CN100372969C - Nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides and its production method - Google Patents
Nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides and its production method Download PDFInfo
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Abstract
The present invention relates to nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides, which is characterized in that the aggregate powder is prepared from nano ZrO2 powder particles which comprise 0.3 to 30 wt% of Al2O3 and 3 to 9 wt% of Y2O3; the average crystal size of the particles is from 5 nm to 60 nm; nano oxide particles in the aggregate powder come into contact with each other in a body surface way, and the nonexposed position is a purity cavity. The method of the present invention comprises the following steps: water is added in the particles of nano tertiary compound oxides, and aquosity suspended colloids are obtained; the nano-structured aggregate powder is prepared by spray drying, sieving, heat treatment and plasma densifying. The present invention has the advantages of few technical processes and simple operation; the nano-structured aggregate powder can be continuously produced in an industrial way on a large scale with low cost; the product of the present invention can meet the technical requirements for hot spraying, such as plasma spraying, flame spraying, electric arc spraying, etc.
Description
Technical field
The present invention relates to a kind of aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides material and production technique thereof, this powdered material is specially adapted to thermospray (plasma spraying or flame plating) prepared thermal barrier coating or high-sintering process prepares structural ceramics.
Background technology
Zirconium white (ZrO
2) have excellent physics and chemical property, be a kind of important 26S Proteasome Structure and Function stupalith.Common ZrO
2℃ exist mutually at normal temperature to 1170, change cubic phase when being heated to 1170 ℃～2370 ℃ into, become cube phase (2700 ℃ of left and right sides fusions) by tetragonal phase converting in the time of more than 2370 ℃ with monocline.Because pure ZrO
2High temperature phase (cube phase or cubic phase) can be transformed into low temperature phase (monocline phase) along with the reduction of temperature, and be attended by the volumetric expansion about 5～7%.Pure ZrO
2This crystal transition and volume change, if as structural ceramics and function ceramics coated material,, make ceramic product or coating cracking and spalling failure being subjected to can causing excessive thermal stress under the thermal cycle conditions.Obtain high temperature phase ZrO stable under the room temperature
2, just need be at ZrO
2Middle some other oxide compound that mixes as yttrium oxide, calcium oxide, magnesium oxide, cerium oxide, Y2O3 etc., forms ZrO
2Composite oxides.The ZrO that other is oxide-doped
2Composite oxides have application widely at structural ceramic material and ceramic material field.
ZrO
2Be applied to the research of thermal barrier coating, after succeeing on the whirlpool steam turbine of the seventies in 20th century, both at home and abroad to ZrO
2The research of coating reaches a peak in the eighties in 20th century, and a large amount of studies show that, yttrium oxide (Y
2O
3) stable ZrO
2Material (Y wherein
2O
3Massfraction is 6～8%), Y2O3 (Al
2O
3)/Y
2O
3Stable ZrO
2Material, and cerium oxide/Y
2O
3Stable ZrO
2Materials etc. all have superior thermal shock resistance.
The ZrO that aluminium and yttrium are stable
2As the heat barrier coat material of widespread use, compare with other ceramic coating material, have high temperature resistant, corrosion-resistant, wear-resistant, high intensity and fracture toughness property, high coefficient of linear expansion (near metal matrix, is about 10 * 10
-6/ K) and low thermal conductivity excellent properties such as (1W/mK), especially when 1000 ℃ of high temperature, its thermal conductivity numerical value is minimum in all dense ceramic material, it is mutually compound with metallic matrix with coating form, and makes it can stand higher use temperature when improving metal fever end pieces opposing high temperature corrosion ability.
Since 20 end of the centurys, along with the maturation of nanosecond science and technology and nano powder preparation technology, nanometer ZrO
2The preparation of coating has become the emphasis of research gradually, utilizes the nanostructure ceramic heat-barrier coating of nanotechnology exploitation to be meant the microstructure of ceramic coating such as the nanometer level (2～100nm) that crystal grain, hole etc. are in ultra-fine size.Thereby mechanics and physicals to coating produce material impact, obtain the performance more excellent than ordinary hot barrier coating.
Thermal barrier coating often uses being higher than under 1000 ℃ the condition, and the speed of growth of nano crystal particles is very fast under the high temperature, can make the performance degradation of nanostructure thermal barrier coating.Al
2O
3Doping also have and suppress ZrO under the high temperature
2The effect that crystal grain is grown up makes coating in use still keep nanostructure, and big variation does not take place performance.
The key of preparation nanostructure thermal barrier coating is a hot-spraying nano structure aggregate powder of AI/Yt, and it must keep nanostructure, and satisfies the requirement of spraying coating process, as granular size and distribution thereof, particle shape, flowability etc.Because the mobile extreme difference of nano-powder can not satisfy the powder feeding requirement of spraying coating process.During thermospray, have only particle just can possess the required quality of plasma thermal sprayed when a certain size and density, granular mass is too little, can not obtain enough kinetic energy, and spray is less than workpiece surface.Prepare Al
2O
3/ Y
2O
3Stable ZrO
2The nanocrystalline structure thermal barrier coating, used nano-powder must pass through mist projection granulating and densification process, and nano raw material is made coacervate micron spraying powder, adopts plasma spraying or HVOF (High Velocity Oxygen Fuel) Technology to be deposited as coating again.So Al
2O
3/ Y
2O
3Stabilized nanoscale structure ZrO
2The exploitation of aggregate powder of AI/Yt and production technique thereof, it is the prerequisite of preparation nanostructure thermal barrier coating, its key is to keep nanocrystalline structure constant, is satisfied with plasma spraying or HVOF (High Velocity Oxygen Fuel) processing requirement again, and obtains the due high-performance of nanostructure thermal barrier coating.
The nanometer ZrO of present used for hot spraying
2The powder of coacervate mainly adopts spray-drying process and microemulsion method (reverse micelle method) preparation.These methods respectively have its characteristics, but also have many deficiencies.As spray-drying process is with nano level ZrO
2Micro mist mixes with a certain amount of binding agent, adds an amount of water or other solvents and is mixed with certain density slip.Adopt certain pressure that it is ejected in the drying tower, the surface tension by self is agglomerated into sphere when dry in hot blast.Shrink because aggregate powder of AI/Yt is a nature, the loose density of powder is little, and is mobile poor.Powder seems in the hot-spraying techniques process, and some " wafts ", can not obtain enough kinetic energy, so its coating density is not too high, can't obtain higher binding strength.Because the various organic additives that add in this method, it is clean all to volatilize under the hot conditions of thermal spray process utmost point short period of time again, is present in the coating with the form of tiny carbon granules, and the performance of coating is had a negative impact.Microemulsion method is a kind of milling method that development in recent years is got up.The powder that makes is spherical in shape, and globule size unanimity, weak point are the raisings of production cost, is difficult to realize mass-producing.In addition, what have is used in combination above-mentioned preparation method with plasma spraying pyrolyzing method, supercritical drying etc., only carried out some limited research and discussions, then too wide in the gap apart from production practical application and mass-producing.
Purpose of the present invention just provides a kind of aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides, it does not contain harmful impurity, the aggregate density height, good fluidity, the needs of nanostructure hot-spraying techniques and high-sintering process can be satisfied, higher coating density and higher binding strength can be obtained.
Another object of the present invention provides the production method of aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides, and this technical matters flow process is few, working method is simple, turnout is big, and is safe and reliable, and low cost of manufacture is suitable for suitability for industrialized production.
Summary of the invention
Aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides that the present invention proposes is characterized in that this aggregate powder of AI/Yt is by containing 0.3～30wt%Al
2O
3With 3～9wt%Y
2O
3Nanometer ZrO
2Powder granule constitutes, and the particulate average mean crystal size is 5nm～60nm, is the body surface contact between the nano-oxide particles in the aggregate powder of AI/Yt, and Jie Chu place is not pure cavity.。
Aforesaid aggregate powder of AI/Yt is characterized in that crystalline structure is respectively monocline ten cubic phases (cube phase) or pure cubic phase (cube phase) mutually.
The production method of aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that comprising the steps:
Preparation aluminium/yttrium/zirconium ternary composite nano oxide powder granule, wherein Al
2O
3Be 0.3～30wt%, Y
2O
3Be 3～9wt%;
With aluminium/yttrium stabilized nano level ZrO
2Powder granule mixes with water, is prepared into the water nano suspensoid;
Adopt drying process with atomizing that the water nano suspensoid is made the micron order aggregate powder of AI/Yt;
Aggregate powder of AI/Yt is heat-treated;
Powder after adopting plasma technology to thermal treatment carries out densification, obtains the aluminium/yttrium stable zirconium oxide agglomerate body powder of nanostructure.
The production method of aforesaid aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that used aluminium/yttrium stabilized nanoscale Zirconium powder feed particles granularity is between 5～60nm.
The production method of aforesaid aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that water nano particle suspension colloidal medium is a water, and the weight ratio of nano particle and water is 1: 1～3.
The production method of aforesaid aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that spray drying process can be one of two fluid-types or centrifugal spray-drying process.
The production method of aforesaid aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that the thermal treatment of spray-dried powders was carried out 5～30 minutes at 200～600 ℃.
The production method of aforesaid aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides, the plasma body densificationization that it is characterized in that aggregate powder of AI/Yt can be direct-current plasma or high-frequency induction plasma body.
The production method of aforesaid aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that ternary composite Nano ZrO
2The preparation process of powder granule is: it is water-soluble to get zirconium oxychloride, makes that zirconium ion concentration is 0.2～0.5 mol in the aqueous solution, adds the aluminum nitrate and the yttrium nitrate solution of 0.1 mol, control Y
2O
3At ZrO
2Doping in the powder is 3～9wt%, Al
2O
3Doping be 0.3～30wt%; Add a certain amount of ethanol, the ammoniacal liquor of Dropwise 5 0% volume ratio is greater than 9 until the pH value of solution value under brute force stirs; Ceramic membrane separation of hydrogen oxide precipitation, distilled water wash precipitation detect in filtrate less than chlorion; Centrifugal or the press filtration with throw out is got precipitation of hydroxide and is mixed with the butanols of 2 times of weight ratios, with milling treatment of colloid or powerful the stirring; Place distillation drying and dehydrating device,,, in 450～800 ℃ of calcining powders 2 hours, obtain ternary composite nano oxide powder granule raw material in the High Temperature Furnaces Heating Apparatus until the powder complete drying in 150 ℃ of dehydrations.
The production method of the oxide agglomerate body powder of ternary composite nanostructure, concrete steps are as follows:
(1) preparation of ternary composite nano oxide powder.Can adopt the existent method preparation, but we advise adopting following method preparation, compared with the prior art it have accurate, the advantages such as crystal size even, good dispersity of doping of element.It is water-soluble to get zirconium oxychloride, makes that zirconium ion concentration is 0.2～0.5 mol in the aqueous solution, adds the aluminum nitrate and the yttrium nitrate solution of 0.1 mol, control Y
2O
3At ZrO
2Doping in the powder is 3～9wt%, Al
2O
3Doping be 0.3～30wt%.Add a certain amount of ethanol, Dropwise 5 0% ammoniacal liquor (volume ratio) under brute force stirs is greater than 9 until the pH value of solution value.Ceramic membrane separation of hydrogen oxide precipitation, the distilled water wash precipitation detects less than chlorion (Silver Nitrate check) in filtrate.Centrifugal or the press filtration with throw out is got precipitation of hydroxide and is mixed with 2 times butanols (weight ratio), with milling treatment of colloid or powerful the stirring.Place distillation drying and dehydrating device,,, calcined powders 2 hours in 450～800 ℃ in the High Temperature Furnaces Heating Apparatus until the powder complete drying in 150 ℃ of dehydrations.Obtain ternary composite nano oxide powder granule raw material.
(2) the stable dispersion suspension colloid of preparation nano-powder.An amount of pure water will be added in the ternary composite nano oxide powder, the consumption of water is 1～3 times (weight ratio) of powder quality, inject colloidal mill after stirring, handled continuously 5～30 minutes, be prepared into nano-powder suspensoid with proper concn and certain viscosity.
(3) aqueous colloidal of ternary composite nano oxide powder is made the micron order aggregate powder of AI/Yt (granulation) with certain particle size distribution by drying process with atomizing.Spray pattern is centrifugal or two fluid-types, and the slip of atomizing relies on the surface tension of self to be shrunk to sphere, by warm air the water in the slip is volatilized fast, the dry spherical powder that forms of droplet.Spray-dired inlet temperature is 120～300 ℃, and air outlet temperature is controlled at 80～180 ℃, and the height of temperature is regulated and exceeded with the powder thorough drying.To collect in the exsiccant aggregate powder of AI/Yt suction cyclonic separator by exhausting subsequently.This process aggregate powder of AI/Yt still is a nanostructure, and granularity is 5～100 μ m, is shaped as sphere.
(4) screening.Because spray-dired spherical agglomerates powder has certain particle distribution (5～100 μ m), pass through mechanical grading, choose the powder (40～100 μ m) that meets the finished product size range that the plasma spraying thermal barrier coating uses, other powder are made colloid, mist projection granulating once more more again.
The thermal treatment of (5) prilling powders.With charging tray 200～600 ℃ of thermal treatments of carrying out 5～30 minutes in the van-type High Temperature Furnaces Heating Apparatus of packing into of a prilling powder of 40～100 μ m granularities.Remove the residual water-content in the powder, eliminate the relaxation phenomena and the internal stress at nano particle interface in the powder, reduce the grain breakage rate in the plasma body densificationization powder feeding process, improve product quality and productive rate.
(6) densification of coacervate.Because the aggregate powder of AI/Yt structure of a granulation is looser, broken easily, in thermal spray process, easily float, sedimentation effect is not high, and the coating of formation is not fine and close.Need carry out densification (the fine and close nodularization of plasma) to the aggregate powder of AI/Yt of a granulation.The plasma body that adopts can be high-frequency induction plasma body or direct-current plasma, and temperature is 5000～10000 ℃, and gases used is air, argon gas, hydrogen and nitrogen.Adopt the mode of quenching (water-cooled or air cooling) to collect powder, crystalline is grown up in the control powder.Strictly control the power parameter and the operational throughput of grain aggregate powder of AI/Yt once, manufacture not only densification but also keep nanocrystalline structure constant.
(7) aluminium/yttrium/Zr ternary compound oxides nanostructure coacervate hot spray powder finished product.With collect through the aggregate powder of AI/Yt of plasma body densificationization in 100～300 ℃ of oven dry, sieve again, obtain the powder-product of finished product powder index request.
The gordian technique and the craft feature of product of the present invention are:
(1) do not use any additives (caking agent, suspension agent, dispersion agent, wetting agent, tensio-active agent) in the aqueous colloidal preparation process, but directly utilize the natural characteristics (particle surface unsaturation chemical bond is many, surfactivity big, be easy to the absorption bonding) of nano-powder and the key bridge reactive force of water, in spray process, form aggregate powder of AI/Yt.All technological process can not introduced any impurity, has avoided pollution, has guaranteed high purity, high-specific surface area and certain surfactivity of product.
(2) the nanocrystal granularity in spray drying technology of Cai Yonging (prilling process) and transient plasma densification technology (secondary granulation method) the restriction aggregate powder of AI/Yt grows up, keep its grain-size constant substantially, for the realization of follow-up plasma spraying nano coating is laid a good foundation.
(3) aluminium/when the nano oxidized zirconium coating of yttrium compound was worked under hot conditions, crystalline growth velocity was slow, and coating performance is stable, long service life.
(4) it is relatively low that nano raw material prepares the aggregate powder of AI/Yt cost, is easy to promote.
(5) because spray drying technology (prilling process) and plasma body densificationization technology (secondary granulation method) all belong to sophisticated industrial agglomeration technique, by the control of technical parameter and the transformation of critical process process, the whole preparation process flow process is few, equipment is simple, processing parameter is easy to control, is suitable for serialization scale operation.
Description of drawings
Fig. 1 is the structural representation of embodiment of the invention aggregate powder of AI/Yt inside.Wherein, 1 aggregate powder of AI/Yt, 2 nano particles, 3 body surface contact surfaces, 4 pure cavitys.
Fig. 2 is the sem photograph of the aggregate powder of AI/Yt of a granulation of the embodiment of the invention.
Fig. 3 is the sem photograph of the aggregate powder of AI/Yt of embodiment of the invention secondary granulation.
Concrete embodiment
In order to be illustrated more clearly in the present invention, enumerate following specific embodiment.
Embodiment 1:
Get 20 kilograms of zirconium oxychlorides and be dissolved in 100 premium on currency, add the aluminum nitrate and the yttrium nitrate solution of 0.1 mol, control Y
2O
3At ZrO
2Doping in the powder is 4wt%, Al
2O
3Doping be 2wt%.Add a certain amount of ethanol, Dropwise 5 0% ammoniacal liquor (volume ratio) under brute force stirs is greater than 9 until the pH value of solution value.Ceramic membrane separation of hydrogen oxide precipitation, the distilled water wash precipitation detects less than chlorion (Silver Nitrate check) in filtrate.Centrifugal or the press filtration with throw out is got precipitation of hydroxide and is mixed with 2 times butanols (weight ratio), with milling treatment of colloid or powerful the stirring.Place distillation drying and dehydrating device,,, calcined powders 2 hours in 800 ℃ in the High Temperature Furnaces Heating Apparatus until the powder complete drying in 150 ℃ of dehydrations.Obtaining median size is the ternary composite nano oxide powder granule raw material of 20nm.
Get 10 kilograms of nano oxide powders, add 15 kilograms ultra-pure water, stir, use colloidal mill homodisperse 10 minutes, it is stand-by to be prepared into stable suspension slip.
With carrying gas through the pressurized air that purifies, gaseous tension is controlled at 0.3～0.8MPa, take two fluid-type nozzles that slip is sprayed in the drying tower, the slip of atomizing relies on the surface tension of self to be shrunk to conglobation, the intake air temperature of drying tower is controlled at 150 ℃, the air outlet temperature is controlled at 100 ℃, makes aerosol mist drop in thorough drying in the hot blast.To collect in the exsiccant aggregate powder of AI/Yt suction cyclonic separator by exhausting subsequently.
The powder of collecting is sieved with mechanical sub-sieve, present embodiment finished powder size range is between 40～100 μ m (i.e. 150～350 orders), granularity greater than 100 μ m, less than the powder of 40 μ m as foundry returns, when carrying out a granulation next time, make slip again.
With the charging tray 300 ℃ of thermal treatment 20 minutes in the van-type High Temperature Furnaces Heating Apparatus of packing into of a prilling powder of 40～100 μ m granularities.Remove the residual water-content in the powder, eliminate the relaxation phenomena and the internal stress at nano particle interface in the powder, reduce the grain breakage rate in the plasma body densificationization powder feeding process, improve product quality and productive rate.
The using plasma technology is to the heat treated prilling powder densification of process, and plasma power 30kW, argon gas, hydrogen and nitrogen are working gas, by powder feeder the powder of a granulation are delivered to the plasma flame flow center, powder feed rate 60g/ minute.Make powder in the extremely short time, reach fine and close nodularization, spray quenching collection in the entry.The secondary granulation powder of the collecting oven dry of in 100～300 ℃ baking oven or High Temperature Furnaces Heating Apparatus, heating, remove moisture content.Obtain the ternary compound oxides aggregate powder of AI/Yt of nanostructure.
The content of effective of aggregate powder of AI/Yt is greater than 99.9%, and the content that is present in the trace impurity in the nano particle is less than 0.1%.
The loose density of measuring powder with the Hall under meter is 1.95g/cm
3, flowability is 46s/50g; The pattern that scanning electron microscope is measured powder is a dense spherical, and X ray powder crystal diffraction is measured the crystalline structure and the primary particle crystalline mean particle size of powder, and the mean particle size of primary particle is 38nm.
Embodiment 2:
Method by embodiment 1 prepares the ternary compound oxides powder, gets 10 kilograms of powders, adds 15 kilograms ultra-pure water, stirs, and uses colloidal mill homodisperse 10 minutes, and it is stand-by to be prepared into stable suspension slip.
With the centrifugal atomizing dish slip is sprayed in the drying tower, the rotating speed of centrifugal atomizer is 10000r/min, the slip particulate of atomizing relies on the surface tension of self to be shrunk to conglobation, hot blast in dry, the heating and temperature control of drying tower well heater is at 180 ℃, make the moisture rapid evaporation in the droplet, collect the exsiccant aggregate powder of AI/Yt with cyclonic separator.The powder of collecting is sieved with mechanical sub-sieve, and size range is continuing to employ between 40～100 μ m, granularity greater than 100 μ m, less than the powder of 40 μ m as foundry returns, when carrying out a granulation next time, make slip again.
With the charging tray 500 ℃ of thermal treatment 10 minutes in the van-type heat treatment furnace of packing into of the dried powder of 40～100 μ m granularities.Remove the residual water-content in the powder, eliminate the relaxation phenomena and the internal stress at nano particle interface in the powder, reduce the grain breakage rate in the plasma body densificationization powder feeding process, improve product quality and productive rate.
The using plasma technology is to carrying out densification through heat treated prilling powder, and plasma power 30kW, argon gas, hydrogen and nitrogen are working gas, by powder feeder the powder of a granulation are delivered to the plasma flame flow center, powder feed rate 60g/ minute.Make powder in the extremely short time, reach fine and close nodularization, spray quenching collection in the entry.The secondary granulation powder of the collecting oven dry of in 100～300 ℃ baking oven or High Temperature Furnaces Heating Apparatus, heating, remove moisture content.Obtain the ternary compound oxides aggregate powder of AI/Yt of nanostructure.
The powder content of effective is greater than 99.9%, and the content that is present in the trace impurity in the nano particle is less than 0.1%.
The loose density of measuring powder with the Hall under meter is 2.06g/cm
3, flowability is 44s/50g; The pattern that scanning electron microscope is measured powder is fine and close solid sphere, and X ray powder crystal diffraction is measured the crystalline structure and the primary particle crystalline mean particle size of powder, and the mean particle size of primary particle is 40nm.
Embodiment 3:
Method by embodiment 1 prepares ternary oxide nano-powder, wherein Al
2O
3Content be 3wt%, Y
2O
3Content be 8wt%, 600 ℃ of calcining temperatures, crystalline median size 10nm.
Get 10 kilograms of nano oxide powders, add 20 kilograms ultra-pure water, stir, use colloidal mill homodisperse 10 minutes, it is stand-by to be prepared into stable suspension slip.
With carrying gas through the pressurized air that purifies, gaseous tension is controlled at 0.3～0.8MPa, take two fluid-type nozzles that slip is sprayed in the drying tower, the slip of atomizing relies on the surface tension of self to be shrunk to conglobation, the intake air temperature of drying tower is controlled at 200 ℃, the air outlet temperature is controlled at 130 ℃, makes aerosol mist drop in thorough drying in the hot blast.To collect in the exsiccant aggregate powder of AI/Yt suction cyclonic separator by exhausting subsequently.
The powder of collecting is sieved with mechanical sub-sieve, and present embodiment finished powder size range is between 40～100 μ m, granularity greater than 100 μ m, less than the powder of 40 μ m as foundry returns, when carrying out a granulation next time, make slip again.
With the charging tray 300 ℃ of thermal treatment 20 minutes in the van-type High Temperature Furnaces Heating Apparatus of packing into of a prilling powder of 40～100 μ m granularities.Remove the residual water-content in the powder, eliminate the relaxation phenomena and the internal stress at nano particle interface in the powder, reduce the grain breakage rate in the plasma body densificationization powder feeding process, improve product quality and productive rate.
The using plasma technology is to the heat treated prilling powder densification of process, and plasma power 50kW, argon gas, hydrogen and nitrogen are working gas, by powder feeder the powder of a granulation are delivered to the plasma flame flow center, powder feed rate 100g/ minute.Make powder in the extremely short time, reach fine and close nodularization, spray quenching collection in the entry.The secondary granulation powder of the collecting oven dry of in 100～300 ℃ baking oven or High Temperature Furnaces Heating Apparatus, heating, remove moisture content.Obtain the aggregate powder of AI/Yt finished product after the screening.
The content of effective of aggregate powder of AI/Yt is greater than 99.9%, and the content that is present in the trace impurity in the nano particle is less than 0.1%.
The loose density of measuring powder with the Hall under meter is 1.94g/cm
3, flowability is 48s/50g; The pattern that scanning electron microscope is measured powder is fine and close solid sphere, and X ray powder crystal diffraction is measured the crystalline structure and the primary particle crystalline mean particle size of powder, and the mean particle size of primary particle is 36nm.
Embodiment 4:
Method by embodiment 1 prepares ternary oxide nano-powder, wherein Al
2O
3Content be 3wt%, Y
2O
3Content be 8wt%, 600 ℃ of calcining temperatures, crystalline median size 10nm.
Get 10 kilograms of nanometer ternary oxide powders, add 20 kilograms ultra-pure water, stir, use colloidal mill homodisperse 10 minutes, it is stand-by to be prepared into stable suspension slip.
With the centrifugal atomizing dish slip is sprayed in the drying tower, the rotating speed of centrifugal atomizer is 15000r/min, the slip particulate of atomizing relies on the surface tension of self to be shrunk to conglobation, hot blast in dry, the heating and temperature control of drying tower well heater is at 130 ℃, make the moisture rapid evaporation in the droplet, collect the exsiccant aggregate powder of AI/Yt with cyclonic separator.The powder of collecting is sieved with mechanical sub-sieve, and size range is continuing to employ between 40～100 μ m, granularity greater than 100 μ m, less than the powder of 40 μ m as foundry returns, when carrying out a granulation next time, make slip again.
With the charging tray 400 ℃ of thermal treatment 20 minutes in the van-type High Temperature Furnaces Heating Apparatus of packing into of a prilling powder of 40～100 μ m granularities.Remove the residual water-content in the powder, eliminate the relaxation phenomena and the internal stress at nano particle interface in the powder, reduce the grain breakage rate in the plasma body densificationization powder feeding process, improve product quality and productive rate.
The using plasma technology is to the heat treated prilling powder densification of process, and plasma power 30kW, argon gas, hydrogen and nitrogen are working gas, by powder feeder the powder of a granulation are delivered to the plasma flame flow center, powder feed rate 80g/ minute.Make powder in the extremely short time, reach fine and close nodularization, spray quenching collection in the entry.The secondary granulation powder of the collecting oven dry of in 100～300 ℃ baking oven or High Temperature Furnaces Heating Apparatus, heating, remove moisture content.Obtain the aggregate powder of AI/Yt finished product after the screening.The content of effective of aggregate powder of AI/Yt is greater than 99.9%, and the content that is present in the trace impurity in the nano particle is less than 0.1%.
The loose density of measuring powder with the Hall under meter is 2.10g/cm
3, flowability is 38s/50g; The pattern that scanning electron microscope is measured powder is fine and close solid sphere, and X ray powder crystal diffraction is measured the crystalline structure and the primary particle crystalline mean particle size of powder, and the mean particle size of primary particle is 45nm.
Nanostructure ternary compound oxides aggregate powder of AI/Yt of the present invention becomes thermal barrier coating through the plasma spraying prepared, coat-thickness 300～400 μ m.Through to its Performance Detection, to compare with the micrometer structure coating of routine, the microhardness of nano-structured coating is 1.5～1.8 times of conventional micron coating; Anti-thermal shock (thermal shocking) performance improves at least 2～3 times; Shock resistance (reflection coating toughness and cracking resistance line extended capability) obviously strengthens; Bond Strength of Coating has improved 1.5 times; Effect of heat insulation has improved 1.5～2 times.Ternary composite nanostructure Zirconium oxide heat barrier coating has important application prospects in industries such as aerospace, large-scale gas turbine, boats and ships, automobile, machinery, chemical industry.
The protection domain of present patent application is not subjected to above-mentioned restriction of giving an example.By the disclosed aluminium/yttrium of present patent application/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides, mainly utilize characteristics such as its heat-conduction coefficient is low, coefficient of linear expansion is big, high-temperature stability is good, can be widely used in hot-spraying techniques and prepare various high temperature resistance thermal barrier coatings and high temperature resistance abrasion performance, corrosion-resistant finishes, high-sintering process prepares structural ceramics etc.
Nanostructure ternary compound oxides aggregate powder of AI/Yt of the present invention can also adopt and cold pressing or hot binding high temperature (microwave) sintering process prepares high performance structure ceramic, and densification temperature can reduce by 200～300 ℃.
Claims (8)
1. aluminium/yttrium/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that this aggregate powder of AI/Yt is by containing 0.3～30Wt%Al
2O
3With 3～9Wt%Y
2O
3Nanometer ZrO
2Powder granule constitutes, and the particulate average mean crystal size is 5nm～60nm, is the body surface contact between the nano-oxide particles in the aggregate powder of AI/Yt, and Jie Chu place is not pure cavity.
2. aggregate powder of AI/Yt as claimed in claim 1 is characterized in that crystalline structure is respectively monocline phase+four directions phase or pure cubic phase.
3. the production method of the described aluminium/yttrium of claim 1/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that comprising the steps:
Preparation aluminium/yttrium/zirconium ternary composite nano oxide powder granule, wherein Al
2O
2Be 0.3～30wt%, Y
2O
3Be 3～9wt%;
With aluminium/yttrium stabilized nano level ZrO
2Powder granule mixes with water, is prepared into the water nano suspensoid;
Adopt drying process with atomizing that the water nano suspensoid is made the micron order aggregate powder of AI/Yt;
Aggregate powder of AI/Yt is heat-treated;
Powder after adopting plasma technology to thermal treatment carries out densification, obtains the aluminium/yttrium stable zirconium oxide agglomerate body powder of nanostructure.
4. the production method of aluminium/yttrium as claimed in claim 3/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that used aluminium/yttrium stabilized nanoscale Zirconium powder feed particles granularity is between 5～60nm.
5. the production method of aluminium/yttrium as claimed in claim 4/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that water nano particle suspension colloidal medium is a water, and the weight ratio of nano particle and water is 1: 1～3.
6. the production method of aluminium/yttrium as claimed in claim 5/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that spray drying process can be one of two fluid-types or centrifugal spray-drying process.
7. the production method of aluminium/yttrium as claimed in claim 6/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that the thermal treatment of spray-dried powders was carried out 5～30 minutes at 200～600 ℃.
8. the production method of aluminium/yttrium as claimed in claim 3/nano-structured aggregate powder of AI/Yt/Zr ternary compound oxides is characterized in that ternary composite Nano ZrO
2The preparation process of powder granule is: it is water-soluble to get zirconium oxychloride, makes that zirconium ion concentration is 0.2～0.5 mol in the aqueous solution, adds the aluminum nitrate and the yttrium nitrate solution of 0.1 mol, control Y
2O
3At ZrO
2Doping in the powder is 3～9wt%, Al
2O
3Doping be 0.3～30wt%; Add a certain amount of ethanol, the ammoniacal liquor of Dropwise 5 0% volume ratio is greater than 9 until the pH value of solution value under brute force stirs; Ceramic membrane separation of hydrogen oxide precipitation, distilled water wash precipitation detect in filtrate less than chlorion; Centrifugal or the press filtration with throw out is got precipitation of hydroxide and is mixed with the butanols of 2 times of weight ratios, with milling treatment of colloid or powerful the stirring; Place distillation drying and dehydrating device,,, in 450～800 ℃ of calcining powders 2 hours, obtain ternary composite nano oxide powder granule raw material in the High Temperature Furnaces Heating Apparatus until the powder complete drying in 150 ℃ of dehydrations.
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| CN1397597A (en) * | 2001-09-13 | 2003-02-19 | 湖北葛店开发区地大纳米材料制造有限公司 | Process for preparing nano zirconium oxide powder |
| CN1562887A (en) * | 2004-03-31 | 2005-01-12 | 南京工业大学 | Composite powder of zirconia in high square phase and alumina and preparation method |
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| CN1369462A (en) * | 2002-03-21 | 2002-09-18 | 武汉发瑞精密陶瓷有限公司 | Superfine powder as raw material of high-performance zirconium oxide ceramics and its preparing process |
| CN1562887A (en) * | 2004-03-31 | 2005-01-12 | 南京工业大学 | Composite powder of zirconia in high square phase and alumina and preparation method |
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