CN103159478A - Nd2O3-Yb2O3 modified La2Zr2O7-(Zr0.92Y0.08)O1.96 multi-phase thermal barrier coating material - Google Patents
Nd2O3-Yb2O3 modified La2Zr2O7-(Zr0.92Y0.08)O1.96 multi-phase thermal barrier coating material Download PDFInfo
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Abstract
The present invention discloses an Nd2O3-Yb2O3 modified La2Zr2O7-(Zr0.92Y0.08)O1.96 multi-phase thermal barrier coating material, wherein Nd<3+> is adopted to substitute a La<3+> lattice position in La2Zr2O7 to form (La,Nd)2Zr2O7, and Yb<3+> with a relatively small ion radius is adopted to substitute Zr<4+> in (Zr0.92Y0.08)O1.96 to form a cubic phase (Zr,Y,Yb)O2-delta so as to further reduce thermal conductivity of the material and increase phase stability, such that a thermal insulation effect, a use temperature and a thermal cycle life of the coating are increased. The multi-phase material is prepared by using an in-situ reaction self-generation method, wherein the grain size of the two phases is in a range of 40-55 nm after calcination is performed for 12 h at a temperature of 1200 DEG C, and the modified material can maintain good phase stability after calcination for 100 h at a temperature of 1450 DEG C, and can bear sintering at a temperature of 1400 DEG C.
Description
Technical field
The present invention relates to a kind of Nd
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96Complex phase thermal barrier coating lagging material.
Background technology
Follow the increase of aero gas turbine engine thrust-weight ratio, before the whirlpool, temperature further promotes, when adopting more advanced cooling technology in design, the requirement blade surface will bear the high temperature more than 1200 ℃, therefore the use temperature limit that has exceeded present superalloy develops the high-temp heat barrier coating trend that is inevitable.
Functional requirement according to thermal barrier coating, as the thermal barrier coating lagging material, at first have low thermal conductivity and the characteristic such as corrosion-resistant, next is from the Service Environment of coating, coated material also will have the characteristic of higher heat shock resistance damage, for improving this specific character, require material to have ability and the characteristic such as good phase stability and fracture toughness property of good high temperature sintering resistant.
Yet, traditional heat barrier coat material 3～4mol%Y
2O
3Stable ZrO
2(be called for short YSZ) although have good fracture toughness property, lower thermal conductivity and the advantage such as corrosion-resistant, phase stability descends and the factors such as the phase transformation volume effect brought and high temperature easy-sintering under hot conditions, can only use below temperature at 1200 ℃; Has high temperature without phase transformation, 1400 ℃ of high temperature sinterings of ability and the thermal conductivity pyrochlore constitution La than YSZ low 30%
2Zr
2O
7Material, though can improve use temperature and the effect of heat insulation of thermal barrier coating, because the toughness of the relative YSZ of this material is relatively poor lower with thermal expansivity, coating is easily peeled off in the thermal shocking process.Although can further reduce La by rear-earth-doped
2Zr
2O
7Thermal conductivity, as (La
0.7Nd
0.3)
2Zr
2O
7Compare La
2Zr
2O
7Thermal conductivity approximately low by 13%, but fracture toughness property does not improve.
Utilize YSZ and La
2Zr
2O
7Advantage is carried out compoundly separately, has obtained obvious improvement before the material after compound or some Performance Ratio of coating are compound.The YSZ that adds 5mol% can make La
2Zr
2O
7The fracture toughness property of material is by 1.4MPam
1/2Be increased to 1.9MPam
1/2(suitable with YSZ); Add the La of 5mol%
2Zr
2O
7Thermal conductivity in the time of making 1200 ℃ of YSZ coatings is reduced to 1.2W/mK by 2.1W/mK, and material drops to 0.75 in the relative density of 1300 ℃ of sintering after 10 hours by 0.84.But work as La
2Zr
2O
7When phase content surpassed 1mol%, in material, the phase stability of YSZ descended, and use temperature and the thermal cycle life of coating are greatly affected, and still can not satisfy the service requirements of gas turbine engine of future generation thermal barrier coating more than 1200 ℃.
Summary of the invention
The purpose of this invention is to provide a kind of Nd
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material.At La
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96On the basis of composite diphase material, adopt Nd
2O
3Doped and substituted La
2Zr
2O
7Part La lattice position mutually forms low (La, the Nd) of thermal conductivity
2Zr
2O
7Compound, Yb
2O
3Doped and substituted (Zr
0.92Y
0.08) O
1.96In the Zr configuration become stable Emission in Cubic, play the thermal conductivity that reduces material and the effect that improves phase stability.Develop with this complex phase thermal barrier coating lagging material that novel having mutually stablized, thermal conductivity is low and the high temperature sintering resistant ability is strong, improve gas turbine engine efficient, reduce fuel oil consumption, need reach the service requirements of temperature more than 1200 ℃ thereby bring huge society and economic benefit and satisfy gas turbine engine of future generation with thermal barrier coating.
According to an aspect of the present invention, provide a kind of Nd
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material is characterized in that: described composite diphase material is 99.99% Ln by purity
2O
3(Ln=La, Nd, Yb, Y) and purity are 99.99% ZrO
2Form, composition range is 60～90mol%ZrO
2, 4～30mol%LaO
1.5, 1～10mol%NdO
1.5, 1～10mol%YbO
1.5And 2-7mol%YO
1.5
According to a further aspect of the present invention, provide preparation above-mentioned Nd
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The method of complex phase heat barrier coat material is characterized in that comprising:
Ln (NO take purity as 99.99%
3)
36H
2O (Ln=La, Nd, Y) and Zr (NO
3)
43H
2O is raw material, prepares respectively the aqueous solution of 0.1～0.3mol/L,
Press the design mix weighing, add appropriate citric acid, polyoxyethylene glycol and concentrated nitric acid, magnetic agitation is to clear colloidal sol,
Air with 0.1-0.3MPa is atomised to colloidal sol in 300 ℃ of-600 ℃ of corundum crucibles, then temperature is risen to 900～1200 ℃ of calcinings 0.5～12 hour.
Description of drawings
Fig. 1 is 1200 ℃ of calcining 73ZrO after 12 hours
2-(23-x) LaO
1.5-0.5xNdO
1.5-0.5xYbO
1.5-4YO
1.5(x=7,9,11,14,16,18) composite diphase material room temperature powder X-ray RD collection of illustrative plates.
Fig. 2 is 1200 ℃ of calcining 73ZrO after 12 hours
2-(23-x) LaO
1.5-0.25xNdO
1.5-0.75xYbO
1.5-4YO
1.5(x=7,9,11) composite diphase material room temperature powder X-ray RD collection of illustrative plates.
Fig. 3 is 1200 ℃ of calcining 62ZrO after 12 hours
2-(35.8-x) LaO
1.5-0.5xNdO
1.5-0.5xYbO
1.5-2.2YO
1.5(x=10.8,14.2,17.8) composite diphase material room temperature powder X-ray RD collection of illustrative plates.
Fig. 4 is 1200 ℃ of calcining 73ZrO after 12 hours
2-(23-x) LaO
1.5-0.5xNdO
1.5-0.5xYbO
1.5-4YO
1.5The grain-size of (x=7,9,11,14,16,18) composite diphase material and doped parameterx Relations Among figure.
Fig. 5 is 73ZrO
2-14LaO
1.5-4.5NdO
1.5-4.5YbO
1.5-4YO
1.5With unmodified material through 1450 ℃ the calcining 100 hours after room temperature powder X-ray RD collection of illustrative plates.
Fig. 6 is 73ZrO
2-14LaO
1.5-4.5NdO
1.5-4.5YbO
1.5-4YO
1.5With unmodified material through 1450 ℃ the calcining 100 hours after monoclinic zirconia content balance figure.
Fig. 7 (a) is 73ZrO
2-16LaO
1.5-3.5NdO
1.5-3.5YbO
1.5-4YO
1.5, Fig. 7 (b) is that in contrast unmodified material is through the backscattered electron image of 1400 ℃ of sintering after 50 hours.
Fig. 8 is 73ZrO
2-14LaO
1.5-2.25NdO
1.5-6.75YbO
1.5-4YO
1.5Material is through the backscattered electron image of 1400 ℃ of sintering after 50 hours.
Fig. 9 is 62ZrO
2-21.6LaO
1.5-8.9NdO
1.5-8.9YbO
1.5-2.2YO
1.Material is through the backscattered electron image of 1400 ℃ of sintering after 50 hours.
Embodiment
According to one embodiment of present invention, provide a kind of Nd
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96Complex phase heat barrier coat material, its chemical constitution are 60～90mol%ZrO
2, 4～30mol%LaO
1.5, 1～10mol%NdO
1.5, 1～10mol%YbO
1.5And 2-7mol%YO
1.5
According to Nd of the present invention
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material can be 62ZrO
2-(35.8-x) LaO
1.5-0.5xNdO
1.5-0.5xYbO
1.5-2.2YO
1.5(x=10.8,14.2,17.8) or
73ZrO
2-(23-x) LaO
1.5-0.25xNdO
1.5-0.75xYbO
1.5-4YO
1.5(x=7,9,11) or
73ZrO
2-(23-x) LaO
1.5-0.75xNdO
1.5-0.25x YbO
1.5-4YO
1.5(x=7,9,11) or
73ZrO
2-(23-x)LaO
1.5-0.5xNdO
1.5-0.5xYbO
1.5-4YO
1.5(x＝7、9、11、14、16、18)。
Nd according to an embodiment of the invention
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material, 1200 ℃ of calcinings are after 12 hours, and the grain-size of two-phase is all between 40～55nm; 1450 ℃ of calcinings are after 100 hours, and the 49mol% of the monoclinic phase content in the material component zirconium white before by modification is reduced to 0mol%; 1400 ℃ of long-time sintering of material ability.
Nd of the present invention
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The advantage of complex phase heat barrier coat material is:
(1) pass through Nd
2O
3-Yb
2O
3La after modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material, La in material
2Zr
2O
7More than the content of phase can reach 10mol%, and 1400 ℃ of sintering of ability, so after modification, use temperature and the effect of heat insulation of coating will be greatly improved;
(2) pass through Nd
2O
3-Yb
2O
3La after modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material, after 1450 ℃ of calcining 100h, monoclinic zirconia content by modification before 49mol% be reduced to 0mol%, so after modification, use temperature and the thermal cycle life of coating is greatly improved;
(3) pass through Nd
2O
3-Yb
2O
3La after modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material forms and compares La
2Zr
2O
7(Zr
0.92Y
0.08) O
1.96(La, the Nd) that thermal conductivity is low
2Zr
2O
7(Zr, Y, Yb) O
2-δ, so the coating effect of heat insulation after modification is further enhanced;
(4) pass through Nd
2O
3-Yb
2O
3La after modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material is the preparation method who adopts the self-generating of spray pyrolysis reaction in－situ, the grain-size of material is little, mixing uniformity and interfacial bonding property good, so after modification, the thermal cycle life of coating is further enhanced.
The present invention is described in further detail below in conjunction with drawings and Examples.
According to an aspect of the present invention, provide a kind of Nd
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material is for La thermal conductivity is low, that the high temperature sintering resistant ability is strong and mutually stable
2Zr
2O
7Interpolation can significantly improve traditional thermal barrier coating (Zr
0.92Y
0.08) O
1.96Effect of heat insulation and high temperature sintering resistant ability thereof, but the too high meeting of addition causes (Zr
0.92Y
0.08) O
1.96Phase stability descend and the problem that can not use as high-temp heat barrier coating, at La
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96Develop a kind of mutually stable Nd that has on the basis of composite diphase material
2O
3-Yb
2O
3The La of modification modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material, this material can substitute traditional thermal barrier material YSZ, improve effect of heat insulation and the use temperature of coating, reduce energy consumption and also bring huge society and economic benefit, and further satisfy gas turbine engine of new generation and need reach with coating and hold the requirement of warm ability more than 1200 ℃.
Nd according to an embodiment of the invention
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material is 99.99% Ln by purity
2O
3(Ln=La, Nd, Yb, Y) and purity are 99.99% ZrO
2Form, composition range is 60～90mol%ZrO
2, 4～30mol%LaO
1.5, 1～10mol%NdO
1.5, 1～10mol%YbO
1.5And 2-7mol%YO
1.5
Nd according to an embodiment of the invention
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material is to adopt the preparation of spray pyrolysis reaction in－situ self-generating method.The method comprises:
Prepare certain density standard water solution, put into the vial magnetic agitation by the solution that component proportions takes,
Add appropriate citric acid, polyoxyethylene glycol and concentration and be 65～68% concentrated nitric acid,
Adopt the air-atomizing pyrolysis plant, the purity take pressure as 0.3MPa is atomised to temperature in the corundum crucible of 600 ℃ with colloidal sol as 99.99% air,
Temperature is risen to 1200 ℃ of one scheduled times of calcining.
Phase composite, phase stability and the anti-caking power of material to preparation analyzed:
(1) phase composite of complex phase coated material and grain-size analysis
The Multi-functional X ray diffractometer (XRD) that to adopt the model that Dutch PANalytical company produces be X ' Pert PRO, be furnished with the super detector of X ' Celerator carries out phase and forms test, and the x ray is Cu target k
α 1, wavelength
According to phase composite, phase content and the lattice parameter thereof of material with Nd
2O
3-Yb
2O
3The Changing Pattern of add-on determines that the series material that obtained in 12 hours 1200 ℃ of calcinings is by (La, Nd)
2Zr
2O
7(Zr, Y, Yb) O
2-δTwo kinds of compounds form, wherein (Zr, Y, Yb) O
2-δIt is Emission in Cubic.
Adopt the Scherrer formula: D=0.89 λ/Bcos θ, λ in formula, θ and B are respectively the halfwidth of x beam wavelength, diffraction angle and diffraction peak, and in Calculating material, the grain-size of two-phase is all less than 60nm.
(2) phase stability is estimated.
The composite diphase material of 1200 ℃ of preparations is taken out a little put into corundum crucible, calcining after 100 hours, adopts XRD that sample is carried out the phase test and analyzes in 1450 ℃ of program control High Temperature Furnaces Heating Apparatuss.After high-temperature calcination, the sample before modification all has monoclinic zirconia to occur mutually, and Nd
2O
3-Yb
2O
3Sample after modification is still stable Emission in Cubic.
(3) anti-caking power
Powder before and after modification is carried out respectively compression molding under 500MPa pressure, put into 1400 ℃ of sintering of program control High Temperature Furnaces Heating Apparatus 50 hours, temperature rate is 2 ℃/minute, adopts field emission scanning electron microscope to observe the sintered compact surface topography, shows material 1400 ℃ of sintering of ability after modification.
The present invention develops that a kind of stable, anti-sintering mutually, low thermal conductance, grain-size are little, the complex phase heat barrier coat material of two-phase good uniformity, can improve use temperature, effect of heat insulation and the thermal cycle life of coating, need reach with coating and hold the requirement of warm ability more than 1200 ℃ thereby bring huge society and economic benefit and further satisfy gas turbine engine of new generation.
Embodiment 1:
73ZrO processed
2-(23-x) LaO
1.5-0.5x NdO
1.5-0.5xYbO
1.5-4YO
1.5(x=7,9,11,14,16,18) composite diphase material
Ln (NO take purity as 99.99%
3)
36H
2O (Ln=La, Nd, Y, Yb) and Zr (NO
3)
43H
2O is raw material, and compound concentration is the standard water solution of 0.1mol/L.Adopting precision is 10
-4Required each raw material of the accurate weighing of the electronic balance of g, put into the glass beaker magnetic agitation of the 1L volume that fills the 500ml ultrapure water, pour in the standard capacity bottle of 1L after the dissolving fully, pour in the standard capacity bottle after rinsing beaker with the 100ml ultrapure water again, 4 times so repeatedly, adopting at last precision is that the 0.1ml drop-burette drips ultrapure water, until standby after standard capacity bottle scale.
The employing capacity is that 25ml, precision are the drop-burette of 0.1ml, presses 73ZrO
2-(23-x) LaO
1.5-0.5xNdO
1.5-0.5xYbO
1.5-4YO
1.5(x=7,9,11,14,16,18) (mol ratio) carries out accurate weighing, magnetic stirrer stirred after 0.5 hour, adding additive citric acid, polyoxyethylene glycol and concentration is 65～68% concentrated nitric acid, addition is respectively 8g/100ml, 5g/100ml and 10ml/100ml, and magnetic agitation obtained the colloidal sol of clear in 0.5 hour.
Adopt the air-atomizing pyrolysis plant, aeroscope is 99.99%, and pressure is 0.3MPa, and it is that the diameter of 600 ℃ is 20cm, high in the corundum crucible of 50cm that colloidal sol is atomised to temperature, after the colloidal sol atomizing is complete, temperature is risen to 1200 ℃ of insulations after 12 hours, cool to room temperature with the furnace.
Adopt agate to grind alms bowl above-mentioned powder is levigate, the Multi-functional X ray diffractometer that the model of producing in Dutch PANalytical company is X ' Pert PRO, be furnished with the super detector of X ' Celerator carries out the phase test, and the x ray is Cu target k
α 1, wavelength
Result sees also Fig. 1.
Adopt agate to grind alms bowl above-mentioned powder is levigate, the Multi-functional X ray diffractometer that the model of producing in Dutch PANalytical company is X ' Pert PRO, be furnished with the super detector of X ' Celerator carries out the phase test, and the x ray is Cu target k
α 1, wavelength
Adopt formula: the grain-size of two-phase in D=0.9 λ/Bcos θ Calculating material, λ in formula, θ and B are respectively the halfwidth of wavelength, diffraction angle and the diffraction peak of x ray.Result sees also Fig. 4.
1200 ℃ of synthetic powder are taken out part put into corundum crucible, calcining after 100 hours in 1450 ℃ of program control High Temperature Furnaces Heating Apparatuss cools to room temperature with the furnace after being cooled to 800 ℃ with the rate of temperature fall of 1 ℃/minute, adopts agate to grind alms bowl and carries out phase after levigate and form test.Adopt formula: M
m/ M
C, t '=0.82[I
m(111)+I
m(111)]/I
C, t '(111) calculate the molar content of monoclinic zirconia phase, I in formula
m(111) and I
m(111) be respectively (111) and the XRD diffraction peak intensity of (111) crystal face of monoclinic zirconia (being called for short m), I
C, t ' (111)XRD diffraction peak intensity for (111) crystal face of cubic zirconia (be called for short c) and metastable tetragonal zirconia zirconium white (abbreviation t ').The result of 1450 ℃ of calcinings after 100 hours sees also Fig. 5 and Fig. 6.
1200 ℃ of synthetic powder are put into circular stainless steel mould compression molding (pressure is 500MPa), and pressed compact thickness is 2mm.Adopt program control High Temperature Furnaces Heating Apparatus sintering, be warming up to 1400 ℃ and be incubated 50 hours with the constant temperature rise rate of 2 ℃/min in air atmosphere, cool to room temperature with the furnace after being cooled to 800 ℃ with the rate of temperature fall of 2 ℃/minute.Adopt field emission scanning electron microscope to observe the surface topography of sample, as shown in Fig. 7 (a).As seen, compare through the situation of the backscattered electron image of 1400 ℃ of sintering after 50 hours with the unmodified material in contrast that Fig. 7 (b) shows, the densification degree of the material sintered compact of the present embodiment after modification is obviously reduced.
Embodiment 2:
73ZrO processed
2-(23-x) LaO
1.5-0.25x NdO
1.5-0.75xYbO
1.5-4YO
1.5(x=7,9,11) composite diphase material
Ln (NO take purity as 99.99%
3)
36H
2O (Ln=La, Nd, Y, Yb) and Zr (NO
3)
43H
2O is raw material, and compound concentration is the standard water solution of 0.1mol/L.Adopting precision is 10
-4Required each raw material of the accurate weighing of the electronic balance of g, put into the glass beaker magnetic agitation of the 1L volume that fills the 500ml ultrapure water, pour in the standard capacity bottle of 1L after the dissolving fully, pour in the standard capacity bottle after rinsing beaker with the 100ml ultrapure water again, 4 times so repeatedly, adopting at last precision is that the 0.1ml drop-burette drips ultrapure water, until standby after standard capacity bottle scale.
The employing capacity is that 25ml, precision are the drop-burette of 0.1ml, presses 73ZrO
2-(23-x) LaO
1.5-0.25xNdO
1.5-0.75xYbO
1.5-4YO
1.5(x=7,9,11) (mol ratio) carries out accurate weighing, magnetic stirrer stirred after 0.5 hour, adding additive citric acid, polyoxyethylene glycol and concentration is 65～68% concentrated nitric acid, addition is respectively 8g/100ml, 5g/100ml and 10ml/100ml, and magnetic agitation obtained the colloidal sol of clear in 0.5 hour.
Adopt the air-atomizing pyrolysis plant, aeroscope is 99.99%, and pressure is 0.3MPa, and it is that the diameter of 600 ℃ is 20cm, high in the corundum crucible of 50cm that colloidal sol is atomised to temperature, after the colloidal sol atomizing is complete, temperature is risen to 1200 ℃ of insulations after 12 hours, cool to room temperature with the furnace.
Adopt agate to grind alms bowl above-mentioned powder is levigate, the Multi-functional X ray diffractometer that the model of producing in Dutch PANalytical company is X ' Pert PRO, be furnished with the super detector of X ' Celerator carries out the phase test, and the x ray is Cu target k
α 1, wavelength
Result sees also Fig. 2.
1200 ℃ of synthetic powder are put into circular stainless steel mould compression molding (pressure is 500MPa), and pressed compact thickness is 2mm.Adopt program control High Temperature Furnaces Heating Apparatus sintering, be warming up to 1400 ℃ and be incubated 50 hours with the constant temperature rise rate of 2 ℃/min in air atmosphere, cool to room temperature with the furnace after being cooled to 800 ℃ with the rate of temperature fall of 2 ℃/minute.Adopt field emission scanning electron microscope to observe the surface topography of sample, result sees also Fig. 8.
Embodiment 3:
62ZrO processed
2-(35.8-x) LaO
1.5-0.5xNdO
1.5-0.5xYbO
1.5-2.2YO
1.5(x=10.8,14.2,17.8) composite diphase material
Ln (NO take purity as 99.99%
3)
36H
2O (Ln=La, Nd, Y, Yb) and Zr (NO
3)
43H
2O is raw material, and compound concentration is the standard water solution of 0.1mol/L.Adopting precision is 10
-4Required each raw material of the accurate weighing of the electronic balance of g, put into the glass beaker magnetic agitation of the 1L volume that fills the 500ml ultrapure water, pour in the standard capacity bottle of 1L after the dissolving fully, pour in the standard capacity bottle after rinsing beaker with the 100ml ultrapure water again, 4 times so repeatedly, adopting at last precision is that the 0.1ml drop-burette drips ultrapure water, until standby after standard capacity bottle scale.
The employing capacity is that 25ml, precision are the drop-burette of 0.1ml, presses 62ZrO
2-(35.8-x) LaO
1.5-0.5xNdO
1.5-0.5xYbO
1.5-2.2YO
1.5(x=10.8,14.2,17.8) (mol ratio) carries out accurate weighing, magnetic stirrer stirred after 0.5 hour, adding additive citric acid, polyoxyethylene glycol and concentration is 65～68% concentrated nitric acid, addition is respectively 8g/100ml, 5g/100ml and 8ml/100ml, and magnetic agitation obtained the colloidal sol of clear in 0.5 hour.
Adopt the air-atomizing pyrolysis plant, aeroscope is 99.99%, and pressure is 0.3MPa, and it is that the diameter of 600 ℃ is 20cm, high in the corundum crucible of 50cm that colloidal sol is atomised to temperature, after the colloidal sol atomizing is complete, temperature is risen to 1200 ℃ of insulations after 12 hours, cool to room temperature with the furnace.
Adopt agate to grind alms bowl above-mentioned powder is levigate, the Multi-functional X ray diffractometer that the model of producing in Dutch PANalytical company is X ' Pert PRO, be furnished with the super detector of X ' Celerator carries out the phase test, and the x ray is Cu target k
α 1, wavelength
Result sees also Fig. 3.
1200 ℃ of synthetic powder are put into circular stainless steel mould compression molding (pressure is 500MPa), and pressed compact thickness is 2mm.Adopt program control High Temperature Furnaces Heating Apparatus sintering, be warming up to 1400 ℃ and be incubated 50 hours with the constant temperature rise rate of 2 ℃/min in air atmosphere, cool to room temperature with the furnace after being cooled to 800 ℃ with the rate of temperature fall of 2 ℃/minute.Adopt field emission scanning electron microscope to observe the surface topography of sample, result sees also Fig. 9.
Claims (6)
1. Nd
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material is characterized in that: described composite diphase material is 99.99% Ln by purity
2O
3(Ln=La, Nd, Yb, Y) and purity are 99.99% ZrO
2Form, composition range is 60～90mol%ZrO
2, 4～30mol%LaO
1.5, 1～10mol%NdO
1.5, 1～10mol%YbO
1.5And 2-7mol%YO
1.5
2. Nd according to claim 1
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material is characterized in that: described complex phase heat barrier coat material is 62ZrO
2-(35.8-x) LaO
1.5-0.5xNdO
1.5-0.5xYbO
1.5-2.2YO
1.5(x=10.8,14.2,17.8).
3. Nd according to claim 1
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material is characterized in that: described complex phase heat barrier coat material is 73ZrO
2-(23-x) LaO
1.5-0.25xNdO
1.5-0.75xYbO
1.5-4YO
1.5(x=7,9,11).
4. Nd according to claim 1
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material is characterized in that: described complex phase heat barrier coat material is 73ZrO
2-(23-x) LaO
1.5-0.5xNdO
1.5-0.5xYbO
1.5-4YO
1.5(x=7,9,11,14,16,18).
5. one kind prepares Nd claimed in claim 1
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The method of complex phase heat barrier coat material is characterized in that:
Ln (NO take purity as 99.99%
3)
36H
2O (Ln=La, Nd, Y) and Zr (NO
3)
43H
2O is raw material, prepares respectively the aqueous solution of 0.1～0.3mol/L,
Press the design mix weighing, add appropriate citric acid, polyoxyethylene glycol and concentrated nitric acid, magnetic agitation is to clear colloidal sol,
Adopt the 0.1-0.3MPa air that colloidal sol is atomised in 300 ℃ of-600 ℃ of corundum crucibles, then temperature is risen to 900～1200 ℃ of calcinings got final product in 0.5～12 hour.
6. the Nd of method according to claim 5 preparation
2O
3-Yb
2O
3The La of modification
2Zr
2O
7-(Zr
0.92Y
0.08) O
1.96The complex phase heat barrier coat material is characterized in that: 1450 ℃ of calcinings are after 100 hours, and in material, the 49mol% of the monoclinic phase content of zirconium white in mutually before by modification is reduced to 0mol%; 1400 ℃ of sintering of material ability after modification.
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