CN104086201A - High-purity alumina fiber and preparation method thereof - Google Patents
High-purity alumina fiber and preparation method thereof Download PDFInfo
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- CN104086201A CN104086201A CN201410351742.9A CN201410351742A CN104086201A CN 104086201 A CN104086201 A CN 104086201A CN 201410351742 A CN201410351742 A CN 201410351742A CN 104086201 A CN104086201 A CN 104086201A
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Abstract
The invention discloses a preparation method of a high-purity alumina fiber. The alumina fiber takes anhydrous aluminium chloride and aluminium micro powder as raw materials and acetic acid or lactic acid as a stabilizer and a spinning auxiliary and is added with an oxide second phase (MgO, SiO2, Y2O3, ZrO2 and the like) with mass fraction of 0-2%, so that mechanical properties of the alumina fiber at room temperature and high temperature are improved. An alumina fibreboard is composed of alumina fibers, an inorganic binder, an organic binder and an additive in a mass ratio of (30-40) to (55-65) to (0-1) to (4-5). A preparation method of the alumina fibreboard is characterized by comprising the following steps: preparing colloid, carrying out centrifugal spinning, preparing alumina fibers, preparing a wet blank, carrying out high temperature treatment, and machining, so that the alumina fibreboard finished product is obtained. The high-purity alumina fiber product has excellent thermal insulation properties and mechanical properties, and an operating temperature is increased, so that an operating temperature range of a similar product is expanded.
Description
Technical field
The invention belongs to fire-resistant material heat insulation technology field, be specifically related to a kind of preparation method of high purity aluminium oxide fiber and the product making thereof.
Background technology
Sapphire whisker belongs to development situation of high-performance inorganic fibers, and its main component is α-Al
2o
3, there is the various ways such as long fibre, short fiber, whisker.Compare with steel fiber with carbon fiber, there is high strength, high-modulus, the premium properties such as high temperature resistant, also have good high-temperature oxidation resistance and electrical insulating property.Sapphire whisker good surface activity, is easy to compound with the body material such as metal, pottery; Also there is the advantages such as thermal conductivity is little, thermal expansivity is low, good thermal shock simultaneously; In addition, sapphire whisker raw materials cost is low and production technique is simple, has higher cost performance.
At present, commercial sapphire whisker mainly contains FP, the PRD-166 series that du pont company produces in the world, the Nextel series that Minnesota Mining and Manufacturing Company produces, the Saffil series that ICI company of Britain produces, the Altex series that Japanese Sumitomo company produces etc.These sapphire whiskers have important application in fields such as space flight and aviation, military project, high-performance sports equipment and high-temperature structural materials.
Due to Al
2o
3very high (the T of fusing point
m>2040 DEG C), and the viscosity of melt is very low, cannot prepare continuous sapphire whisker with traditional melt spinning method.1979, du pont company adopted slurry process to produce FP sapphire whisker the earliest, by α-Al
2o
3(diameter≤0.5 μ m) powder mixes under certain condition with aluminium chlorohydroxide and magnesium chloride, and adds dispersion agent, auxiliary rheological agents etc. to make the spun slurry of certain viscosity, and dry-spinning, after being dried, is sintered to the high temperature of 1800 DEG C, obtains α-Al
2o
3polycrystalline fibre, its alumina content is 99.9%.Young's modulus is 410GPa, and tensile strength is 1.55GPa.But step-down is answered in the inefficacy of this sapphire whisker, be only 0.4%, thereby application is restricted.SUMITOMO CHEMICAL chemical company adopts the legal production of pre-polymerization with Al
2o
3for main component, and contain B
2o
3, SiO
2polycrystalline alumina fiber.First aggregate under certain conditions poly-aluminium alkoxide compound with aluminum alkyls and water, be dissolved in organic solvent, then add silicon ester or silicoorganic compound, mixture is made can spunbond magma, through dry-spinning, obtains precursor fibre.In 600 DEG C of air, be cracked into the inorganic fibre that contains the component such as aluminum oxide and silicon oxide again, finally sintering more than 1000 DEG C, obtains the continuous alumina fiber of crystallite state of aggregation, and its diameter is in 10um left and right.Because precursor is linear polymer form, advantage is that spinning properties is good, easily obtains continuous fiber, and shortcoming is to adopt organic alkoxide, and production cost is higher.ICI company of Britain adopts fore-telling inside door method to produce Saffil sapphire whisker.First oxyacetic acid aluminium and water are mixed into aluminum salt solution, then mix with water soluble molecules, polysiloxane such as polyethylene oxides that make can spunbond magma, through spinning, be dried, sinter into alumina short fibre.Fiber is mainly δ-Al
2o
3phase, also has a small amount of α-Al
2o
3phase.Diameter, in 3um left and right, is mainly used as the reinforcement of metal-base composites.In addition, also have investigator to adopt matrix fiber pickling process to prepare sapphire whisker, this method adopts inorganic salt solution impregnation matrix fiber, removes matrix fiber and obtains ceramic fiber through sintering.Advantage is that technique is simple, can obtain complex-shaped sapphire whisker product.Shortcoming is that cost is higher and fiber quality is poor.
In addition, sol-gel method is a kind of novel method of preparing sapphire whisker, compare traditional scorification, have the following advantages: sintering temperature is approximately lower 400～500 DEG C than traditional method, product purity is high, good uniformity, crystal grain performance tiny and fiber is controlled, designability strong and product diversification, has become the main method of preparing sapphire whisker.Common sol-gel method needs following three steps:
(1) prepare colloidal sol according to raw material and suitable spin finish aid, and colloidal sol to have suitable viscosity and rheological property with
Just can spinning.
(2) adopt centrifugal spinning, method of electrostatic spinning or other spinning processes to obtain gelled fibre.
(3) formulate rational heat treating regime and obtain final sapphire whisker.
In high purity aluminium oxide fiber, alumina content will reach more than 95%, is more preferably more than 98%, preferably more than 99.5%.If alumina content is lower than 95%, Young's modulus and thermotolerance all can reduce.Published U.S. Patent number US 5,145,734 has described a kind of preparation method of high purity aluminium oxide continuous fibre.Its process is by the γ-Al of 1 part
2o
3it is 5% polyethylene oxide solution that micro mist (average particulate diameter is 0.02um) and 6 parts contain massfraction, add in the polymeric aluminum chlorides solution of 10 parts (massfraction of aluminum oxide is 23.5%), after mix and blend, concentrating under reduced pressure obtains the spinning solution that viscosity is 6500P.After thermal treatment in spinning, rare gas element, obtaining purity is 99.7%, α-Al that mean diameter is 5～24um
2o
3fiber.U.S. Patent number US 5,514,631 also provides a kind of similar preparation Al
2o
3the method of-5wt.%MgO fiber.Fiber is by discontinuous α-Al
2o
3phase and Spinel composition, average grain size is 0.2～0.4um, density can reach the more than 95% of theoretical value.Published U.S. Patent number US 4,101,615 provides a kind of Al
2o
3and Al
2o
3-SiO
2the preparation method of fiber, but its aluminium source, silicon source are all organic alkoxide, preparation process complexity, and cost is higher, is unsuitable for suitability for industrialized production.U.S. Patent number US 5,002,906 and US 3,865,599 also adopt sol-gel method and different starting material to prepare to have the polymorph A l of second-phase doping
2o
3fiber.
Sapphire whisker plate is a kind of important engineering materials, and its Application Areas is very extensive, on the high-temperature industrial furnace and other high temperature services of the industrial sector such as metallurgical, mechanical, ceramic, as liner and lagging material.Because its density is low, thermal insulation is good, thermal capacitance is little, not only can reduce the weight of stove, can also there is good energy-saving effect.
As ceramic fiber series products, at high temperature can there is crystallization efflorescence in various degree in sapphire whisker plate, causes fiberboard surface to occur falling the slag slag phenomenon that falls.This can accelerating fibers plate itself damage, reduce its work-ing life.Fiberboard (for example 1500 DEG C, 24h) under long-time hot conditions simultaneously, fiberboard there will be larger contraction.Someone proposes at fiberboard external coating one deck silicon sol or other air-setting high-temperature resistant coatings for this reason.This has alleviated to a certain extent the slag that falls and has fallen the phenomenon of slag, but can increase cost and preparation cycle extends.
Published patent No. CN 101,135,131B has described a kind of inorganic fiberboard and method for making thereof.After it uses inorganic fibre cotton for main raw material slurrying, by adding filler, organic bond, additive to make after certain density slurry, adopt wet method vacuum forming, at a certain temperature bake drying, make inorganic fiberboard.Its inorganic fibre cotton is Al
2o
3content is one or the compound use of 40～44%, 45～47% or 47～49% 3 kinds of ceramic fiber cottons.Can directly be used in the more serious place of airflow scouring, but its Al
2o
3content is lower, and compared with high purity aluminium oxide fiber, its Young's modulus reduces, and therefore intensity is not high.Published U.S. Patent number US 0,321,993A1 has described a kind of preparation technology of ceramic beaverboard, and the ceramic fiber of its use contains Al
2o
3and SiO
2, mineral binder bond is the mixture of silicon sol and water glass.Owing to not using organic binder bond, therefore fiberboard can not produce the volatile matter such as black smoke in use.But the use temperature of fiberboard not high (≤1200 DEG C).
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the invention provides and a kind ofly possess higher force and learn the sapphire whisker plate of performance, good thermal insulation property and heat-shock resistance, the present invention also provides the preparation method of high purity aluminium oxide fiber and products thereof.
Technical scheme: for solving the problems of the technologies described above, a kind of sapphire whisker plate of the present invention, its raw material is made up of sapphire whisker, mineral binder bond, organic binder bond and additive, and its mass ratio is: (30～40): (55～65): (0～1): (4～5).
Preferably, described mineral binder bond is one or more mixture of polymeric aluminum chlorides solution, silicic acid sol.
Preferably, described organic binder bond is one or more the mixture in carboxymethyl cellulose, polyacrylamide.
Preferably, described additive is one or more mixture of alumina powder, Spinel micropowder, zirconium white micro mist, yttrium aluminum garnet micro mist, fine silica powder.
The preparation method of above-mentioned sapphire whisker plate, its preparation process comprises as follows:
(1) prepare sapphire whisker presoma colloid: a, be 1.7～2.1 by liquor alumini chloridi and aluminium powder according to the stoichiometric ratio of Al/Cl (mol ratio), preferably 1.8～2.0, join in the reactor that there is heating, reflux, 100 DEG C of heating 2～3h, filter and obtain pale asphyxia polymerize aluminum chloride mother liquor; B, by the polymerize aluminum chloride mother liquor obtaining, adds a certain amount of acetic acid or lactic acid as stablizer and spin finish aid, can be also other oxide compound second-phases (MgO, SiO
2, ZrO
2deng) precursor sol, vacuumize at 65～70 DEG C and be concentrated into certain viscosity, its viscosity number is 20～35Pas, obtains sapphire whisker precursor sol;
(2) centrifugal spinning: adopt homemade centrifugal box-spinning machine spinning, according to the difference of the viscosity of prepared colloid, adjust suitable wind speed, rotating speed and temperature, finally obtain the uniform presoma macrofiber of diameter;
(3) prepare sapphire whisker: by dry 24h at 55～65 DEG C of gelled fibres obtaining, thermal treatment 2h at 900～1200 DEG C, obtains required polycrystalline alumina fiber;
(4) the wet base of system: be (30～40) by sapphire whisker, mineral binder bond, organic binder bond, additive according to weight ratio: (55～65): (0～1): (4～5), carry out abundant slurrying, adopt vacuum forming, dehydration is produced the wet base with definite shape and size in corresponding mould;
(5) high temperature, mechanical process: the base that will wet is through 90～100 DEG C of dry 48h, remove moisture, impel goods internal bond agent gel, sclerosis, obtain dry body, dry body is carried out to pyroprocessing according to required different temperature, the wherein organic substance decomposing such as polyacrylamide, the further densification of sapphire whisker plate, by fiberboard cut, surperficial deburring, finally obtain having the sapphire whisker plate of certain service requirements.
Further, oxide compound second-phase is MgO, SiO
2, ZrO
2or Y
2o
3.
Further, the precursor sol of described oxide compound second-phase is respectively magnesium acetate solution, silicate solution, acetic acid and closes the one in zirconium solution, acetic acid yttrium solution.
Further, in described mineral binder bond, water weight percent content is 84.5～85.8%.
The sapphire whisker plate obtaining by present method, and the comparative result of a kind of mullite fiber brick (publication number CN 101628818A):
Fiberboard principal crystalline phase is α-Al
2o
3, remaining also has the generation of a small amount of second-phase according to the difference of additive.
Beneficial effect: sapphire whisker plate prepared by the inventive method in terms of existing technologies, because alumina content is very high, has very high Young's modulus and mechanical strength, has improved the mechanical property of fiberboard; Reduced size deviation and the thermal conductivity of product simultaneously, improved the heat-insulating property of goods, the use temperature of sapphire whisker plate is very high, than aluminosilicate fiberboard, mullite fiber plate, has expanded the use temperature scope of refractory materials.
Brief description of the drawings
Fig. 1 is prepared alumina gel fiber.
Fig. 2 is Al
2o
3fiber is in the XRD figure spectrum of 1200 DEG C of insulation 2h.
Fig. 3 is prepared a kind of sapphire whisker plate.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further described.
Embodiment mono-:
Get Aluminum chloride anhydrous 40g, be dissolved in 500ml water, liquor alumini chloridi and 38.0g aluminium powder are poured in the reactor with reflux, 90～100 DEG C of heating 2～2.5h, obtain polymerize aluminum chloride mother liquor (Al after cold filtration
2o
3massfraction 14.8%).Then add 20ml lactic acid as deflocculant and spin finish aid, 65～70 DEG C vacuumize after concentrated 1.5～2h, make the colloid that viscosity is 20～35Pa.s.
Adopt homemade centrifugal box-spinning machine centrifugal spinning, colloidal sol forms pure white and soft gelled fibre under the second traction effect of centrifugal force and hot blast, and with one cydariform fibroblast cover collect.As shown in Figure 1, Fibre diameter is 15～20um, and length is 30～80cm, and smooth surface, fibre section are rounded.Wherein, the diameter that gets rid of silk head is 45mm, is highly 35mm, has been uniformly distributed 12 apertures that diameter is 0.5mm around.The rotating speed of whizzer is 2000～3500r/min, and the temperature in fibroblast cover is 50～65 DEG C, and relative humidity is 20%～40%.Long 20～the 80cm of gelled fibre, diameter is 15～20um.After 55～75 DEG C of dry 24h, be placed in heat treatment furnace, with 1 DEG C of min
-1be warming up to 500 DEG C from 100 DEG C, then with 3 DEG C of min
-1be warming up to 700 DEG C, insulation 1h, finally with 5 DEG C of min
-1be warming up to 1200 DEG C, insulation 2h, obtains polycrystalline alumina fiber.Fiber principal crystalline phase is α-Al
2o
3, as shown in Figure 2.
Get above-mentioned prepared sapphire whisker 400g, then add polymeric aluminum chlorides solution 550g, alumina powder 50g, fully stirs, slurrying.Ensure, in the uniform situation of slurrying, should to shorten churning time as far as possible, prevent that sapphire whisker from excessively shortening, affect the mechanical property of fiberboard.Then adopt vacuum forming to produce wet base in corresponding mould, after the demoulding, at 90～100 DEG C, dry 48h, removes moisture, impels wet base internal junction mixture to carry out gel, and wet base sclerosis, obtains dry body.Sintering 3h at 1600 DEG C, the volatile gases of generation is overflowed from fiberboard, obtains α-Al
2o
3fiberboard blank.Blank is cut according to required size, after surperficial deburring is processed, obtain having certain service requirements sapphire whisker plate, as shown in Figure 3.The density of resulting product is 0.50g/cm
3; Refractoriness is 1600～1700 DEG C; Reheating permanent line changes: 1400 DEG C × 2h≤0.21%; Cold conditions ultimate compression strength:>=2.4Mpa; 1000 DEG C of thermal conductivitys: <0.2W/ (mK).
Embodiment bis-:
Get the sapphire whisker 350g obtaining in embodiment mono-, add polymeric aluminum chlorides solution 600g, polyacrylamide 10g, Spinel micropowder 40g, fully stirs, slurrying, and shortens churning time as far as possible.Adopt manual shaping method to suppress to produce wet base in corresponding mould, 90 DEG C of dry 50h, remove moisture, internal junction mixture gel, obtain dry body.
By dry body sintering 2h at 1600 DEG C, obtaining principal crystalline phase is α-Al
2o
3fiberboard blank.Cut according to required size, after surface treatment, obtain final sapphire whisker plate.The density of goods is 0.54/cm
3; Refractoriness is 1600～1700 DEG C; Reheating permanent line changes: 1400 DEG C × 2h≤0.3%; Cold conditions ultimate compression strength:>=2.4Mpa; 1000 DEG C of thermal conductivitys: <0.24W/ (mK).
Embodiment tri-:
Get Aluminum chloride anhydrous 40g, be dissolved in 500ml water, by liquor alumini chloridi and 35.6g aluminium powder (n (Al): (Cl)=1.8) put in the trident flask with reflux by a certain percentage, 90 DEG C of heating 2～3h, obtain polymeric aluminum chlorides solution (Al after cold filtration
2o
3massfraction 14.2%).
Get above-mentioned prepared polymeric aluminum chlorides solution, according to Al
2o
3with the chemical constitution that MgO mass ratio is 98:1, measure magnesium basic carbonate (the chemical formula 4Mg (OH) of 2.0g
2mgCO
3) be dissolved in 10g glacial acetic acid, form clear solution.After mixing, add 30ml glacial acetic acid as spin finish aid and stablizer.67 DEG C vacuumize after concentrated 2h, obtain the colloid that viscosity is 30P.s.Spinning on homemade centrifugal box-spinning machine, obtaining length is 30～50cm, the gelled fibre of diameter 15～20um.Wherein, the rotating speed of whizzer is 3000r/min, and the temperature in fibroblast cover is 60 DEG C, and relative humidity is 30%.Gelled fibre, after 65 DEG C of dry 24h, is placed in heat treatment furnace, with 2 DEG C of min
-1be warming up to 900 DEG C, after insulation 2h, obtain the sapphire whisker of doping.
Get sapphire whisker 400g, add polymeric aluminum chlorides solution 550g, polyacrylamide 10g, Spinel micropowder 40g, fully stirs, slurrying.Ensureing, in the uniform situation of slurrying, should to shorten the churning time that adds sapphire whisker later as far as possible.Adopt vacuum forming in mould, to produce wet base, at 90～100 DEG C, dry 50h, removes moisture, impels wet base internal junction mixture gel, and wet base sclerosis, obtains dry body.By dry body sintering 2h at 1650 DEG C, make sapphire whisker plate blank.Cut according to required size, after surface treatment, obtain final sapphire whisker plate.The density of goods is 0.46/cm
3; Refractoriness is 1500～1700 DEG C; Reheating permanent line changes: 1400 DEG C × 2h≤0.4%; Cold conditions ultimate compression strength:>=2.3Mpa; 1000 DEG C of thermal conductivitys: <0.3W/ (mK).
Embodiment tetra-:
Get Aluminum chloride anhydrous 40g, be dissolved in 500ml water, by liquor alumini chloridi and 40.4g aluminium powder by a certain percentage (wherein the stoichiometric ratio of Al/Cl is 2.0) put in the reactor with reflux, 100 DEG C of heating 2～2.5h, obtain polymerize aluminum chloride mother liquor (Al after cold filtration
2o
3massfraction 15.5%).
Get prepared polymeric aluminum chlorides solution, according to m (Al
2o
3): m (SiO
2the ratio of)=99:1, measures tetraethoxy (TEOS) 3.5ml, the blend of TEOS and dehydrated alcohol is joined in the mixing solutions of nitric acid and acetic acid, and TEOS fast hydrolyzing, obtains silicate solution.Wherein TEOS, dehydrated alcohol, concentrated nitric acid, acetic acid, water are 10:5:1:1:15 according to volume ratio.Silicate solution is joined in polymerize aluminum chloride, then add 40ml glacial acetic acid, as deflocculant.65～70 DEG C vacuumize after concentrated 2.0～2.5h, make the colloid that viscosity is 25～30P.s.
By colloid spinning on homemade centrifugal box-spinning machine of preparation, obtaining staple length is 10～60cm, the gelled fibre of diameter 6～10um.Wherein, the rotating speed of whizzer is 3300r/min, and the temperature in fibroblast cover is 50～65 DEG C, and relative humidity is 30%～40%.Gelled fibre, after 55～65 DEG C of dry 24h, is placed in heat treatment furnace, with 3 DEG C of min
-1temperature rise rate be warming up to 900 DEG C, insulation 1.5h after, obtain sapphire whisker.
Get sapphire whisker 350g, add polymeric aluminum chlorides solution 600g, polyacrylamide 10g, fine silica powder 40g, fully stirs, slurrying.Ensureing, in the uniform situation of slurrying, should to shorten the churning time that adds sapphire whisker later as far as possible.Then adopt vacuum forming to produce wet base in corresponding mould, at 90～100 DEG C, dry 48h, removes moisture, impels wet base internal junction mixture gel, and wet base sclerosis, obtains dry body.
By dry body sintering 2.5h at 1500 DEG C, make sapphire whisker plate blank.The sapphire whisker plate blank obtaining is cut according to required size, after surface treatment, obtain final sapphire whisker plate.The density of goods is 0.44g/cm
3; Refractoriness is 1500～1600 DEG C; Reheating permanent line changes: 1400 DEG C × 2h≤0.2%; Cold conditions compressive strength:>=2.1Mpa; 1000 DEG C of thermal conductivitys: <0.2W/ (mK).
Embodiment five:
Get Aluminum chloride anhydrous 40g, be dissolved in 500ml water, by liquor alumini chloridi and 38.0g aluminium powder by a certain percentage (wherein the stoichiometric ratio of Al/Cl is 1.9) put in the reactor with reflux, 90～100 DEG C of heating 2～2.5h, obtain transparent polymeric aluminum chloride mother liquor (Al after cold filtration
2o
3massfraction 14.8%).
According to Al
2o
3and ZrO
2mass ratio is 98:2, measures the zirconyl carbonate (ZrO of 4.5g
2content>=40%) be dissolved in 10ml glacial acetic acid, form acetic acid and close zirconium clear solution.Acetic acid is closed to zirconium solution and join in polymeric aluminum chlorides solution, and add 20ml glacial acetic acid, as spin finish aid and stablizer.65 DEG C of heating in water bath, vacuumize concentrated 2.5h, make the colloid that viscosity is 35P.s.
Adopt homemade centrifugal box-spinning machine centrifugal spinning, colloidal sol forms the pure white and good gelled fibre of toughness under the second traction effect of centrifugal force and hot blast, and with one cydariform fibroblast cover collect.Wherein, the rotating speed of whizzer is 3000r/min, and the temperature in fibroblast cover is 50～60 DEG C, and relative humidity is 20%～40%.The gelled fibre length obtaining is 15～60cm, diameter 10～15um.Gelled fibre, after 55～65 DEG C of dry 24h, is placed in heat treatment furnace, with 2 DEG C of min
-1temperature rise rate be warming up to 1000 DEG C, insulation 1h after, obtain polycrystalline alumina fiber.
Get sapphire whisker 400g, add polymeric aluminum chlorides solution 550g, carboxymethyl cellulose 10g, zirconium white micro mist 40g, fully stirs, slurrying.Ensureing, in the uniform situation of slurrying, should to shorten the churning time that adds sapphire whisker later as far as possible.Adopt vacuum forming to produce wet base in corresponding mould, wet 100 DEG C of dry 48h of base, remove moisture, wet base internal junction mixture gel, and sclerosis, obtains dry body.By dry body sintering 2h at 1600 DEG C, make sapphire whisker plate blank.Cut according to required size, after surface finish, obtain final sapphire whisker plate.The density of goods is 0.6g/cm
3; Refractoriness is 1600 DEG C; Reheating permanent line changes: 1400 DEG C × 2h≤0.3%; Cold conditions compressive strength:>=2.2Mpa; 1000 DEG C of thermal conductivitys: <0.15W/ (mK).
Embodiment six:
Get Aluminum chloride anhydrous 40g, be dissolved in 500ml water, by liquor alumini chloridi and 40.4g aluminium powder by a certain percentage (wherein the stoichiometric ratio of Al/Cl is 2.0) put in the reactor with reflux, 90～100 DEG C of heating 2～2.5h, obtain pale asphyxia polymerize aluminum chloride mother liquor (Al after cold filtration
2o
3massfraction 15.5%).
Get prepared polymeric aluminum chlorides solution, by m (Al
2o
3): m (Y
2o
3)=98:2, measures acetic acid yttrium (the chemical formula Y (Ac) of 6.342g
34H
2o) be dissolved in polymeric aluminum chlorides solution, then add 30ml acetic acid as deflocculant and spin finish aid, adopt magnetic stirrer to stir for some time, until acetic acid yttrium dissolves completely.70 DEG C vacuumize after concentrated 1.5～2h, make the colloid that viscosity is about 20～30P.s.
Adopt homemade centrifugal box-spinning machine centrifugal spinning, adopt homemade centrifugal box-spinning machine centrifugal spinning, colloidal sol forms the pure white and good gelled fibre of toughness under the second traction effect of centrifugal force and hot blast, and with one cydariform fibroblast cover collect.Wherein, the rotating speed of whizzer is 3500r/min, and the temperature in fibroblast cover is 55 DEG C, and relative humidity is 30%.The longest 70cm of reaching of gelled fibre obtaining, mean diameter 16um.Gelled fibre, after 60 DEG C of dry 24h, is placed in heat treatment furnace, with 2 DEG C of min
-1temperature rise rate be warming up to 500 DEG C, then with 5 DEG C of min
-1temperature rise rate be warming up to 1000 DEG C, insulation 1h after, obtain polycrystalline alumina fiber.
Get prepared sapphire whisker 300g, add polymeric aluminum chlorides solution 650g, alumina powder 30g, yttrium aluminum garnet micro mist 20g, fully stirs, slurrying.Ensure, in the uniform situation of slurrying, should to shorten the churning time that adds sapphire whisker later as far as possible, prevent that sapphire whisker from excessively shortening, affect the mechanical property of fiberboard.Then adopt manual shaping method to suppress to produce wet base in corresponding mould, wet base is dry 50h at 90 DEG C, removes moisture, impels wet base internal junction mixture to carry out gel, and wet base sclerosis, obtains dry body.1550 DEG C of high temperature sintering 3h, make sapphire whisker plate blank.According to required size cutting, after surperficial deburring, obtain final sapphire whisker plate.The extrudate density obtaining is 0.49g/cm
3; Refractoriness is 1550 ± 50 DEG C; Reheating permanent line changes: 1400 DEG C × 2h≤0.4%; Cold conditions compressive strength:>=2.2Mpa; 1000 DEG C of thermal conductivitys: <0.3W/ (mK).
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a sapphire whisker plate, is characterized in that: raw material comprises sapphire whisker, mineral binder bond, organic binder bond and additive, and its mass ratio is: (30 ~ 40): (55 ~ 65): (0 ~ 1): (4 ~ 5).
2. sapphire whisker plate according to claim 1, is characterized in that: described mineral binder bond is one or more mixture of polymeric aluminum chlorides solution, silicate solution.
3. sapphire whisker plate according to claim 1, is characterized in that: described organic binder bond is one or more the mixture in carboxymethyl cellulose, polyacrylamide.
4. sapphire whisker plate according to claim 1, is characterized in that: described additive is one or more mixture of alumina powder, Spinel micropowder, zirconium white micro mist, yttrium aluminum garnet micro mist, fine silica powder.
5. a preparation method for the sapphire whisker plate described in claim 1 ~ 4, is characterized in that: preparation process is as follows:
(1) prepare sapphire whisker presoma colloid: a, be that mol ratio is 1.7 ~ 2.1 by liquor alumini chloridi and aluminium powder according to the stoichiometric ratio of Al/Cl, join in the reactor that there is heating, reflux, 100 DEG C of heating 2 ~ 3h, after reacting completely, filter and obtain pale asphyxia polymerize aluminum chloride mother liquor; B, by the polymerize aluminum chloride mother liquor obtaining, adds acetic acid or lactic acid as stablizer and spin finish aid, or the precursor sol of oxide compound second-phase, 65 ~ 70 DEG C of heating in water bath, vacuumize and be concentrated into certain viscosity, its viscosity number is 20 ~ 35Pas, obtains sapphire whisker precursor sol;
(2) centrifugal spinning: adopt homemade centrifugal box-spinning machine centrifugal spinning to obtain the uniform gelled fibre of diameter;
(3) prepare sapphire whisker: by 55 ~ 65 DEG C of dry 24h of the gelled fibre obtaining, thermal treatment 2h at 900 ~ 1200 DEG C, obtains needed polycrystalline alumina fiber;
(4) the wet base of system: by sapphire whisker, mineral binder bond, organic binder bond, additive, according to weight ratio be: 30 ~ 40:55 ~ 65:0 ~ 1:4 ~ 5, carry out abundant slurrying, adopt vacuum forming, dehydration, in corresponding mould, produce the wet base with definite shape and size;
(5) high temperature, mechanical process: the base that will wet is through 90 ~ 100 DEG C of dry 48h, remove moisture, impel goods internal bond agent gel, sclerosis, obtain dry body, dry body is carried out to pyroprocessing according to required different temperature, make the further densification of sapphire whisker plate, by fiberboard cut, surperficial deburring, finally obtain thering is sapphire whisker plate.
6. the preparation method of sapphire whisker plate according to claim 5, is characterized in that: oxide compound second-phase is MgO, SiO
2, ZrO
2or Y
2o
3.
7. the preparation method of sapphire whisker plate according to claim 5, is characterized in that: the precursor sol of described oxide compound second-phase is respectively magnesium acetate solution, silicate solution, acetic acid and closes the one in zirconium solution, acetic acid yttrium solution.
8. the preparation method of sapphire whisker plate according to claim 5, is characterized in that: in described mineral binder bond, water weight percent content is 84.5 ~ 85.8%.
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| CN105418165A (en) * | 2015-11-09 | 2016-03-23 | 东莞华晶粉末冶金有限公司 | Alumina composite whisker and preparation method and composite thereof |
| CN106187254A (en) * | 2016-07-06 | 2016-12-07 | 南京理工宇龙新材料科技股份有限公司 | A kind of high strength fiberboard and preparation method thereof |
| CN107999049A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | Siliceous hydrated alumina composition and formed body and preparation method and application and catalyst and preparation method |
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| CN107999049A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | Siliceous hydrated alumina composition and formed body and preparation method and application and catalyst and preparation method |
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| CN111253169A (en) * | 2020-01-20 | 2020-06-09 | 山东鲁阳浩特高技术纤维有限公司 | Alumina fiber integral module and preparation method thereof |
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| CN111210167B (en) * | 2020-02-20 | 2023-06-20 | 山东鲁阳浩特高技术纤维有限公司 | Regulation and control method of alumina fiber blanket blank |
| CN111410544A (en) * | 2020-04-29 | 2020-07-14 | 成都天道化工技术有限公司 | Method for manufacturing non-flexible refractory fiber product |
| CN113173772A (en) * | 2021-05-10 | 2021-07-27 | 河南省西峡开元冶金材料有限公司 | Polycrystalline alumina fiber liner and manufacturing method thereof |
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