CN109592981A - A kind of porous rare earth titanate heat-barrier material and its preparation method and application - Google Patents
A kind of porous rare earth titanate heat-barrier material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of porous rare earth titanate heat-barrier material and its preparation method and application, the porous rare earth titanate heat-barrier material have porous structure, group become (Re2O3)X(TiO2)1‑X, wherein Re is at least one of Y, lanthanide series, X=0.2~0.8, preferably X=0.4~0.7；The porosity of the porous rare earth titanate heat-barrier material is 10~90%, and pore size is 0.1~500 micron.
Description
Technical field
The present invention relates to a kind of porous rare earth titanate heat-barrier material that can be used for high temperature, high humidity and nuclear reactor and its systems
Preparation Method belongs to Material Field.
Background technique
Nuclear power is most effective one of the approach using nuclear energy of the mankind as the least electric energy of greenhouse gas emission.In the world
The nuclear power station run now has more than 400, mainly two generation heap-type of presurized water reactor and boiling-water reactor.After Fukushima accidents in 2011
Each state is all promoting exploitation and is building more advanced and safe third generation presurized water reactor, and technical characteristics are using passive
Shutdown mode, can the reliable shutdown not against exterior power in emergency.Additionally by simplified pipeline and valve pump
Design, and reacted in high temperature thermal and hydric environment with water for zircaloy material cladding tubes and generate hydrogen, add dehydrogenation unit.?
Above reactor setting against gravity can circular flow cooling water tank, by will be stagnant by reactor core fusant when major accident
The technology (IVR) stayed in pressure vessel avoids the generation of nuclear leakage.US Westinghouse company has been introduced since two thousand seven in China
AP1000 type third generation pressurized-water reactor complete set technology, it is downpayment to build 4 units, engineering technology verified
Batch popularization is carried out afterwards.The autonomy-oriented intellectual property that the approach for introducing and absorbing and innovating again will be taken to obtain nuclear power technology simultaneously, is opened
Send out the more powerful presurized water reactors such as CAP1400.The fault-tolerant design concept of accident is proposed in recent years, by increasing safety allowance
The safety of nuclear power station is improved with depth of defense.Forth generation nuclear power station is also at verifying and experimental stage at present, by
The four generation nuclear reactor heap-type that GIF is defined include high temperature gas-cooled fast reactor, sodium-cooled fast reactor, lead cold dome, molten salt reactor, overcritical water cooling
Heap and ultra-high-temperature reactor.Current each big state of nuclear power is all researching and developing four generation heaps in investment huge fund.Tsinghua University, Chinese core is built and Huaneng Group
Group starts the common construction Shandong thermal power 250MW Rongcheng Shidao Bay modular high temperature gas cooled reactor of providing funds for 2012, and 2017
Start to load fuel.Chinese Academy of Sciences's Shanghai Applied Physics started to build seat of honour 2MW solid-state molten salt reactor in 2017.
The reactor core inner part of presurized water reactor all suffers from different degrees of high temperature and irradiation during military service to be influenced, and to be born
280-350 DEG C or so of hydro-thermal corrosion, the following forth generation nuclear reactor will be run under 500-950 DEG C of temperature field, and be on active service
Time limit is not less than 60 years.Based on these harsh Service Environments, the heat-barrier material of efficient stable is for improving the thermal efficiency and safety
Operation is of great significance.
Heat-barrier material used in nuclear reactor can be divided into out-pile, heap chamber and reactor core according to the position of installation.Heap chamber is main
It is for the ooling channel in each loop include that hot pipe section and cold tube section carry out isothermal holding.The thermal insulation material of hot pipe section is normal
Using mineral wool, calcium silicates and reflective metals part.But since fiber and granular heat-barrier material may go through pipeline
Crack simultaneously deposits to below reactor core, and main trend is using metallic reflection part at present.Patent ZL2012205668713.4 is provided
A kind of design of strip flex foils.Cold tube section mainly utilizes foam glass, glass fibre and various foamed plastics.Greatly
Partial heat preservation module is designed as the heat shield group detachable and interchangeable, the heat insulating member of presurized water reactor is usually customized by more than 10,000
At.Out-pile then mainly uses calcium silicate thermal insulation layer, accounts for 90% or more.It has durability and high tenacity, and can inhibit slow Ovshinsky
The stress corrosion cracking (SCC) of body stainless steel.Steam turbine is then mainly kept the temperature using calcium silicates or glass mat.
The reactor core heat-barrier material of pressurized water reactor and Supercritical-Pressure Light Water Cooled Reactor is required to reduce the pressure vessel of metal material,
The temperature of load-bearing part and cladding tubes etc., avoids creep failure, while slowing down hydro-thermal corrosion rate, extends service life.Oxide
Ceramic material has superior high-temperature stability, such as aluminium oxide, zirconium oxide, magnesium aluminate spinel etc. than non-oxide ceramics.Its
In, most widely used at present is that yttrium stable zirconium oxide is ceramic (YSZ).It has low thermal conductivity and good at normal temperature
Mechanical strength.The Supercritical-Pressure Light Water Cooled Reactor of Canada's design makes the temperature of pressure vessel using the heat-barrier material of 10mm oxidation zirconium base
100 DEG C or so are reduced to from 650 DEG C.But since reactor operating temperature is usually fluctuated at 300 DEG C or more, it will lead to its Xiang Dan
Monoclinic phase transformation, causes volume expansion and structure is destroyed.Simultaneously because needing good Flouride-resistani acid phesphatase as material is used in nuclear reactor
Swelling and water-fast hot corrosion resistance are fallen to avoid when contacting with coolant (water) by fast erosion.Researcher has found titanate
Base ceramic material has good anti-neutron irradiation performance, and is resistant to hydro-thermal corrosion, such as Dy2TiO5Have been used for Russia
The control bar material of VVER nuclear reactor.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of heat-insulated material of rare earth titanate with porous structure
Material, period also have certain mechanical strength with low thermal conductivity and high stability while, will not be in high temperature and water
It is undergone phase transition in thermal medium, the heat-barrier material of nuclear reactor can be used for for a long time and do not have to replacement.
On the one hand, the present invention provides a kind of porous rare earth titanate heat-barrier material, the porous rare earth titanate is heat-insulated
Material have porous structure, group become (Re2O3)X(TiO2)1-X, wherein Re is at least one of Y, lanthanide series, X
=0.2~0.8, preferably X=0.4~0.7；The porosity of the porous rare earth titanate heat-barrier material is 10~90%, hole
Diameter size is 0.1~500 micron.
In the present invention, the porosity of the porous rare earth titanate heat-barrier material is 10~90%, pore size 0.1
~500 microns.Porous structure makes rare earth titanate heat-barrier material have low thermal conductivity and high stability, and has
Certain mechanical strength will not be undergone phase transition in high temperature and hydro-thermal medium, the heat-barrier material of nuclear reactor can be used for for a long time and
Without replacement.Essentially consisting in titanate crystals itself has stable cubic phase or tetragonal phase crystal form, rather than by adulterating come steady
Determine crystal structure.Such as there are structures caused by phase transformation to expand for the stable zirconia ceramic thermal insulation layer of conventional yttrium or cerium etc.
It is even disintegrated, especially when the operation temperature area of nuclear reaction works since there may be heating and cooling process repeatedly, phase transformation causes
Structural strength reduction be difficult to avoid that.And the titanate dense material itself through high temperature sintering has lower thermal conductivity (2W/
Km or so), while there is excellent mechanical property.Moreover, titanate crystals can tolerate neutron irradiation and high-temperature water heat erosion,
And there is no phase transformation in the use temperature range of nuclear reactor.The present invention can reduce thermal conductivity by constructing porous structure again
An order of magnitude effect, and certain intensity is made it have by high temperature sintering, meet the need being on active service for a long time in nuclear reactor
It wants.In addition, although the porous rare earth titanate heat-barrier material porosity prepared by the present invention is 10~90%, compared to than
The big nanometer of surface area or fibrous material have compared with low water absorption.Titanate crystallization degree after high temperature sintering is high, table
Area is smaller, and pore structure is complete, and hole wall is thicker, is not connected between partial hole, thus water absorption rate compared to loose powder and
Fiber is lower.The water absorption rate minimum 0.2% of dense body material of the invention, porosity 68% increases to 0.6%.
Preferably, the Re is at least one of Y, La, neodymium, promethium, holmium, erbium, thulium, ytterbium, lutetium, preferably Y.
Preferably, in the composition of the porous rare earth titanate heat-barrier material also comprising aluminium oxide, magnesia, chromium oxide,
At least one of silica, iron oxide, content are no more than the 5% of the porous rare earth titanate heat-barrier material quality.
On the other hand, the present invention also provides a kind of preparation method such as above-mentioned porous rare earth titanate heat-barrier material, packets
It includes: after rare earth source, titanium source and solvent are mixed, obtaining slurry；
Pore creating material drying and molding again is added in gained slurry, obtains green body, or addition foaming agent is straight in gained slurry
Moulding by casting is connect, green body is obtained；
Gained green body is sintered 2~30 hours at 1000~1500 DEG C, obtains the porous rare earth titanate heat-barrier material.
The method that the present invention uses synthesis in solid state, and by the way that pore creating material is added or combines subsequent burning using the method for foaming
Knot prepares the rare earth titanate heat-barrier material with porous structure, also has lower thermal conductivity, aperture size is in 0.1-500
Micron, porosity is adjustable in 10-90%.Porous rare earth titanate heat-barrier material can be used as the heat-insulated of nuclear reactor in the present invention
Material (thermal insulation) has low thermal conductivity in room temperature to 800 DEG C of temperature ranges, higher mechanical strong
Degree.
Preferably, the titanium source is TiO2, Ti2O3At least one of with Ti, the rare earth source is the rare earth containing Re
At least one of oxide, hydroxide and nitrate.
Preferably, the solvent is water or liquid organic solvent, the solid content of the preferably described slurry is 30~
80wt%%, preferably 30~60wt%.
Preferably, further include sintering aid in the slurry, the sintering aid be aluminium oxide, magnesia, chromium oxide,
At least one of silica, iron oxide, content are no more than the 5wt% of powder gross mass.
Preferably, the pore creating material be PMMA, polystyrene, at least one of polyethylene ball, ion exchange resin,
The percent by volume that the preferably described pore creating material accounts for solid feed in slurry is 10~80%, preferably 30~70%.In the body
Product than that can meet lower thermal conductivity and higher mechanical property etc. simultaneously in range.It is the basic of heat-barrier material that low-heat, which is led,
Condition, and mechanical property is the necessary condition of material steady operation under the service conditions such as pressure, temperature variation.
Preferably, the foaming agent be at least one of hydrogen peroxide, azodiisobutyronitrile, sodium borohydride, preferably
The percent by volume that the foaming agent accounts for solid feed in slurry is 10~80%, preferably 30~70%.
Preferably, the green body carries out dumping, the temperature of the dumping is 300~600 DEG C, and the time is 3~10 hours.
In another aspect, the present invention also provides a kind of porous rare earth titanate heat-barrier material as described above have irradiation,
Application in high temperature and high humidity environment.Porous rare earth titanate heat-barrier material can be used under high temperature, super-humid conditions in the present invention
Insulation；It can also be used for the inside and outside environment with irradiation and superheated vapor corrosion of nuclear reactor, rare earth used is oxygen at this time
Change yttrium.
Porous rare earth titanate heat-barrier material prepared by the present invention, thermal conductivity are lower than corresponding dense material, and and oxygen
Change zirconium and aluminium oxide ceramics is suitable, but do not undergo phase transition in long term high temperature environment or dusting, and there is certain resistance to hydro-thermal
Corrosive nature.
Porous titanate base heat-barrier material of the present invention and preparation method thereof, has the positive effect that:
1, it can be used for nuclear reactor inner pressure vessel and the heat-insulated ceramic material of pipeline the invention proposes a kind of, can have simultaneously
Standby lower thermal conductivity and stability, good mechanical strength, water-fast hot corrosion resistance and anti-radiation performance；
2, the bright thermal conductivity and mechanical performance in the adjustable heat-barrier material of proposed porous structure of we.By changing pore creating material
Ratio and sintering temperature etc. can change porosity and aperture size；
3, rare earth titanate based porous materials proposed by the invention can lead to avoid high temperature circulation and long service process phase transformation
The volume expansion of cause and structure are destroyed, and since the neutron absorption cross-section of titanium and part rare earth element is smaller, it is possible to reduce right
The absorption of thermal neutron；
4, preparation method simple process of the invention can carry out large-scale production, be expected to the core structure as long service
And thermal insulation layer.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for being equipped with the nuclear reactor of porous metatitanic acid yttrium ceramics, and wherein heat-barrier material can be placed in not
It becomes rusty between steel, reduces steel plate temperature outside；
Fig. 2 is that the SEM of the mixed powder of titanium source and rare earth source obtained by embodiment 1 schemes, micron-sized dilute as we know from the figure
Native oxide and the titanium dioxide of nanometer are evenly dispersed, are conducive to subsequent synthesis and sintering；
Fig. 3 is that the SEM of the porous rare earth titanate heat-barrier material prepared by embodiment 1 schemes, as we know from the figure micron-sized Kong Jun
Even distribution, and tactical rule；
Fig. 4 is the XRD diagram of the porous rare earth titanate heat-barrier material obtained by embodiment 2；
Fig. 5 is the sample photo of the porous metatitanic acid yttrium ceramics obtained by embodiment 2.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The composition of porous rare earth titanate heat-barrier material is mainly (R in the present invention2O3)X-(TiO2)1-X, wherein R represent Y,
La or other lanthanide series rare-earth elements (such as one or more of neodymium, promethium, holmium, erbium, thulium, ytterbium, lutetium etc.), X=0.2~0.8, more
Excellent range be it is small=0.4~0.7.The present invention is prepared by sintering with porous structure using the method for synthesis in solid state
Rare earth titanate heat-barrier material also has lower thermal conductivity, and aperture size is at 0.1~500 micron, and porosity is 10~90%
It is adjustable.For acceleration of sintering, can also be no more than comprising above-mentioned in the composition of the porous rare earth titanate heat-barrier material
Sintering aid (for example, aluminium oxide, magnesia, chromium oxide, silica, iron oxide etc.) component of 5wt%.
The present invention is that presoma mixes with the compound (rare earth source) of compound containing Ti (titanium source) and rare earth element,
And be added a certain proportion of pore creating material or be added foaming agent, then by drying, tabletting, sintering, post-processing and etc. prepare it is more
Hole rare earth titanate heat-barrier material.Illustrate to following exemplary the preparation of porous rare earth titanate heat-barrier material provided by the invention
Method.
Rare earth source, titanium source and solvent are mixed (for example, ball milling mixing according to the composition of porous rare earth titanate heat-barrier material
Deng) after, obtain slurry.Wherein, the ratio of Re need to choose OK range value according to composition in Ti and rare earth source in titanium source, such as
For Re2Ti2O7, Re:Ti=0.9~1.1；For Re2TiO5, Re:Ti=1.8:2.2.The titanium source can be TiO2, Ti2O3With
At least one of Ti.The rare earth source can be at least one in the rare earth oxide containing Re, hydroxide and nitrate
Kind.It further include sintering aid in the slurry.The solvent can be water or liquid organic solvent.The solid content of the slurry can be
30-80wt%, preferably 30-60wt%.The sintering aid can be in aluminium oxide, magnesia, chromium oxide, silica, iron oxide
At least one, content be no more than powder gross mass 5wt%.It further include dispersing agent in the slurry, the dispersing agent can be
At least one of citric acid, polyethylene glycol, poly amic acid and polyacrylic acid potassium.The additional amount and rare earth of the dispersing agent
The ratio of source and titanium source gross mass is 1:(80~100).As an example, titanium oxide, rare earth oxygen can be used in the preparation of the material
The powders such as compound and aluminium oxide, magnesia, chromium oxide, silica, iron oxide can be used as material powder, can also use hydrogen
Oxide or other other compounds that can be changed into above-mentioned oxide after the heating are material powder.Then by above-mentioned raw materials
Powder prepares biscuit (for example, with the methods of dry-pressing, isostatic cool pressing, casting molding) after mixing, and obtaining through sintering has one
Determine the material of the porosity.
It can be in above-mentioned slurry to improve the porosity by the pore creating material particle that Organic polymer compositions are added.Used makes
Hole agent includes but is not limited to organic polymer, such as polymethyl methacrylate materials (PMMA), ion exchange resin, polyphenyl
Ethylene, polyethylene ball etc..The particle size of the pore creating material is between 0.1~500 micron.The pore creating material accounts for solid in slurry
The percent by volume of state raw material (rare earth source and titanium source) can be 10~80%.
Green body is prepared by way of foaming agent is added in above-mentioned slurry, and using the method for pouring technology, with
Improve the porosity of final gained porous rare earth titanate heat-barrier material.Foaming agent used include but is not limited to hydrogen peroxide,
Azodiisobutyronitrile etc..It is uniformly mixed material powder proportionally, with the methods of dry-pressing, isostatic cool pressing, casting molding, burns
Knot obtains the material with certain porosity.The foaming agent account for solid feed in slurry percent by volume can for 10~
80%.
Slurry drying and the molding again for having pore creating material will be added, obtains green body.The mode of the forming can for dry-pressing at
Type, cold isostatic compaction etc..The dry-pressing formed pressure can be 10~200MPa, and the dwell time can be 1~30 second.It is described
The pressure of cold isostatic compaction can be 30~300MPa, and the dwell time can be 1~60 second, the temperature of the drying can for 60~
100 DEG C, the time is 0.5~10 hour.
Porous rare earth titanate heat-barrier material is obtained after above-mentioned gained green body is carried out dumping, sintering.The temperature of the dumping
Degree can be 300~600 DEG C, and the time can be 3~10 hours.The temperature of the sintering can be 1000~1500 DEG C, and sintering time can
It is 2~30 hours.In the present invention, dumping and sintering can carry out under atmospheric condition, including oxygen, air, inert atmosphere are (such as
Argon gas etc.) etc..Wherein sintering atmosphere is preferably air and oxygen atmosphere.As an example, first by gained green body (biscuit)
Dumping processing is carried out in 300-600 DEG C of low temperature, organic matter is removed, is then sintered synthesis, sintering temperature is in 1000-
Between 1500 DEG C, the sintered heat insulating time at 2-30 hours, can be sintered, including but not limited to air under different atmosphere, argon gas and
Under oxygen atmosphere.
The example of preparation method as a porous rare earth metatitanic acid alkali ceramic insulating material, the porous rare earth metatitanic acid
The composition of alkali ceramic insulating material is Re2TiO5And Re2Ti2O7, R represents Y and lanthanide series rare-earth elements, using synthesis in solid state
Technique, its step are as follows: by the compound of titaniferous, including TiO2, Ti2O3And Ti powder etc. and rare earth oxide, hydroxide, nitre
Hydrochlorate etc. is mixed according to certain molar ratio, then using water or liquid organic solvent as medium, is carried out ball milling or is sanded mixed
Material.The time of mixing was at 0.5-48 hours.A certain proportion of pore creating material is added in the slurry, continuess to mix 0.5-5 hours.Slurry
Material carries out drying at 60-100 DEG C or in advance filter then to dry again, and (crossing grit number can be 80-200 mesh for sieving.),
Remove bulky grain.The powder of acquisition carries out tabletting, is carrying out dumping and sintering after isostatic cool pressing processing.Dumping and sintering can be
It is carried out under atmospheric condition, including oxygen, air, argon gas etc..
In the present invention, in the porous rare earth titanate heat-barrier material, rare earth can be any one in Y and group of the lanthanides
Or multiple combinations.Prepared thermal insulation ceramics are the blocks by high temperature sintering, can carry out post-processing processing, be prepared into institute
Need shape and specification.
Porous rare earth titanate heat-barrier material prepared by the present invention have lower water absorption rate, higher mechanical strength,
Good water-fast hot corrosion resistance and certain radiation resistance ability, in high temperature, high humidity so that having under the conditions of nuclear reactor good
Good application prospect.Water absorption rate (institute's water absorption and heat-insulated material of porous rare earth titanate heat-barrier material prepared by the present invention
The mass percent of material) it can be 0.1~2%.The present invention measures prepared porous rare earth titanate using four-point bending method
The bending resistance breaking strength of heat-barrier material can be 10~200MPa.The present invention is surveyed using guarded heat flow meter technique thermal conductivity (thermal resistance) tester
The thermal conductivity of prepared porous rare earth titanate heat-barrier material is obtained at 30 DEG C, range can be 0.05~2.5W/mK, preferably
For 0.05~1.5W/mK.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. be also only an example in OK range, i.e. those skilled in the art can be done by the explanation of this paper
Selection in suitable range, and do not really want to be defined in hereafter exemplary specific value.
1 Y of embodiment2TiO5Porous heat-insulating ceramics
Titania powder (10g) and yttrium oxide are added citric acid (0.2g) and are used as dispersing agent according to molar ratio 1:1 ingredient,
Water (30g) was used as ball-milling medium, using zirconium oxide balls ball milling 4 hours.It is added in spreading mass and accounts for whole solid feeds
The PMMA of volume ratio 50% continues ball milling 1 hour, is then dried at 80 DEG C as pore creating material.By sieving, dry-pressing at
After type and isostatic cool pressing, biscuit is obtained.Biscuit is handled 2 hours in 600 DEG C of progress dumpings, then under the conditions of air atmosphere
It is sintered at 1200 DEG C 10 hours, obtains porous metatitanic acid yttrium ceramic insulating material.It is made into diameter 50mm, thickness 5mm
Disk be used for heat-insulated test, thermal conductivity at 30 DEG C, be 0.18W/mK.The porous metatitanic acid yttrium ceramic insulating material of gained
The porosity is 50%, breaking strength 50MPa.Water absorption rate is 0.3% after static 30 days in air.At 500 DEG C, through 45KeV
Ne ion bombardment 50dpa irradiation damage dosage, sample swelling rate less than 0.3%, do not find crystal phase variation and hole.?
The deionized water of deoxygenation is added in autoclave, carries out water resistant heat erosion test at 300 DEG C, porous structure base is taken out after 50 hours
This is complete, and does not have aSi:H film.
2 Y of embodiment2Ti2O7Porous heat-insulating ceramics
Polyethylene glycol (5g) is added as dispersing agent, ethyl alcohol according to molar ratio 2:1 ingredient in Ti powder (50g) and yttrium oxide
(50g) is used as ball-milling medium, is recycled mixing 1 hour using sand mill.The polyphenyl second of volume ratio 70% is added in spreading mass
Alkene ball continues to be sanded 0.5 hour, then be dried at 60 DEG C as pore creating material.It is dry-pressing formed and cold etc. quiet by sieving
After pressure, biscuit is obtained.1 hour is handled in 500 DEG C of progress dumpings to biscuit, then under the conditions of oxygen atmosphere 1300 DEG C into
Row sintering 5 hours, obtains porous metatitanic acid yttrium (Y2Ti2O7) ceramic insulating material.It is made into diameter 50mm, thickness 5mm's
Disk is used for heat-insulated test, and thermal conductivity is 0.12W/mK at 30 DEG C.The gas of the porous metatitanic acid yttrium ceramic insulating material of gained
Porosity is 68%, breaking strength 60MPa.Water absorption rate is 0.6% after static 30 days in air.At 600 DEG C, through 45KeV's
The irradiation damage dosage of Ar ion bombardment 30dpa, sample swelling rate do not find crystal phase variation and hole less than 0.2%.In height
The deionized water that deoxygenation is added in kettle is pressed, carries out water resistant heat erosion test at 300 DEG C, it is basic that porous structure is taken out after 50 hours
Completely, and there is no aSi:H film.
Embodiment 3
Titania powder (30g) and thulium oxide are added citric acid (0.2g) and are used as dispersing agent according to molar ratio 1:1 ingredient,
Water (50g) was used as ball-milling medium, using zirconium oxide balls ball milling 4 hours.It is added in spreading mass and accounts for solid feed volume ratio
50% PMMA continues ball milling 0.5 hour, is then dried at 80 DEG C as pore creating material.By sieving, it is dry-pressing formed and
After isostatic cool pressing, biscuit is obtained.2 hours is handled in 600 DEG C of progress dumpings to biscuit, then under the conditions of air atmosphere
1300 DEG C are sintered 5 hours, obtain porous metatitanic acid thulium ceramic insulating material.It is made into diameter 50mm, thickness 5mm's
Disk is used for heat-insulated test, and thermal conductivity is 0.10W/mK at 30 DEG C.The gas of the porous lanthanum titanate ceamics heat-barrier material of gained
Porosity is 48%, breaking strength 90MPa, and water absorption rate is 0.5% after static 30 days in air.At 300 DEG C, through 45KeV's
The irradiation damage dosage of Ar ion bombardment 50dpa, sample swelling rate do not find crystal phase variation and hole less than 0.1%.In height
The deionized water that deoxygenation is added in kettle is pressed, carries out water resistant heat erosion test at 300 DEG C, it is basic that porous structure is taken out after 50 hours
Completely, and there is no aSi:H film.
Embodiment 4
Titania powder (100g) and holimium oxide are added citric acid (1g) and are used as dispersing agent according to molar ratio 1:1 ingredient,
Water (70g) was used as ball-milling medium, using zirconium oxide balls ball milling 4 hours.It is added in spreading mass and accounts for solid feed volume ratio
50% PMMA continues ball milling 1 hour, is then dried at 80 DEG C as pore creating material.It is dry-pressing formed and cold by sieving
After equal static pressure, biscuit is obtained.Biscuit is handled 2 hours in 600 DEG C of progress dumpings, then 1200 under the conditions of air atmosphere
It DEG C is sintered 10 hours, obtains porous metatitanic acid holmium ceramic insulating material.It is made into diameter 50mm, the disk of thickness 5mm
For heat-insulated test, thermal conductivity is 0.15W/mK at 30 DEG C.The porosity of the porous metatitanic acid holmium ceramic insulating material of gained
It is 52%, breaking strength 60MPa, water absorption rate is 0.8% after static 30 days in air.At 600 DEG C, the Kr through 100KeV
The irradiation damage dosage of ion bombardment 30dpa, sample swelling rate do not find crystal phase variation and hole less than 0.1%.In high pressure
The deionized water of deoxygenation is added in kettle, carries out water resistant heat erosion test at 300 DEG C, it is substantially complete that porous structure is taken out after 50 hours
It is whole, and there is no aSi:H film.
Embodiment 5
Titania powder (40g) and ytterbium oxide are added citric acid (0.3g) and are used as dispersing agent according to molar ratio 1:1 ingredient,
Water (60g) was used as ball-milling medium, using zirconium oxide balls ball milling 4 hours.It is added in spreading mass and accounts for solid feed volume ratio
60% PMMA continues ball milling 1 hour, is then dried at 80 DEG C as pore creating material.It is dry-pressing formed and cold by sieving
After equal static pressure, biscuit is obtained.Biscuit is handled 2 hours in 600 DEG C of progress dumpings, then 1250 under the conditions of air atmosphere
It DEG C is sintered 8 hours, obtains porous metatitanic acid ytterbium ceramic insulating material.It is made into diameter 50mm, the disk of thickness 5mm
For heat-insulated test, thermal conductivity is 0.2W/mK at 30 DEG C.The porosity of the porous metatitanic acid ytterbium ceramic insulating material of gained is
60%, breaking strength 80MPa.Water absorption rate is 0.8% after static 30 days in air.At 500 DEG C, the Ar ion through 45KeV
The irradiation damage dosage of 30dpa is bombarded, sample swelling rate does not find crystal phase variation and hole less than 0.3%.In autoclave
The deionized water of deoxygenation is added, carries out water resistant heat erosion test at 320 DEG C, taking-up porous structure is substantially complete after 60 hours, and
There is no aSi:H film.
6 Y of embodiment2Ti2O7Porous heat-insulating ceramics
Polyethylene glycol (6g) is added as dispersing agent, ethyl alcohol according to molar ratio 2:1 ingredient in Ti powder (70g) and yttrium oxide
(50g) is used as ball-milling medium, is recycled mixing 1 hour using sand mill.It is added in spreading mass and accounts for solid feed volume ratio
30% polystyrene spheres continue to be sanded 0.5 hour, then be dried at 60 DEG C as pore creating material.By sieving, dry-pressing
After molding and isostatic cool pressing, biscuit is obtained.Biscuit is handled 1 hour in 500 DEG C of progress dumpings, then in oxygen atmosphere condition
Under be sintered at 1300 DEG C 10 hours, obtain porous metatitanic acid yttrium (Y2Ti2O7) ceramic insulating material.It is made into diameter
The disk of 50mm, thickness 5mm are used for heat-insulated test, and thermal conductivity is 0.5W/mK at 30 DEG C.The porous metatitanic acid yttrium ceramics of gained
The porosity of heat-barrier material is 30%, breaking strength 120MPa.Water absorption rate is 0.6% after static 30 days in air.?
600 DEG C, the irradiation damage dosage of the Ar ion bombardment 30dpa through 45KeV, sample swelling rate does not find crystal phase less than 0.2%
Variation and hole.The deionized water of deoxygenation is added in autoclave, carries out water resistant heat erosion test at 350 DEG C, is taken after 50 hours
Porous structure is substantially complete out, and does not have aSi:H film.
7 Y of embodiment2Ti2O7Porous heat-insulating ceramics
Polyethylene glycol (5g) is added as dispersing agent, ethyl alcohol according to molar ratio 2:1 ingredient in Ti powder (30g) and yttrium oxide
(60g) is used as ball-milling medium, is recycled mixing 1 hour using sand mill.It is added in spreading mass and accounts for solid feed volume ratio
10% polystyrene spheres continue to be sanded 0.5 hour, then be dried at 60 DEG C as pore creating material.By sieving, dry-pressing
After molding and isostatic cool pressing, biscuit is obtained.Biscuit is handled 1 hour in 500 DEG C of progress dumpings, then in oxygen atmosphere condition
Under be sintered at 1300 DEG C 20 hours, obtain porous metatitanic acid yttrium (Y2Ti2O7) ceramic insulating material.It is made into diameter
The disk of 50mm, thickness 5mm are used for heat-insulated test, and thermal conductivity is 1.5W/mK at 30 DEG C.The porous metatitanic acid yttrium ceramics of gained
The porosity of heat-barrier material is 12%, breaking strength 180MPa.Water absorption rate is 0.3% after static 30 days in air.?
500 DEG C, the irradiation damage dosage of the Ar ion bombardment 30dpa through 80KeV, sample swelling rate does not find crystal phase less than 0.3%
Variation and hole.The deionized water of deoxygenation is added in autoclave, carries out water resistant heat erosion test at 320 DEG C, is taken after 50 hours
Porous structure is substantially complete out, and does not have aSi:H film.
8 Y of embodiment2TiO5Porous heat-insulating ceramics
Titania powder (60g) and yttrium oxide are added citric acid (0.3g) and are used as dispersing agent according to molar ratio 1:1 ingredient,
Water (40g) was used as ball-milling medium, using zirconium oxide balls ball milling 4 hours.Solid feed volume ratio is added in spreading mass
50% hydrogen peroxide continues ball milling 1 hour as foaming agent, then uses injection forming.Biscuit is arranged at 600 DEG C
Glue is handled 2 hours, is then sintered 10 hours under the conditions of air atmosphere at 1200 DEG C, and porous metatitanic acid yttrium ceramics are obtained
Heat-barrier material.It is made into diameter 50mm, the disk of thickness 5mm is used for heat-insulated test, and thermal conductivity is 0.09W/ at 30 DEG C
mK.The porosity of the porous metatitanic acid yttrium ceramic insulating material of gained is 70%, breaking strength 68MPa, in air static 30
Water absorption rate is 0.4% after it.At 700 DEG C, the irradiation damage dosage of the Ar ion bombardment 30dpa through 120KeV, sample swelling rate
Less than 0.2%, crystal phase variation and hole are not found.The deionized water of deoxygenation is added in autoclave, carries out water resistant at 300 DEG C
It is substantially complete to take out porous structure, and does not have aSi:H film for heat erosion test after 80 hours.
Comparative example 1
Titania powder (50g) and yttrium oxide are added citric acid (0.5g) and are used as dispersing agent according to molar ratio 1:1 ingredient,
Water (60g) was used as ball-milling medium, using zirconium oxide balls ball milling 4 hours.Then it is dried at 80 DEG C.By sieving, dry-pressing
After molding and isostatic cool pressing, biscuit is obtained.Biscuit is handled 2 hours in 600 DEG C of progress dumpings, then in air atmosphere condition
Under be sintered at 1350 DEG C 20 hours, obtain porous metatitanic acid yttrium ceramic insulating material.It is made into diameter 50mm, thickness
The disk of 5mm is used for heat-insulated test, and thermal conductivity is 2.2W/mK at 30 DEG C.The porous metatitanic acid yttrium ceramic insulating material of gained
The porosity be 0.5%, breaking strength 620MPa.Water absorption rate is 0.2% after static 30 days in air.At 600 DEG C, warp
The irradiation damage dosage of the Ar ion bombardment 30dpa of 120KeV, sample swelling rate do not find crystal phase variation and hole less than 0.2%
Hole.The deionized water of deoxygenation is added in autoclave, carries out water resistant heat erosion test at 350 DEG C, porous knot is taken out after 50 hours
Structure is substantially complete, and does not have aSi:H film.
The performance parameter for the porous rare earth titanate heat-barrier material that table 1 is 1-8 of the embodiment of the present invention and prepared by comparative example 1:
Claims (11)
1. a kind of porous rare earth titanate heat-barrier material, which is characterized in that the porous rare earth titanate heat-barrier material has more
Pore structure, group become (Re2O3)X(TiO2)1-X, wherein Re be at least one of Y, lanthanide series, X=0.2~0.8,
Preferably X=0.4~0.7；The porosity of the porous rare earth titanate heat-barrier material be 10~90%, pore size be 0.1~
500 microns.
2. porous rare earth titanate heat-barrier material according to claim 1, which is characterized in that the Re be Y, La, neodymium,
At least one of promethium, holmium, erbium, thulium, ytterbium, lutetium, preferably Y.
3. porous rare earth titanate heat-barrier material according to claim 1 or 2, which is characterized in that the porous rare earth titanium
It also include at least one of aluminium oxide, magnesia, chromium oxide, silica, iron oxide, content in the composition of hydrochlorate heat-barrier material
No more than the 5% of the porous rare earth titanate heat-barrier material quality.
4. a kind of preparation method of the porous rare earth titanate heat-barrier material as described in any one of claim 1-3, feature exist
In, comprising:
After rare earth source, titanium source and solvent are mixed, slurry is obtained；
Pore creating material drying and molding again is added in gained slurry, obtains green body, or addition foaming agent is straight in gained slurry
Moulding by casting is connect, green body is obtained；
Gained green body is sintered 2~30 hours at 1000~1500 DEG C, obtains the porous rare earth titanate heat-barrier material.
5. the preparation method according to claim 4, which is characterized in that the titanium source is TiO2, Ti2O3With in Ti at least
One kind, the rare earth source are at least one of the rare earth oxide containing Re, hydroxide and nitrate.
6. preparation method according to claim 4 or 5, which is characterized in that the solvent be water or liquid organic solvent, it is excellent
The solid content of slurry described in selection of land is 30~80wt%.
7. the preparation method according to any one of claim 4-6, which is characterized in that further include that sintering helps in the slurry
Agent, the sintering aid are at least one of aluminium oxide, magnesia, chromium oxide, silica, iron oxide, and content is no more than powder
The 5wt% of body gross mass.
8. the preparation method according to any one of claim 4-7, which is characterized in that the pore creating material is organic polymer
Object, preferably PMMA, polystyrene, polyethylene ball, ion exchange resin, at least one of starch etc., the preferably described pore-creating
The percent by volume that agent accounts for solid feed in slurry is 10~80%, preferably 30~70%.
9. the preparation method according to any one of claim 4-8, which is characterized in that the foaming agent be hydrogen peroxide,
At least one of azodiisobutyronitrile, sodium borohydride, the preferably described foaming agent account for the volume basis of solid feed in slurry
Than being 10~80%, preferably 30~70%.
10. the preparation method according to any one of claim 4-9, which is characterized in that before sintering, the green body into
Row dumping, the temperature of the dumping are 300~600 DEG C, and the time is 3~10 hours.
11. one kind porous rare earth titanate heat-barrier material as described in any one of claim 1-3 has irradiation, high temperature and height
Application in wet environment.
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