xerogel;
(4) 400 ℃ of-1000 ℃ of following roastings by the xerogel that step (3) is obtained, obtain 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 powder of single MgO additive, i.e. Al 2 (1-x)Mg xTi 1+xO 5Solid solution powder.
4, synthetic processing method according to claim 3 by the stable aluminium titanates of single MgO additive, step (5) is done following change: grind the mixed with titanium, aluminium, the magnesium oxide presoma that are obtained by step (4), pressed by powder after levigate is become piece, 1250 ℃-1650 ℃ calcinings down, obtain by the stable aluminium titanates porcelain piece of single MgO additive.
5, according to claim 3 or 4 described synthetic methods, it is characterized in that said step (1) is when the colloidal sol of synthesizing titanium-containing, aluminium, magnesium three components, add methyl ethyl diketone and Glacial acetic acid as sequestrant, building-up process is carried out under 10 ℃-30 ℃ room temperature, the pH value of formed colloidal sol is 3.5-4.5, the pH value of colloidal sol is not done any adjustment.
6, according to claim 3 or 4 described synthetic methods, the temperature that it is characterized in that the insulation water-bath of said step (2) is 40 ℃-50 ℃, and the wet gel that obtains after the insulation is complete bulk.
7, according to claim 3 or 4 described synthetic methods, it is characterized in that said step (3) from wet gel, remove solvent, when changing wet gel into xerogel, make the whole quick freezing of wet gel with liquid nitrogen earlier, use the vacuum lyophilization mode to freeze then and remove solvent the piece from wet gel.
8, according to claim 3 or 4 described synthetic methods, it is characterized in that said by the stable aluminium titanates of single MgO additive after through 1100 ℃, 10 hours thermolysis test, its rate of decomposition is 0.
CNB2004100408568A 2004-10-18 2004-10-18 Process for synthesizing heat-stable aluminium titanate Expired - Fee Related CN100336774C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2004100408568A CN100336774C (en) 2004-10-18 2004-10-18 Process for synthesizing heat-stable aluminium titanate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2004100408568A CN100336774C (en) 2004-10-18 2004-10-18 Process for synthesizing heat-stable aluminium titanate

Publications (2)

Publication Number Publication Date
CN1762900A true CN1762900A (en) 2006-04-26
CN100336774C CN100336774C (en) 2007-09-12

Family

ID=36747259

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004100408568A Expired - Fee Related CN100336774C (en) 2004-10-18 2004-10-18 Process for synthesizing heat-stable aluminium titanate

Country Status (1)

Country Link
CN (1) CN100336774C (en)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100569697C (en) * 2007-10-30 2009-12-16 景德镇陶瓷学院 A kind of method that adopts sol-gel technology to prepare aluminium titanate film
WO2011002536A2 (en) * 2009-04-08 2011-01-06 Energ2, Inc. Manufacturing methods for the production of carbon materials
WO2011008938A1 (en) * 2009-07-15 2011-01-20 E.I. Du Pont De Nemours And Company Aluminium magnesium titanate composite ceramics
US8709971B2 (en) 2005-11-21 2014-04-29 University Of Washington Activated carbon cryogels and related methods
US8797717B2 (en) 2006-11-15 2014-08-05 University Of Washington Electrodes and electric double layer capacitance devices comprising an activated carbon cryogel
US8916296B2 (en) 2010-03-12 2014-12-23 Energ2 Technologies, Inc. Mesoporous carbon materials comprising bifunctional catalysts
US9112230B2 (en) 2009-07-01 2015-08-18 Basf Se Ultrapure synthetic carbon materials
US9269502B2 (en) 2010-12-28 2016-02-23 Basf Se Carbon materials comprising enhanced electrochemical properties
US9412523B2 (en) 2010-09-30 2016-08-09 Basf Se Enhanced packing of energy storage particles
US9409777B2 (en) 2012-02-09 2016-08-09 Basf Se Preparation of polymeric resins and carbon materials
CN107473735A (en) * 2017-09-29 2017-12-15 无锡特科精细陶瓷有限公司 A kind of preparation method of alumina titanate ceramics
CN107500757A (en) * 2017-09-29 2017-12-22 无锡特科精细陶瓷有限公司 A kind of preparation method for being densified alumina titanate ceramics
CN108147451A (en) * 2017-12-29 2018-06-12 陕西瑞科新材料股份有限公司 A kind of preparation method of aluminium titanates for precious metal catalyst agent carrier
KR20180113187A (en) * 2015-08-28 2018-10-15 에너지2 테크놀로지스, 인코포레이티드 Novel materials exhibiting extremely durable lithium intercalation and methods for their preparation
US10195583B2 (en) 2013-11-05 2019-02-05 Group 14 Technologies, Inc. Carbon-based compositions with highly efficient volumetric gas sorption
US10454103B2 (en) 2013-03-14 2019-10-22 Group14 Technologies, Inc. Composite carbon materials comprising lithium alloying electrochemical modifiers
US10490358B2 (en) 2011-04-15 2019-11-26 Basf Se Flow ultracapacitor
US10522836B2 (en) 2011-06-03 2019-12-31 Basf Se Carbon-lead blends for use in hybrid energy storage devices
US10590277B2 (en) 2014-03-14 2020-03-17 Group14 Technologies, Inc. Methods for sol-gel polymerization in absence of solvent and creation of tunable carbon structure from same
US10763501B2 (en) 2015-08-14 2020-09-01 Group14 Technologies, Inc. Nano-featured porous silicon materials
CN112174690A (en) * 2020-10-12 2021-01-05 南京理工大学 Method for preparing hollow aluminum titanate fiber by using kapok fiber
US11174167B1 (en) 2020-08-18 2021-11-16 Group14 Technologies, Inc. Silicon carbon composites comprising ultra low Z
US11335903B2 (en) 2020-08-18 2022-05-17 Group14 Technologies, Inc. Highly efficient manufacturing of silicon-carbon composites materials comprising ultra low z
US11611071B2 (en) 2017-03-09 2023-03-21 Group14 Technologies, Inc. Decomposition of silicon-containing precursors on porous scaffold materials
US11639292B2 (en) 2020-08-18 2023-05-02 Group14 Technologies, Inc. Particulate composite materials

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3096814B1 (en) * 1999-11-08 2000-10-10 勉 福田 Method for producing aluminum titanate sintered body
JP3489030B1 (en) * 2002-04-26 2004-01-19 勉 福田 Method for producing aluminum titanate-based sintered body
JP4766645B2 (en) * 2003-02-18 2011-09-07 株式会社Ｌｉｘｉｌ Damping member

Cited By (62)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8709971B2 (en) 2005-11-21 2014-04-29 University Of Washington Activated carbon cryogels and related methods
US10600581B2 (en) 2006-11-15 2020-03-24 Basf Se Electric double layer capacitance device
US8797717B2 (en) 2006-11-15 2014-08-05 University Of Washington Electrodes and electric double layer capacitance devices comprising an activated carbon cryogel
US10141122B2 (en) 2006-11-15 2018-11-27 Energ2, Inc. Electric double layer capacitance device
CN100569697C (en) * 2007-10-30 2009-12-16 景德镇陶瓷学院 A kind of method that adopts sol-gel technology to prepare aluminium titanate film
US8580870B2 (en) 2009-04-08 2013-11-12 Energ2 Technologies, Inc. Manufacturing methods for the production of carbon materials
WO2011002536A3 (en) * 2009-04-08 2013-09-06 Energ2, Inc. Manufacturing methods for the production of carbon materials
US8906978B2 (en) 2009-04-08 2014-12-09 Energ2 Technologies, Inc. Manufacturing methods for the production of carbon materials
WO2011002536A2 (en) * 2009-04-08 2011-01-06 Energ2, Inc. Manufacturing methods for the production of carbon materials
US9112230B2 (en) 2009-07-01 2015-08-18 Basf Se Ultrapure synthetic carbon materials
US9580321B2 (en) 2009-07-01 2017-02-28 Basf Se Ultrapure synthetic carbon materials
US10287170B2 (en) 2009-07-01 2019-05-14 Basf Se Ultrapure synthetic carbon materials
WO2011008938A1 (en) * 2009-07-15 2011-01-20 E.I. Du Pont De Nemours And Company Aluminium magnesium titanate composite ceramics
US8916296B2 (en) 2010-03-12 2014-12-23 Energ2 Technologies, Inc. Mesoporous carbon materials comprising bifunctional catalysts
US9680159B2 (en) 2010-03-12 2017-06-13 Basf Se Mesoporous carbon materials comprising bifunctional catalysts
US9412523B2 (en) 2010-09-30 2016-08-09 Basf Se Enhanced packing of energy storage particles
US9985289B2 (en) 2010-09-30 2018-05-29 Basf Se Enhanced packing of energy storage particles
US9269502B2 (en) 2010-12-28 2016-02-23 Basf Se Carbon materials comprising enhanced electrochemical properties
US10490358B2 (en) 2011-04-15 2019-11-26 Basf Se Flow ultracapacitor
US10522836B2 (en) 2011-06-03 2019-12-31 Basf Se Carbon-lead blends for use in hybrid energy storage devices
US11725074B2 (en) 2012-02-09 2023-08-15 Group 14 Technologies, Inc. Preparation of polymeric resins and carbon materials
US11401363B2 (en) 2012-02-09 2022-08-02 Basf Se Preparation of polymeric resins and carbon materials
US11732079B2 (en) 2012-02-09 2023-08-22 Group14 Technologies, Inc. Preparation of polymeric resins and carbon materials
US9409777B2 (en) 2012-02-09 2016-08-09 Basf Se Preparation of polymeric resins and carbon materials
US11718701B2 (en) 2012-02-09 2023-08-08 Group14 Technologies, Inc. Preparation of polymeric resins and carbon materials
US10714744B2 (en) 2013-03-14 2020-07-14 Group14 Technologies, Inc. Composite carbon materials comprising lithium alloying electrochemical modifiers
US11495793B2 (en) 2013-03-14 2022-11-08 Group14 Technologies, Inc. Composite carbon materials comprising lithium alloying electrochemical modifiers
US10454103B2 (en) 2013-03-14 2019-10-22 Group14 Technologies, Inc. Composite carbon materials comprising lithium alloying electrochemical modifiers
US10814304B2 (en) 2013-11-05 2020-10-27 Group14 Technologies, Inc. Carbon-based compositions with highly efficient volumetric gas sorption
US10195583B2 (en) 2013-11-05 2019-02-05 Group 14 Technologies, Inc. Carbon-based compositions with highly efficient volumetric gas sorption
US11707728B2 (en) 2013-11-05 2023-07-25 Group14 Technologies, Inc. Carbon-based compositions with highly efficient volumetric gas sorption
US10590277B2 (en) 2014-03-14 2020-03-17 Group14 Technologies, Inc. Methods for sol-gel polymerization in absence of solvent and creation of tunable carbon structure from same
US11661517B2 (en) 2014-03-14 2023-05-30 Group14 Technologies, Inc. Methods for sol-gel polymerization in absence of solvent and creation of tunable carbon structure from same
US10711140B2 (en) 2014-03-14 2020-07-14 Group14 Technologies, Inc. Methods for sol-gel polymerization in absence of solvent and creation of tunable carbon structure from same
US11611073B2 (en) 2015-08-14 2023-03-21 Group14 Technologies, Inc. Composites of porous nano-featured silicon materials and carbon materials
US11942630B2 (en) 2015-08-14 2024-03-26 Group14 Technologies, Inc. Nano-featured porous silicon materials
US10763501B2 (en) 2015-08-14 2020-09-01 Group14 Technologies, Inc. Nano-featured porous silicon materials
US11437621B2 (en) 2015-08-28 2022-09-06 Group14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
US10147950B2 (en) 2015-08-28 2018-12-04 Group 14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
KR20180113187A (en) * 2015-08-28 2018-10-15 에너지2 테크놀로지스, 인코포레이티드 Novel materials exhibiting extremely durable lithium intercalation and methods for their preparation
US10923722B2 (en) 2015-08-28 2021-02-16 Group14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
US10784512B2 (en) 2015-08-28 2020-09-22 Group14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
US11646419B2 (en) 2015-08-28 2023-05-09 Group 14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
US10756347B2 (en) 2015-08-28 2020-08-25 Group14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
US10608254B2 (en) 2015-08-28 2020-03-31 Group14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
KR102528934B1 (en) 2015-08-28 2023-05-08 그룹14 테크놀로지스, 인코포레이티드 Novel material exhibiting extremely durable lithium intercalation and its preparation method
US11495798B1 (en) 2015-08-28 2022-11-08 Group14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
US11611071B2 (en) 2017-03-09 2023-03-21 Group14 Technologies, Inc. Decomposition of silicon-containing precursors on porous scaffold materials
CN107473735B (en) * 2017-09-29 2019-08-02 无锡特科精细陶瓷有限公司 A kind of preparation method of alumina titanate ceramics
CN107473735A (en) * 2017-09-29 2017-12-15 无锡特科精细陶瓷有限公司 A kind of preparation method of alumina titanate ceramics
CN107500757A (en) * 2017-09-29 2017-12-22 无锡特科精细陶瓷有限公司 A kind of preparation method for being densified alumina titanate ceramics
CN107500757B (en) * 2017-09-29 2019-08-02 无锡特科精细陶瓷有限公司 A kind of preparation method densifying alumina titanate ceramics
CN108147451A (en) * 2017-12-29 2018-06-12 陕西瑞科新材料股份有限公司 A kind of preparation method of aluminium titanates for precious metal catalyst agent carrier
CN108147451B (en) * 2017-12-29 2020-03-20 陕西瑞科新材料股份有限公司 Preparation method of aluminum titanate for noble metal catalyst carrier
US11611070B2 (en) 2020-08-18 2023-03-21 Group14 Technologies, Inc. Highly efficient manufacturing of silicon-carbon composites materials comprising ultra low Z
US11335903B2 (en) 2020-08-18 2022-05-17 Group14 Technologies, Inc. Highly efficient manufacturing of silicon-carbon composites materials comprising ultra low z
US11174167B1 (en) 2020-08-18 2021-11-16 Group14 Technologies, Inc. Silicon carbon composites comprising ultra low Z
US11639292B2 (en) 2020-08-18 2023-05-02 Group14 Technologies, Inc. Particulate composite materials
US11492262B2 (en) 2020-08-18 2022-11-08 Group14Technologies, Inc. Silicon carbon composites comprising ultra low Z
US11804591B2 (en) 2020-08-18 2023-10-31 Group14 Technologies, Inc. Highly efficient manufacturing of silicon-carbon composite materials comprising ultra low Z
US11498838B2 (en) 2020-08-18 2022-11-15 Group14 Technologies, Inc. Silicon carbon composites comprising ultra low z
CN112174690A (en) * 2020-10-12 2021-01-05 南京理工大学 Method for preparing hollow aluminum titanate fiber by using kapok fiber

Also Published As

Publication number Publication date
CN100336774C (en) 2007-09-12

Similar Documents

Publication Publication Date Title
CN100336774C (en) Process for synthesizing heat-stable aluminium titanate
Landi et al. Alkali-bonded ceramics with hierarchical tailored porosity
TWI424958B (en) Lsx type zeolite having a controlled particle size distribution
CN1946653A (en) Magnesium aluminum titanate crystal structure and method for producing same
Feng et al. Novel facile nonaqueous precipitation in-situ synthesis of mullite whisker skeleton porous materials
Sarkar et al. Nanostructured Al 2 O 3–ZrO 2 composite synthesized by sol–gel technique: powder processing and microstructure
Dilsiz et al. Study of sol–gel processing for fabrication of low density alumina microspheres
RU2536593C1 (en) Method of producing zirconium dioxide-based ceramic for restoration dentistry
CN103570049A (en) Method for preparing completely dispersed alpha aluminum oxide nano particles
Li et al. Controlled synthesis of α-Al2O3 via the hydrothermal-pyrolysis method
CN1673173A (en) Nano crystal adding alumina ceramic material and its low temperature liquid phase sintering process
CN101700910B (en) Preparation method of spherical nanoscale niobium pentaoxide powder
Marocco et al. The multifarious aspects of the thermal conversion of Ba-exchanged zeolite A to monoclinic celsian
Wu et al. Influence of silica phase transformation on synthesis of cordierite ceramic
CN102476819A (en) Preparation method of nano alpha-alumina powder
Kozlova et al. On the Thermal Decomposition of Cerium (IV) Hydrogen Phosphate Ce (PO 4)(HPO 4) 0.5 (H 2 O) 0.5
Guo et al. Peptization mechanism of aluminum phosphate sol
Belyakov et al. Boehmite nanoparticles with different functional properties for preparing products with specific parameters
CN1472141A (en) Technology for preparing high-purity nano barium titanate powder
CN1272280C (en) Preparation method of niobium doped barium sodium titanate nano-powder
JP5925535B2 (en) Gallium-indium composite oxide powder
JP2002068829A (en) Porcelain and its manufacturing method
RU2713141C1 (en) Method of producing highly pure fine-crystal barium titanate
Li et al. The in-situ formation of Mg-Al hydrotalcite and its effect on the properties of MgO-bonded alumina castables
JP2000012308A (en) Manufacture of thermistor element

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee