CN102181962A - Method for preparing thin-diameter zirconium oxide fibers and fiber board thereof - Google Patents
Method for preparing thin-diameter zirconium oxide fibers and fiber board thereof Download PDFInfo
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- CN102181962A CN102181962A CN 201010503092 CN201010503092A CN102181962A CN 102181962 A CN102181962 A CN 102181962A CN 201010503092 CN201010503092 CN 201010503092 CN 201010503092 A CN201010503092 A CN 201010503092A CN 102181962 A CN102181962 A CN 102181962A
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Abstract
The invention relates to a method for preparing thin-diameter zirconium oxide fibers and a fiber board thereof. The method comprises the following steps of: preparing poly zirconium sol spinning solution by adopting basic zirconium carbonate, glacial acetic acid, water and yttrium nitrate as raw materials, obtaining thin-diameter poly zirconium sol fibers by ultrahigh-speed centrifugal swinging and high-speed hot airflow blowing and drafting, and performing thermal treatment and sintering on the thin-diameter poly zirconium sol fibers to obtain the thin-diameter zirconium oxide fibers; and performing vacuum suction molding and pressure leveling to prepare a wet fiber board blank by adopting the thin-diameter zirconium oxide fibers as a raw material and adopting poly zirconium sol spinning solution diluted by adding water as adhesive, and drying and calcining the wet blank to obtain the zirconium oxide fiber board. The raw materials are easily obtained, the preparation of the adhesive is simple and convenient, and the method has low cost and no pollution and is suitable for large-batch industrialized production; the prepared thin-diameter zirconium oxide fibers have good bending flexibility; and the prepared zirconium oxide fiber board has uniform thickness, flat surface, accurate and controllable thickness, and good mechanical property and high-temperature bending resistance.
Description
Technical field
The invention belongs to the inorganic fire proof material field, the preparation method of particularly a kind of thin diameter Zirconium oxide fibre and fiberboard thereof.
Background technology
Superhigh temperature refractory heat-insulating fibrous material has important application prospects in fields such as space flight and superhigh temperature electric stoves, zirconia (ZrO
2) the long-term serviceability temperature of fiber and fiber board products thereof can reach more than 1800 ℃, and the heat preservation and insulation excellence, high temeperature chemistry stable in properties, corrosion-resistant, anti-oxidant, non-volatile, pollution-free is the most top in the world current a kind of High-grade Refractory Fibre material.If can realize its suitability for industrialized production, and large-scale application will bring into play its heatproof height, heat insulation good, energy-saving and cost-reducing performance advantage in fields such as China's space flight and superhigh temperature electric stove manufacturings, promotes the product up-gradation and the technological progress of association area energetically.
Pure zirconia has monocline (m), four directions (t) and cube (c) three kinds of different solid-state forms under different temperatures:
Reversible transition can take place in these three kinds of solid-state forms when heating and cooling, the high temperature phase of pure zirconia (cube phase is with mutually cubic) structure can not be stabilized to room temperature, and the phase transformation of four directions → monocline follows about 8% volumetric expansion meeting to cause structure cracked, mixes Y
2O
3, CaO, MgO or CeO
2Deng oxide and ZrO
2Form solid solution, cube phase and/or tetragonal phase structure are remained, promptly played the effect of stable high temperature phase.In several stabilizing agents, Y
2O
3Stablizing effect best.Mix the Y of 2～3mol%
2O
3The yttrium that can at room temperature obtain to have fabulous mechanical property is stablized tetragonal zirconia polycrystal body (Y-TZP), mixes the above Y of 8mol%
2O
3Can at room temperature obtain complete stable cubic zirconia (c-ZrO
2).For the Zirconium oxide fibre that uses as fire-resistant heat insulating material since in room temperature to prolonged and repeated heating and cooling between high temperature, undergo phase transition for avoiding it, should control its crystalline phase is c-ZrO
2
The technology of preparing of Zirconium oxide fibre is mainly grasped in developed country's hand, the Zircar company of the U.S., Britain's ICI Imperial Chemical Industries, day this product river refractory Company etc. have realized its suitability for industrialized production, and China only can small lot preparation, and there is gap in developed countries such as performance and the U.S., Britain, Japan.Very expensive from the Zirconium oxide fibre and the goods price of external import, and because the status of its strategic materials, the import of China often is restricted.Therefore, research and development China has the Zirconium oxide fibre technology of preparing of independent intellectual property right and realizes its suitability for industrialized production, has important practical significance.Shandong University and Institutes Of Technology Of Nanjing have the excellent research basis aspect the Study on Preparation Technology of Zirconium oxide fibre, and all realized the small lot batch manufacture of Zirconium oxide fibre with business tie-up, but still have complex manufacturing at present, pollute big, deficiency such as yield poorly, and the diameter of prepared Zirconium oxide fibre mechanical property thick, fiberboard is relatively poor.
As patent ZL200410024262.7, with zirconium oxychloride, acetylacetone,2,4-pentanedione, triethylamine is main raw material, with methyl alcohol is retarder thinner, the synthetic poly-acetyl acetone zirconium precursor body of reaction, adopt oxolane to remove by filter the by-product hydrochloric acid triethylamine, to gather the acetyl acetone zirconium again and be dissolved in methyl alcohol acquisition spinning solution, obtain a presoma short cellucotton, obtain the zirconia short cellucotton through special atmosphere heat treatment again through the centrifugal silk that gets rid of; Patent ZL200910013781.7, with zirconium oxychloride, acetylacetone,2,4-pentanedione, triethylamine is main raw material, with ethanol is retarder thinner, the synthetic zirconium organic polymer that contains of reaction, adopt acetone to remove by filter the insoluble matter triethylamine hydrochloride, product is dissolved in methyl alcohol obtains spinning solution, get rid of silk through high speed centrifugation and obtain to contain the zirconium organic polymer fiber, obtain Zirconium oxide fibre through special atmosphere heat treatment and superhigh temperature sintering again; Two kinds of methods all exist cost of material height, adhesive-preparing technology step complexity, organic reagent to pollute big, Treatment for Reuse need increase problems such as cost, and all adopt special atmosphere heat treatment, the electric furnace of required usefulness must consider to feed special atmosphere when carrying out structural design, equipment is difficult to maximize.
The prepared Zirconium oxide fibre diameter of prior art is usually about 10 μ m, because diameter is still thicker relatively, the fiber bending flexility is relatively poor, fiber is difficult for weak when being used to prepare zirconium oxide fiber board, very difficult formation fiber is arranged layer by layer, superimposed satisfactory texture closely, causes the mechanical property of fiberboard and high temperature bending resistance relatively poor.If the diameter of Zirconium oxide fibre generally can be reduced by 1 times, to 5 μ m, fiber cross section is long-pending can to descend about 4 times, can significantly improve the crooked pliability of fiber, promotes the mechanical property and the high temperature bending resistance of zirconium oxide fiber board.
In addition, also there is certain deficiency in the technology of preparing of existing zirconium oxide fiber board, as patent ZL200910013782.1 and ZL200810020282.6, when carrying out the fiberboard moulding, only adopt vacuum filtering shape process, have that fiberboard thickness is inhomogeneous, upper surface out-of-flatness, thickness be difficult to deficiencies such as accurately control.
Summary of the invention
The present invention is directed to the deficiency of the technology of preparing existence of existing Zirconium oxide fibre and fiberboard thereof, provide a kind of raw material to be easy to get, glue is easy, cost is low, the preparation method of pollution-free, the thin diameter Zirconium oxide fibre that is fit to mass industrialized production, and utilize this thin diameter Zirconium oxide fibre prepare thickness evenly, the method for all good zirconium oxide fiber board of accurately controlled, the mechanical property of surfacing, thickness and high temperature bending resistance.
The preparation method of the thin diameter Zirconium oxide fibre of the present invention is: adopt zirconium oxycarbonate, glacial acetic acid, water, yttrium nitrate as the poly-zirconium colloidal sol spinning solution of feedstock production, get rid of silk and high speed thermal current winding-up drawing-off and obtain thin diameter and gather the zirconium gelatinous fibre through ultrahigh speed is centrifugal, obtain thin diameter Zirconium oxide fibre through the heat treatment sintering again.
The preparation method of zirconium oxide fiber board of the present invention is: adopting thin diameter Zirconium oxide fibre is raw material, poly-zirconium colloidal sol spinning solution thin up is a binding agent, adopt the method for vacuum filtering shape process and pressurization leveling to prepare the wet base of fiberboard, oven dry, calcining obtains zirconium oxide fiber board.
The present invention compared with prior art, its remarkable advantage:
(1) raw material of the present invention's employing is zirconium oxycarbonate, glacial acetic acid, water and yttrium nitrate, be the market common chemical raw materials, not only cost is low, the purity height, and nontoxic, avoided adopting the volatilizations that organic reagent brought such as methyl alcohol, triethylamine, acetylacetone,2,4-pentanedione, oxolane to pollute to the harm of human body and the cost of material of costliness.Estimate that according to the current market price the technology of the present invention is produced the cost of material of 1 kilogram of Zirconium oxide fibre less than 100 yuan, far below the cost of material of existing other technologies such as patent ZL200410024262.7 and ZL200910013781.7.
(2) glue method of the present invention is compared with prior art more easy, only needs the direct hybrid reaction of zirconium oxycarbonate, glacial acetic acid and water, and a step can obtain the splendid poly-zirconium colloidal sol spinning solution of spinnability, does not need the admixture spin finish aid to get final product the centrifugal silk that gets rid of.And most prior art is because the spinning solution spinnability of preparation is relatively poor, must in spinning solution, assist fine by organic high molecular polymers such as admixture polyvinyl alcohol, polyethylene glycol, Carboxymethyl Cellulose, but these organic polymers are present in the precursor fibre, can damage fibre structure during decomposes, reduce fibre strength.
(3) the centrifugal silk that gets rid of of the ultrahigh speed of the present invention's employing is jetted into fine technology with the high speed thermal current, the high speed centrifugation power of colloid by ten thousand rotating motors throws away from the aperture of 0.2mm～0.5mm, fibre diameter is thinner, again by the winding-up of high speed thermal current, fiber surface is subjected to the rubbing action of high velocity air and drafted elongation, diameter further reduces, and finally can obtain the thin diameter Zirconium oxide fibre of diameter 3 μ m～6 μ m.
(4) the thin diameter Zirconium oxide fibre that the present invention obtained is compared with the thick diameter Zirconium oxide fibre of prior art for preparing, cross-sectional area descends about 4 times, crooked pliability is improved greatly, when utilizing this thin diameter Zirconium oxide fibre to prepare fiberboard, fiber is easier to be arranged layer by layer, superimposed closely, the mechanical property of fiberboard and high temperature resistance flexural deformation performance are all good.Contrast test shows: utilize the compression strength of the zirconium oxide fiber board of thick diameter Zirconium oxide fibre preparation to have only 0.2MPa～0.5MPa usually, the fiberboard two ends are propped, middle span 200mm can take place significantly crooked sagging at 1650 ℃ of calcining 24h; And utilizing the compression strength of the zirconium oxide fiber board of thin diameter Zirconium oxide fibre preparation of the present invention can reach 0.5MPa～0.8MPa, any flexural deformation does not take place at 1650 ℃ of calcining 24h in similarity condition.
(5) technology of the present invention's vacuum filtering shape process that adopts and leveling preparation zirconium oxide fiber board that pressurizes, overcome prior art only adopt vacuum filtering shape process and cause that fiberboard thickness is inhomogeneous, surface irregularity, thickness be difficult to deficiencies such as accurately control, thickness uniformity, the surface smoothness at prepared four diagonal angles of zirconium oxide fiber board is good, thickness can accurately be controlled at 20mm, 30mm, 50mm, 60mm, 70mm, 80mm, 90mm, 100mm, agree with mutually with the market demand, need not to polish again processing.
(6) the present invention need not feed special atmosphere when the poly-zirconium gelatinous fibre of thin diameter is calcined in heat treatment, so electric furnace designs and produces simply, and the heat treatment cost is low, and production equipment maximizes easily, is convenient to realize mass industrialized production.
(7) prepared thin diameter Zirconium oxide fibre of the present invention and fiberboard thereof can be used as the superhigh temperature fire-resistant heat insulating material, are widely used in space flight and superhigh temperature electric stove field, and because of production cost is lower, mechanical property and resistance to elevated temperatures are better, and market prospects are very wide.
Description of drawings
Fig. 1 is the digital camera photo of the thin diameter Zirconium oxide fibre of the present invention.
Fig. 2 is the digital camera photo of zirconium oxide fiber board of the present invention.
Fig. 3 is the stereoscan photograph of thin diameter Zirconium oxide fibre of the present invention.
The specific embodiment
The preparation method of thin diameter Zirconium oxide fibre of the present invention and fiberboard thereof specifically may further comprise the steps:
(1) the poly-zirconium colloidal sol spinning solution of single step reaction preparation
According to ZrO in the reaction system
2: glacial acetic acid: the mol ratio of water is 1: 2～3: 15～25 ratio, takes by weighing zirconium oxycarbonate (the molecular formula ZrOCO of corresponding mass
3NH
2O, ZrO
2Content 38～42wt%), and measure the glacial acetic acid and the water of corresponding volume is diluted in glacial acetic acid in the water, 70 ℃～80 ℃, stir and the condition of bleeding under, acetic acid aqueous solution is mixed with zirconium oxycarbonate, reaction generates basic zirconium acetate and with CO
2Gas is overflowed, hydrolysis-condensation reaction further takes place in basic zirconium acetate, and forming acetate is the Zr-O-Zr chain polymer of side group, treat that solid all dissolves, reaction solution become transparent after, promptly having obtained poly-aqueous zirconium, is ZrO according to the composition ratio requirement of complete stable cubic phase zircite
2: Y
2O
3Mol ratio be 92～90: 8～10 ratio, in the above-mentioned poly-aqueous zirconium that makes, add phase stabiliser raw material yttrium nitrate (Y (NO
3)
36H
2O), stir and to make its dissolving, decompression distillation is 10Pas～50Pas until obtaining viscosity, has a poly-zirconium colloidal sol spinning solution of good fibre-forming performance to slough excessive moisture under 70 ℃～80 ℃ conditions afterwards.
(2) ultrahigh speed is centrifugal gets rid of silk and high speed thermal current winding-up drawing-off and obtains thin diameter and gather the zirconium gelatinous fibre
The poly-zirconium colloidal sol spinning solution of the above-mentioned high viscosity that makes is injected the centrifugal swaying wire equipment of ultrahigh speed, under the high speed rotation of 20,000 commentaries on classics/min～30,000 commentaries on classics/min, making spinning solution is centrifugal the throwing away of aperture along continuous straight runs of 0.2mm～0.5mm from the aperture, be that 80 ℃～100 ℃, air velocity are under the high speed thermal current winding-up downward for annular of 10m/s～50m/s, blowing direction in temperature immediately, by further drawing-off, curing, obtain the poly-zirconium gelatinous fibre of thin diameter.
(3) heat treatment sintering
The poly-zirconium gelatinous fibre of the thin diameter of above-mentioned acquisition is put into program control heat treatment electric furnace, programming rate with 1 ℃/min～3 ℃/min is warming up to 500 ℃, programming rate with 3 ℃/min～5 ℃/min is warming up to 1100 ℃～1300 ℃ again, and insulation 2h～4h, obtain that diameter 3 μ m of the present invention～6 μ m, crooked pliability are good, crystalline phase is the thin diameter Zirconium oxide fibre of cube phase.
(4) vacuum filtering shape process and pressurization leveling, oven dry, calcining obtain zirconium oxide fiber board
Adopt diameter 3 μ m～6 μ m, the thin diameter Zirconium oxide fibre of cube phase is a raw material, and the viscosity that adopts method for preparing is that the poly-zirconium colloidal sol spinning solution thin up of 10Pas～50Pas is made binding agent, ratio according to poly-zirconium colloidal sol spinning solution: the 5L of 1kg fiber: 100ml～200ml～10L water, take by weighing the thin diameter Zirconium oxide fibre of respective quality, measure the poly-zirconium colloidal sol spinning solution and the water of respective volume, the thin diameter Zirconium oxide fibre weak point that takes by weighing is cut to the length of 2mm～5mm, with the poly-zirconium colloidal sol spinning solution dilute with water of measuring, add together in the slurrying pond, stir more than the 5min, fiber is uniformly dispersed in adhesive solution, form cotton pulp, the bottom is evenly distributed with the 2mm aperture, the formation mould of certain size is put into the slurrying pond, open vacuum-pumping system, the fiber cotton pulp is sucked in the mould, moisture is sucked away, and fiber layer by layer laying in mould, form the wet base of certain thickness fiberboard, take out and the back-off mould, the wet base of fiberboard is fallen within on the supporting plate of flat surfaces, above wet base, cover pressing plate, clamp surface is smooth, four jiaos of its lower surface are equipped with highly consistent double-screw bolt, apply the wet base of pressure extrusion fiberboard of 0.1MPa～0.3MPa downwards, four jiaos of double-screw bolts until pressing plate all contact with the surface of below supporting plate, thereby the thickness that makes fiberboard evenly and reach the numerical value of accurate control, supporting plate is placed 100 ℃～120 ℃ baking oven together with the wet base of fiberboard, baking 20h～30h is to wet base bone dry, fiberboard after the oven dry is placed the high-temperature calcination stove, programming rate with 3 ℃/min～5 ℃/min is warming up to 1600 ℃～1800 ℃, and insulation 2h～4h, it is even to obtain thickness of the present invention, surfacing, thickness is accurately controlled, fiber is arranged layer by layer, superimposed tight, mechanical property and all good zirconium oxide fiber board of high temperature bending resistance.
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1:
(1) the poly-zirconium colloidal sol spinning solution of single step reaction preparation:
According to ZrO in the reaction system
2: glacial acetic acid: the mol ratio of water is 1: 2.5: 20 a ratio, takes by weighing zirconium oxycarbonate (the molecular formula ZrOCO of corresponding mass
3NH
2O, ZrO
2Content 40.6wt%) 1kg, and measure 474mL glacial acetic acid and 1188mL water, glacial acetic acid is diluted in the water, 75 ℃, stir and the condition of bleeding under, with acetic acid aqueous solution and zirconium oxycarbonate hybrid reaction, treat that solid all dissolves, reaction solution become transparent after, promptly obtained poly-aqueous zirconium, be ZrO according to the composition ratio requirement of complete stable cubic phase zircite
2: Y
2O
3Mol ratio be 92: 8 ratio, in the above-mentioned poly-aqueous zirconium that makes, add 220g phase stabiliser raw material yttrium nitrate (Y (NO
3)
36H
2O), stir and to make its dissolving, decompression distillation is 30Pas until obtaining viscosity, has a poly-zirconium colloidal sol spinning solution of good fibre-forming performance to slough excessive moisture under 75 ℃ of conditions afterwards;
(2) ultrahigh speed is centrifugal gets rid of silk and high speed thermal current winding-up drawing-off and obtains thin diameter and gather the zirconium gelatinous fibre
The poly-zirconium colloidal sol spinning solution of the above-mentioned high viscosity that makes is injected the centrifugal swaying wire equipment of ultrahigh speed, under the high speed rotation of 2.5 ten thousand commentaries on classics/min, making spinning solution is centrifugal the throwing away of aperture along continuous straight runs of 0.3mm from the aperture, be that 90 ℃, air velocity are under the high speed thermal current winding-up downward for annular of 30m/s, blowing direction in temperature immediately, by further drawing-off, curing, obtain the poly-zirconium gelatinous fibre of thin diameter.
(3) heat treatment sintering
The poly-zirconium gelatinous fibre of the thin diameter of above-mentioned acquisition is put into program control heat treatment electric furnace, programming rate with 2 ℃/min is warming up to 500 ℃, programming rate with 4 ℃/min is warming up to 1200 ℃ again, and insulation 3h, obtain that diameter 3 μ m of the present invention～6 μ m, crooked pliability are good, crystalline phase is the thin diameter Zirconium oxide fibre of cube phase.
(4) vacuum filtering shape process and pressurization leveling, oven dry, calcining obtain zirconium oxide fiber board
Adopt diameter 3 μ m～6 μ m, cube phase thin diameter Zirconium oxide fibre be raw material, and the viscosity that adopts method for preparing is that the poly-zirconium colloidal sol spinning solution thin up of 30Pas is made binding agent, gather zirconium colloidal sol spinning solution according to 1kg fiber: 150ml: the ratio of 7.5L water, take by weighing the thin diameter Zirconium oxide fibre of 10kg, measure poly-zirconium colloidal sol spinning solution of 1.5L and 75L water, the thin diameter Zirconium oxide fibre weak point that takes by weighing is cut to the length of 2mm～5mm, with the poly-zirconium colloidal sol spinning solution dilute with water of measuring, add together in the slurrying pond, stir 10min, fiber is uniformly dispersed in adhesive solution, form cotton pulp, the bottom is evenly distributed with the 2mm aperture, long * wide * as to put into the slurrying pond for the formation mould of 300mm * 200mm * 44mm deeply, open vacuum-pumping system, the fiber cotton pulp is sucked in the mould, moisture is sucked away, and fiber layer by layer laying in mould, form the wet base of certain thickness fiberboard, take out and the back-off mould, the wet base of fiberboard is fallen within on the supporting plate of flat surfaces, above wet base, cover pressing plate, clamp surface is smooth, four jiaos of its lower surface are equipped with the double-screw bolt that highly is 40.2mm, apply the wet base of pressure extrusion fiberboard of 0.2MPa downwards, four jiaos of double-screw bolts until pressing plate all contact with the surface of below supporting plate, thereby the thickness that makes fiberboard evenly and reach the numerical value of accurate control, supporting plate is placed 110 ℃ baking oven together with the wet base of fiberboard, baking 25h is to wet base bone dry, fiberboard after the oven dry is placed the high-temperature calcination stove, programming rate with 4 ℃/min is warming up to 1700 ℃, and insulation 3h, obtain length of the present invention * wide * thick 300mm * 200mm * 40mm of being, density is 0.8cm
3/ g, crystalline phase be cube phase, thickness evenly, surfacing, fiber arrange layer by layer, superimposed closely, mechanical property and all good zirconium oxide fiber board of high temperature bending resistance.Test shows that the compression strength of zirconium oxide fiber board can reach 0.70MPa, and the fiberboard two ends are propped, and middle span 200mm at 1650 ℃ of calcining 24h, any flexural deformation does not take place.
Embodiment 2:
(1) the poly-zirconium colloidal sol spinning solution of single step reaction preparation:
According to ZrO in the reaction system
2: glacial acetic acid: the mol ratio of water is 1: 3: 25 a ratio, takes by weighing zirconium oxycarbonate (the molecular formula ZrOCO of corresponding mass
3NH
2O, ZrO
2Content 41.4wt%) 1kg, and measure 578mL glacial acetic acid and 1515mL water, glacial acetic acid is diluted in the water, 70 ℃, stir and the condition of bleeding under, acetic acid aqueous solution and zirconium oxycarbonate hybrid reaction are obtained poly-aqueous zirconium, are ZrO according to the composition ratio requirement of complete stable cubic phase zircite
2: Y
2O
3Mol ratio be 91: 9 ratio, in the above-mentioned poly-aqueous zirconium that makes, add 255g phase stabiliser raw material yttrium nitrate (Y (NO
3)
36H
2O), stir and to make its dissolving, decompression distillation is 50Pas until obtaining viscosity, has a poly-zirconium colloidal sol spinning solution of good fibre-forming performance to slough excessive moisture under 70 ℃ of conditions afterwards;
(2) ultrahigh speed is centrifugal gets rid of silk and high speed thermal current winding-up drawing-off and obtains thin diameter and gather the zirconium gelatinous fibre
The poly-zirconium colloidal sol spinning solution of the above-mentioned high viscosity that makes is injected the centrifugal swaying wire equipment of ultrahigh speed, under the high speed rotation of 30,000 commentaries on classics/min, making spinning solution is centrifugal the throwing away of aperture along continuous straight runs of 0.5mm from the aperture, be that 80 ℃, air velocity are under the high speed thermal current winding-up downward for annular of 50m/s, blowing direction in temperature immediately, by further drawing-off, curing, obtain the poly-zirconium gelatinous fibre of thin diameter.
(3) heat treatment sintering
The poly-zirconium gelatinous fibre of the thin diameter of above-mentioned acquisition is put into program control heat treatment electric furnace, programming rate with 3 ℃/min is warming up to 500 ℃, programming rate with 5 ℃/min is warming up to 1300 ℃ again, and insulation 2h, obtain that diameter 3 μ m of the present invention～6 μ m, crooked pliability are good, crystalline phase is the thin diameter Zirconium oxide fibre of cube phase.
(4) vacuum filtering shape process and pressurization leveling, oven dry, calcining obtain zirconium oxide fiber board
Adopt diameter 3 μ m～6 μ m, the thin diameter Zirconium oxide fibre of cube phase is a raw material, and the viscosity that adopts method for preparing is that the poly-zirconium colloidal sol spinning solution thin up of 50Pas is made binding agent, gather zirconium colloidal sol spinning solution according to 1kg fiber: 100ml: the ratio of 10L water, take by weighing the thin diameter Zirconium oxide fibre of 10kg, measure poly-zirconium colloidal sol spinning solution of 1L and 100L water, the thin diameter Zirconium oxide fibre weak point that takes by weighing is cut to the length of 2mm～5mm, with the poly-zirconium colloidal sol spinning solution dilute with water of measuring, add together in the slurrying pond, stir 8min, fiber is uniformly dispersed in adhesive solution, form cotton pulp, the bottom is evenly distributed with the 2mm aperture, long * wide * as to put into the slurrying pond for the formation mould of 300mm * 200mm * 56mm deeply, open vacuum-pumping system, the fiber cotton pulp is sucked in the mould, moisture is sucked away, and fiber layer by layer laying in mould, form the wet base of certain thickness fiberboard, take out and the back-off mould, the wet base of fiberboard is fallen within on the supporting plate of flat surfaces, above wet base, cover pressing plate, clamp surface is smooth, four jiaos of its lower surface are equipped with the double-screw bolt that highly is 50.3mm, apply the wet base of pressure extrusion fiberboard of 0.3MPa downwards, four jiaos of double-screw bolts until pressing plate all contact with the surface of below supporting plate, thereby the thickness that makes fiberboard evenly and reach the numerical value of accurate control, supporting plate is placed 120 ℃ baking oven together with the wet base of fiberboard, baking 20h is to wet base bone dry, fiberboard after the oven dry is placed the high-temperature calcination stove, programming rate with 5 ℃/min is warming up to 1800 ℃, and insulation 2h, obtain length of the present invention * wide * thick 300mm * 200mm * 50mm of being, density is 1.0cm
3/ g, cube crystalline phase, thickness are evenly, surfacing, fiber arrange layer by layer, superimposed closely, mechanical property and all good zirconium oxide fiber board of high temperature bending resistance.Test shows that the compression strength of zirconium oxide fiber board can reach 0.8MPa, and the fiberboard two ends are propped, and middle span 200mm at 1650 ℃ of calcining 24h, any flexural deformation does not take place.
Embodiment 3:
(1) the poly-zirconium colloidal sol spinning solution of single step reaction preparation:
According to ZrO in the reaction system
2: glacial acetic acid: the mol ratio of water is 1: 2: 15 a ratio, takes by weighing zirconium oxycarbonate (the molecular formula ZrOCO of corresponding mass
3NH
2O, ZrO
2Content 38.7wt%) 1kg, and measure 360mL glacial acetic acid and 850mL water, glacial acetic acid is diluted in the water, 80 ℃, stir and the condition of bleeding under, acetic acid aqueous solution and zirconium oxycarbonate hybrid reaction are obtained poly-aqueous zirconium, are ZrO according to the composition ratio requirement of complete stable cubic phase zircite
2: Y
2O
3Mol ratio be 90: 10 ratio, in the above-mentioned poly-aqueous zirconium that makes, add 268g phase stabiliser raw material yttrium nitrate (Y (NO
3)
36H
2O), stir and to make its dissolving, decompression distillation is 10Pas until obtaining viscosity, has a poly-zirconium colloidal sol spinning solution of good fibre-forming performance to slough excessive moisture under 80 ℃ of conditions afterwards;
(2) ultrahigh speed is centrifugal gets rid of silk and high speed thermal current winding-up drawing-off and obtains thin diameter and gather the zirconium gelatinous fibre
The above-mentioned poly-zirconium colloidal sol spinning solution that makes is injected the centrifugal swaying wire equipment of ultrahigh speed, under the high speed rotation of 20,000 commentaries on classics/min, making spinning solution is centrifugal the throwing away of aperture along continuous straight runs of 0.2mm from the aperture, be that 100 ℃, air velocity are under the high speed thermal current winding-up downward for annular of 10m/s, blowing direction in temperature immediately, by further drawing-off, curing, obtain the poly-zirconium gelatinous fibre of thin diameter.
(3) heat treatment sintering
The poly-zirconium gelatinous fibre of the thin diameter of above-mentioned acquisition is put into program control heat treatment electric furnace, programming rate with 1 ℃/min is warming up to 500 ℃, programming rate with 3 ℃/min is warming up to 1100 ℃ again, and insulation 4h, obtain that diameter 3 μ m of the present invention～6 μ m, crooked pliability are good, crystalline phase is the thin diameter Zirconium oxide fibre of cube phase.
(4) vacuum filtering shape process and pressurization leveling, oven dry, calcining obtain zirconium oxide fiber board
Adopt diameter 3 μ m～6 μ m, the thin diameter Zirconium oxide fibre of cube phase is a raw material, and the viscosity that adopts method for preparing is that the poly-zirconium colloidal sol spinning solution thin up of 10Pas is made binding agent, gather zirconium colloidal sol spinning solution according to 1kg fiber: 200ml: the ratio of 5L water, take by weighing the thin diameter Zirconium oxide fibre of 10kg, measure poly-zirconium colloidal sol spinning solution of 2L and 50L water, the thin diameter Zirconium oxide fibre weak point that takes by weighing is cut to the length of 2mm～5mm, with the poly-zirconium colloidal sol spinning solution dilute with water of measuring, add together in the slurrying pond, stir 12min, fiber is uniformly dispersed in adhesive solution, form cotton pulp, the bottom is evenly distributed with the 2mm aperture, long * wide * as to put into the slurrying pond for the formation mould of 300mm * 200mm * 21mm deeply, open vacuum-pumping system, the fiber cotton pulp is sucked in the mould, moisture is sucked away, and fiber layer by layer laying in mould, form the wet base of certain thickness fiberboard, take out and the back-off mould, the wet base of fiberboard is fallen within on the supporting plate of flat surfaces, above wet base, cover pressing plate, clamp surface is smooth, four jiaos of its lower surface are equipped with the double-screw bolt that highly is 20.1mm, apply the wet base of pressure extrusion fiberboard of 0.1MPa downwards, four jiaos of double-screw bolts until pressing plate all contact with the surface of below supporting plate, thereby the thickness that makes fiberboard evenly and reach the numerical value of accurate control, supporting plate is placed 100 ℃ baking oven together with the wet base of fiberboard, baking 30h is to wet base bone dry, fiberboard after the oven dry is placed the high-temperature calcination stove, programming rate with 3 ℃/min is warming up to 1600 ℃, and insulation 4h, obtain length of the present invention * wide * thick 300mm * 200mm * 20mm of being, density is 0.6cm
3/ g, cube crystalline phase, thickness are evenly, surfacing, fiber arrange layer by layer, superimposed closely, mechanical property and all good zirconium oxide fiber board of high temperature bending resistance.Test shows that the compression strength of zirconium oxide fiber board can reach 0.50MPa, and the fiberboard two ends are propped, and middle span 200mm at 1650 ℃ of calcining 24h, any flexural deformation does not take place.
Claims (8)
1. the preparation method of a thin diameter Zirconium oxide fibre, it is characterized in that: adopt zirconium oxycarbonate, glacial acetic acid, water, yttrium nitrate as the poly-zirconium colloidal sol spinning solution of feedstock production, get rid of silk and high speed thermal current winding-up drawing-off and obtain thin diameter and gather the zirconium gelatinous fibre through ultrahigh speed is centrifugal, obtain thin diameter Zirconium oxide fibre through the heat treatment sintering again.
2. the preparation method of thin diameter Zirconium oxide fibre according to claim 1, the concrete operations that it is characterized in that preparing poly-zirconium colloidal sol spinning solution are as follows: according to ZrO in the reaction system
2: glacial acetic acid: the mol ratio of water is 1: 2～3: 15～25 ratio, take by weighing the zirconium oxycarbonate of corresponding mass, and measure the glacial acetic acid and the water of corresponding volume, glacial acetic acid is diluted in the water, 70 ℃～80 ℃, stir and the condition of bleeding under, with acetic acid aqueous solution and zirconium oxycarbonate hybrid reaction, generate the basic zirconium acetate hydrating polymer and with CO
2Gas is overflowed, treat that solid all dissolves, reaction solution become transparent after, promptly obtained poly-aqueous zirconium, be ZrO according to the composition ratio requirement of complete stable cubic phase zircite
2: Y
2O
3Mol ratio be 92～90: 8～10 ratio, in the above-mentioned poly-aqueous zirconium that makes, add phase stabiliser raw material yttrium nitrate, stirring makes its dissolving, decompression distillation is 10Pas～50Pas until obtaining viscosity, has a poly-zirconium colloidal sol spinning solution of good fibre-forming performance sloughing excessive moisture under 70 ℃～80 ℃ conditions afterwards.
3. the preparation method of thin diameter Zirconium oxide fibre according to claim 1, the concrete grammar that it is characterized in that the poly-zirconium gelatinous fibre of the thin diameter of described acquisition is: above-mentioned prepared poly-zirconium colloidal sol spinning solution is injected the centrifugal swaying wire equipment of ultrahigh speed, under the high speed rotation of 20,000 commentaries on classics/min～30,000 commentaries on classics/min, making spinning solution is centrifugal the throwing away of aperture along continuous straight runs of 0.2mm～0.5mm from the aperture, it is 80 ℃～100 ℃ in temperature immediately, air velocity is 10m/s～50m/s, blowing direction is under the downward high speed thermal current winding-up of annular, by further drawing-off, solidify, obtain the poly-zirconium gelatinous fibre of thin diameter.
4. the preparation method of thin diameter Zirconium oxide fibre according to claim 1, the concrete operations that it is characterized in that described heat treatment sintering are as follows: the poly-zirconium gelatinous fibre of the thin diameter of above-mentioned acquisition is put into program control heat treatment electric furnace, programming rate with 1 ℃/min～3 ℃/min is warming up to 500 ℃, programming rate with 3 ℃/min～5 ℃/min is warming up to 1100 ℃～1300 ℃ again, and be incubated 2h～4h, promptly obtain the thin diameter Zirconium oxide fibre of diameter 3 μ m～6 μ m, cube phase.
5. the preparation method of a zirconium oxide fiber board, it is characterized in that: adopting thin diameter Zirconium oxide fibre is raw material, and poly-zirconium colloidal sol spinning solution thin up is a binding agent, adopts the method for vacuum filtering shape process and pressurization leveling to prepare the wet base of fiberboard, oven dry, calcining obtains zirconium oxide fiber board.
6. the preparation method of zirconium oxide fiber board according to claim 5, it is characterized in that concrete grammar is as follows: adopting thin diameter Zirconium oxide fibre is raw material, and to adopt viscosity be that the poly-zirconium colloidal sol spinning solution thin up of 10Pas～50Pas is made binding agent, ratio according to poly-zirconium colloidal sol spinning solution: the 5L of 1kg fiber: 100ml～200ml～10L water, take by weighing the thin diameter Zirconium oxide fibre of respective quality, measure the poly-zirconium colloidal sol spinning solution and the water of respective volume, the thin diameter Zirconium oxide fibre weak point that takes by weighing is cut to the length of 2mm～5mm, with the poly-zirconium colloidal sol spinning solution dilute with water of measuring, add together in the slurrying pond, stir more than the 5min, fiber is uniformly dispersed in adhesive solution, form cotton pulp, the formation mould that the bottom is evenly distributed with the 2mm aperture is put into the slurrying pond, open vacuum-pumping system, the fiber cotton pulp is sucked in the mould, moisture is sucked away, and fiber layer by layer laying in mould, form the wet base of a fiberboard, take out and the back-off mould, the wet base of fiberboard is fallen within on the supporting plate of flat surfaces, above wet base, cover pressing plate, clamp surface is smooth, four jiaos of its lower surface are equipped with highly consistent double-screw bolt, apply the wet base of pressure extrusion fiberboard of 0.1MPa～0.3MPa downwards, four jiaos of double-screw bolts until pressing plate all contact with the surface of below supporting plate, thereby the thickness that makes fiberboard evenly and reach the numerical value of accurate control, supporting plate is placed 100 ℃～120 ℃ baking oven together with the wet base of fiberboard, baking 20h～30h is to wet base bone dry, fiberboard after the oven dry is placed the high-temperature calcination stove, programming rate with 3 ℃/min～5 ℃/min is warming up to 1600 ℃～1800 ℃, and insulation 2h～4h, promptly obtain zirconium oxide fiber board.
7. the preparation method of zirconium oxide fiber board according to claim 5, it is characterized in that: described thin diameter Zirconium oxide fibre is the Zirconium oxide fibre of diameter 3 μ m～6 μ m, cube phase.
8. the preparation method of zirconium oxide fiber board according to claim 5 is characterized in that the preparation method of described poly-zirconium colloidal sol spinning solution is as follows: according to ZrO in the reaction system
2: glacial acetic acid: the mol ratio of water is 1: 2～3: 15～25 ratio, take by weighing the zirconium oxycarbonate of corresponding mass, and measure the glacial acetic acid and the water of corresponding volume, glacial acetic acid is diluted in the water, 70 ℃～80 ℃, stir and the condition of bleeding under, with acetic acid aqueous solution and zirconium oxycarbonate hybrid reaction, generate the basic zirconium acetate hydrating polymer and with CO
2Gas is overflowed, treat that solid all dissolves, reaction solution become transparent after, promptly obtained poly-aqueous zirconium, be ZrO according to the composition ratio requirement of complete stable cubic phase zircite
2: Y
2O
3Mol ratio be 92～90: 8～10 ratio, in the above-mentioned poly-aqueous zirconium that makes, add phase stabiliser raw material yttrium nitrate, stirring makes its dissolving, and decompression distillation is the poly-zirconium colloidal sol spinning solution of 10Pas～50Pas to slough excessive moisture until obtaining viscosity under 70 ℃～80 ℃ conditions afterwards.
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Effective date of registration: 20130513 Address after: 211212, No. 6, Jingang Road, three industrial park, 15 Town, Lishui County, Jiangsu, Nanjing Patentee after: NUST YULONG NEW MATERIALS SCIENCE & TECHNOLOGY CO., LTD. Address before: 210094 Xiaolingwei, Jiangsu, No. 200, Patentee before: Nanjing University of Science and Technology |
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Address after: 211299 building 6, No.15, Jingang Road, Dongping Town, Lishui District, Nanjing City, Jiangsu Province Patentee after: NANJING POLYTECHNIC YULONG NEW MATERIALS POLYTRON TECHNOLOGY Co.,Ltd. Address before: 211212 building 6, No.15, Jingang Road, No.3 Industrial Park, Dongping Town, Lishui County, Nanjing City, Jiangsu Province Patentee before: NUST YULONG NEW MATERIALS SCIENCE & TECHNOLOGY Co.,Ltd. |
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