CN100376505C - Material for thermal barrier coating - Google Patents

Material for thermal barrier coating Download PDF

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CN100376505C
CN100376505C CNB2004800077883A CN200480007788A CN100376505C CN 100376505 C CN100376505 C CN 100376505C CN B2004800077883 A CNB2004800077883 A CN B2004800077883A CN 200480007788 A CN200480007788 A CN 200480007788A CN 100376505 C CN100376505 C CN 100376505C
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heat
coefficient
thermal expansion
composition
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CN1764613A (en
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秋山胜德
永野一郎
志田雅人
太田悟志
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Mitsubishi Heavy Industries Ltd
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Abstract

A thermal barrier coating material, which comprises, as a main component, a composition having an orthorhombic or monoclinic structure (for example, a tabular perovskite structure represented by the empirical formula: A2B2O7) derived from a perovskite structure or a tetragonal layer structure having a c axis/a axis ratio of 3 or more (for example, a K2NiF4 structure a Sr3Ti2O7 structure and a Sr4Ti3O10 structure), a composition represented by the empirical formula: LaTaO4, or a composition having an olivine type structure represented by the empirical formula: M2SiO4 or (MM')2SiO4 wherein M and M' are divalent metal elements. The thermal barrier coating material is novel, is free from problems of the phase transition and the like has a melting point higher than the temperature region for use, and has a thermal conductivity less than that of zirconia and a thermal expansion coefficient greater than that of zirconia.

Description

Heat-proof coating material
Technical field
The present invention relates to the heat-proof coating material of the mechanical part that under hot environment, uses with rotor blade, stator vane, burner and the jet engine etc. of internal combustion turbine applicable to generating.
Background technology
In order to improve the efficient of internal combustion turbine and jet engine, adopt the method for temperature that improves its combustion gases.Therefore, in order to protect the metal member made down, on parts surface, cover heat insulating coat (Thermal Barrier Coating:TBC) at high temperature (for example the blade surface temperature of 1500 ℃ of level internal combustion turbine is about 1400 ℃).As the material of this heat insulating coat, use the low heat conductivity pottery (for example can with reference to spy open flat 8-074505 communique and Te Kai flat 10-183013 communique) of the zirconium white of rare earth class stabilization as representative.Above-mentioned heat insulating coat is by after forming metallic bond layer by decompression plasma spraying etc. on the base material of metal member made, carries out the atmos plasma spraying thereon and implements.
Being sprayed on the heat insulating coat that is provided with on the metal member made by atmos plasma is not fine and close tissue, and portion has a large amount of pores within it.Fig. 1 is the synoptic diagram that shows the tissue of heat insulating coat.As shown in Figure 1, the tissue of heat insulating coat has following structure: in zirconium white mother metal 1, exist diameter to reach the gross blow hole 2, diameter of the tens of μ m pore for the different shapes such as wire pore 4,5 of the spilehole 3 of number μ m, narrow width.Zirconium white mother metal 1 self is the pottery of low heat conductivity, simultaneously has a large amount of above-mentioned these pores 2～5 in inside, has guaranteed the heat-proof quality of material thus, can use under hot environment as the metal member made of base material.
The zirconium white when the high-temperature structural material that heat insulating coat also comprises is not single composition (ZrO 2), but the state (zirconium white of partially stabilizedization) of several moles of % as the rare-earth oxide of stablizer etc. use down having added.Because do not adding the pure zirconia (ZrO of stablizer 2) the middle existence:
～1000℃ 2370℃
Oblique crystal ← → regular crystal ← → cube crystalline substance
2 kinds of phase transitions like this when directly only heating up cooling, are accompanied by the phase transition between oblique crystal, the regular crystal, produce fierce volume change and are destroyed, so that can not be used as high-temperature structural material.Therefore must add the rare-earth oxide of several moles of %,, and not generate the monocline crystalline phase even make tetragonal phase also keep stable at low temperatures as the operating temperature range phase.There is report to point out, even the amount of control stabilization agent and make the zirconium white of partially stabilizedization of regular crystal stabilization, it is at high temperature long-time to use and when circulation heats up cooling repeatedly, also can little by little separate out the monocline crystalline phase, the major issue when this becomes zirconium white and is used for heat insulating coat.
Also there is report to point out, can be in order to La 2Zr 2O 7For the material of cube brilliant pyrochlore type structure of representative replaces zirconium white as heat-proof coating material (can open flat 10-212108 communique, No. the 0848077th, European patent, No. the 6117560th, United States Patent (USP) with reference to the spy).According to these documents, La 2Zr 2O 7Thermal conductivity less than zirconium white, and the oxygen perviousness is less than zirconium white, therefore is suitable as heat-proof coating material.But because La 2Zr 2O 7Coefficient of thermal expansion also less than zirconium white, thereby its problem is, may be between when practical application as the metal member made of base material residual tensile stress.
Summary of the invention
As mentioned above, be heat-proof coating material for zirconium white, guarantee that the stability of phase can not be short of.In addition, for as the material of heat insulating coat, require the fusing point height, thermal conductivity is minimum and coefficient of thermal expansion as far as possible near the metal member made between metal member made, not produce tensile stress as base material.
In order to address the above problem, the present invention aim to provide the problem, the fusing point that do not have phase transition be higher than operating temperature range, thermal conductivity less than zirconium white and coefficient of thermal expansion greater than zirconic novel heat-insulation coated material.
As mentioned above, have the instead zirconic novel heat-insulation coated material of the material that fusing point, thermal conductivity are little, coefficient of thermal expansion is big that is higher than working temperature in order to provide, present inventors have adopted the calculating of first principle to carry out the exploration of material.Aforementioned " calculating of first principle " is the condition of finding the solution quantum-mechanical fundamental equation by change, obtains the method for nano level various physics values.
And, present inventors find that carrying out result calculated under the fusing point with the working temperature that is higher than 1400 ℃, thermal conductivity is as far as possible little, coefficient of thermal expansion is big as far as possible condition is, find by uhligite deutero-iris or monoclinic structure (for example by composition formula A 2B 2O 7The tabular perovskite structure of expression) or c axle/a axial ratio be 3 or the laminate structure of bigger regular crystal (K for example 2NiF 4Structure and Sr 3Ti 2O 7Structure, Sr 4Ti 3O 10Structure) material and by composition formula LaTaO 4The material of expression can satisfy aforementioned condition.These materials are compared the crystalline texture complexity with the zirconium white based material with fluorite type structure with a cube brilliant pyrrhite based material, therefore can expect that it demonstrates lower thermal conductivity, in addition because it is long on the single shaft direction, can expect to demonstrate higher thermal expansivity, think to be suitable as novel heat-proof coating material.
Have by aforementioned component formula A 2B 2O 7In the heat-proof coating material of the present invention of the uhligite deutero-structure of expression, the aforementioned component elements A is preferably selected from any among La, Nd, the Sr, and the aforementioned component element B is preferably selected from any among Ti, Si, Nb, the Ta.Present inventors have confirmed: by using these elements, can obtain the material of coefficient of thermal expansion greater than the little suitable formation heat insulating coating film of zirconium white and thermal conductivity.
In addition, has aforementioned K 2NiF 4Structure, composition formula X 2YO 4In the heat-proof coating material of the present invention of expression, aforementioned component element X is La or Sr preferably, and component Y is Ni or Ti preferably.Present inventors have confirmed: by using these elements, can obtain the material of coefficient of thermal expansion greater than the little suitable formation heat insulating coating film of zirconium white and thermal conductivity.
The above-mentioned heat-proof coating material of enumerating can be brought into play enough high thermal expansivity, low heat conductivity separately, and can easily infer: even from these compositions, select 2 kinds or more compositions to carry out compound, can not damage its high thermal expansivity and low heat conductivity yet, therefore think that it is very suitable as heat-proof coating material.Perhaps also can easily infer,, only otherwise damage crystalline texture, also can not damage high thermal expansivity and low heat conductivity even add other element to above-mentioned heat-proof coating material or in the material of its compoundization.
By other investigation and research, present inventors find to have by composition formula M 2SiO 4Or (MM ') 2SiO 4The material of the olivine-type structure of (wherein M, M ' are the metallic element of divalent) expression meets and has the condition that fusing point, thermal conductivity are little, coefficient of thermal expansion is big that is higher than working temperature.The aforementioned component element M is preferably Mg or Ni, the aforementioned component element M ' be preferably the metallic element that is selected from Ca, Co, Ni, Fe, Mn.These metallic elements mostly are the peridotites group's of natural stable existence mineral greatly.In addition, Mg, Ca are more cheap than rare earth class in the above-mentioned metallic element.
And then because M 2SiO 4Density be zirconic about 1/2～about 5/6, can alleviate the gross weight when constructing as heat insulating coating film, can expect the efficient of internal combustion turbine etc. is produced desirable influence, be fit to practical application.
And then can easily infer, can bring into play high thermal expansivity, low heat conductivity fully separately by these materials that calculating among the present invention and investigation are derived, even carry out compound with the zirconium white based material of present use, as long as formula according to compoundization that illustrates among the aftermentioned embodiment, then can not damage its high thermal expansivity and low heat conductivity, even think that therefore itself and zirconium white based material carry out compound tense and also be enough to as heat-proof coating material.
In addition, present inventors have carried out more deep exploration to the composition of the condition that satisfies the heat-proof coating material be suitable as aforementioned record, found that, contain the oxide compound that forms by alkaline-earth metal or rare earth element and Nb material, and contain by composition formula LaTaO as main body 4La in the composition of expression be selected from the metallic element displacement of Al, V, Cr, Fe, Ga, Y, Rh, In, Ce, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu and the composition that forms as the material of main body with to contain the oxide compound that is formed by alkaline-earth metal and Ta be that the material of main body also satisfies aforementioned requirement.
As the above-mentioned oxide compound that forms by alkaline-earth metal or rare earth element and Nb, confirmed to be selected from Sr 4Nb 2O 9, Sr 5Nb 4O 15, Ca 2Nb 2O 7, YNbO 4, LaNbO 4Oxide compound be preferred oxide compound.In addition, as the above-mentioned oxide compound that forms by alkaline-earth metal and Ta, confirmed Ca 4Ta 2O 9Or BaTa 2O 6Be preferred.
Have again, contain aforementioned record by aforementioned component formula X 2YO 4In the heat-proof coating material of expression, present inventors have confirmed, aforementioned component element X is any among Pr, Nd, the Eu preferably, and aforementioned component element Y is Ni preferably.
The composition that can constitute the heat-proof coating material of the invention described above can mutually or carry out compound back with the zirconium white based material and use.That is, the oxide compound that forms by alkaline-earth metal or rare earth element and Nb, by composition formula LaTaO 4La in the composition of expression is by other metallic element metathetical composition and Ca 4Ta 2O 9, BaTa 2O 6(oxide compound that is formed by alkaline-earth metal and Ta) can carry out compound back mutually and use, and perhaps carries out compound back with known zirconium white based material and uses.And, even the composition formula A of these ceramic compositions and aforementioned record 2B 2O 7(wherein, the aforementioned component elements A is the element that is selected from La, Nd, Sr, and the aforementioned component element B is the element that is selected from Ti, Si, Nb, Ta) expression composition, have by composition formula X 2YO 4The K of expression 2NiF 4Structure, aforementioned component element X be La or Sr, component Y be the composition of Ni or Ti, by composition formula Sr 3Ti 2O 7Perhaps Sr 4Ti 3O 10The expression composition and by composition formula LaTaO 4The composition of expression carries out compound, also can be suitable as heat-proof coating material.
On the other hand, aforementioned Sr-Nb system complex oxide Sr 2Nb 2O 7, Sr 4Nb 2O 9By Nb being replaced solid solution, can further reduce thermal conduction with Ti or Zr.That is, also can be, by Sr as aforesaid oxides 2Nb 2-XTi xO 7(0＜x≤2) or Sr 2Nb 2-XZr xO 7(0＜x≤2) or Sr 4Nb 2-XTi xO 9(0＜x≤2) or Sr 4Nb 2-XZr xO 9The oxide compound of (0＜x≤2) expression.
By replace the part of the most stable electronic state 5 valencys of Nb by 4 valencys, produce the oxygen room, it is more complicated that crystalline texture becomes, and therefore further suppresses phon scattering, hinders heat passage.Yet though also exist the element that other keeps 4 valence electron states in a large number, the ionic radius during owing to other element 4 valencys is not suitable for, and therefore can not keep Sr 2Nb 2O 7And Sr 4Nb 2O 9Structure.Therefore, select Ti and Zr as the element of Nb being replaced solid solution.
And then, because SrYb 2O 4, Sr 4Yb 2O 9And Ca 11Nb 4O 21, La 3NbO 7, DyNbO 4Keep and the similar structure of described crystal structure and have lower thermal conductivity before, thereby can be used for heat-proof coating material.
In addition, with the Sr-Nb system complex oxide similarly, by with Ti or Zr to BaTa 2O 6Ta replace solid solution, can further reduce thermal conduction.That is, can become by BaTa 2-XTi XO 6(0＜x≤2) or BaTa 2-XZr XO 6The oxide compound of (0＜x≤2) expression.
At this moment, by replaced the part of the most stable electronic state 5 valencys of Ta by 4 valencys, produce the oxygen room, it is more complicated that crystalline texture becomes, and therefore further suppresses phon scattering, hinders heat passage.Yet though also exist the element that other keeps 4 valence electron states in a large number, the ionic radius during owing to other element 4 valencys is not suitable for, and therefore can not keep BaTa 2O 6Structure.Therefore, select Ti or Zr as the element of Ta being replaced solid solution.
In addition, with above-mentioned Ba-Ta system complex oxide similarly, by with Ca to LaNiO 4La replace solid solution, can further reduce thermal conduction.That is, can become by La 2-XCa XNiO 4The oxide compound of (0＜x≤2) expression.
At this moment, the most stable electronic state 3 valencys by by divalent displacement La produce the oxygen room, and it is more complicated that crystalline texture becomes, and therefore further suppress phon scattering, hinder heat passage.Yet though also exist the element that other keeps the divalent electronic state in a large number, the ionic radius during owing to other element divalent is not suitable for, and therefore can not keep LaNiO 4Structure.Therefore, select Ca as the element of La being replaced solid solution.
Have, heat-proof coating material of the present invention can be with the composite oxides that contain tungsten oxide as main body again.That is, can contain by composition formula J 6WO 12, J 2WO 6(wherein aforementioned formation element J is selected from rare earth element.) expression composition be main body.
The above-mentioned composition that can constitute heat-proof coating material of the present invention can mutually or carry out compound back with the zirconium white based material and use.Just, though with at Sr-Nb system complex oxide Sr 2Nb 2O 7And Sr 4Nb 2O 9In with Ti or Zr to Nb replace the oxide compound of solid solution, at SrYb 2O 4, Sr 4Yb 2O 9, Ca 11Nb 4O 21, La 3NbO 7, DyNbO 4And BaTa 2O 6In with Ti or Zr Ta is replaced the oxide compound of solid solution and replaces LaNiO with Ca 4The oxide compound of La carry out compoundly, also can be suitable as heat-proof coating material.
Also have, heat-resistant part of the present invention is characterised in that: form the heat-proof coating material heat insulating coating film of the present invention that uses aforementioned record on base material.By this structure, compare with the zirconium white of present use, can show higher coefficient of thermal expansion and lower thermal conductivity, by being provided with by filming that heat-proof coating material of the present invention constitutes, can provide and to realize good thermotolerance, the anti-separability that the simultaneous temperature circulation time is filmed is also good, the heat-resistant part that can withstand prolonged uses.
According to the present invention, by containing by composition formula A 2B 2O 7The composition (particularly component A=La, Nd, Sr, the composition of component B=Ti, Si, Nb, Ta) of expression or have by composition formula X 2YO 4The K of expression 2NiF 4Structure (particularly aforementioned component element X is La, Sr, and component Y is the composition of Ni, Ti) is perhaps by composition formula Sr 3Ti 2O 7, Sr 4Ti 3O 10, or LaTaO 4The composition of expression, and further by 2 kinds of these compositions or carry out compound and the composition that forms as main body, can provide with the zirconium white of present use and compare, what demonstrate higher coefficient of thermal expansion and lower thermal conductivity is suitable for the heat insulating coating film material.
In addition, according to the present invention, by having by composition formula M 2SiO 4Or (MM ') 2SiO 4The composition of the olivine-type structure of expression (particularly component M=Mg, Ni, and the composition of component M '=Ca, Co, Ni, Fe, Mn) as main body, can provide with the zirconium white of present use and compare, demonstrate higher coefficient of thermal expansion and lower thermal conductivity, cheap heat insulating coating film material.
In addition, according to the present invention, by containing the oxide compound that forms by alkaline-earth metal or rare earth element and Nb, perhaps by composition formula LaTaO 4La in the composition of expression be selected from the metallic element displacement of Al, V, Cr, Fe, Ga, Y, Rh, In, Ce, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu and the composition that forms as the material of main body, the perhaps oxide compound that forms by alkaline-earth metal and Ta, can provide with the zirconium white of present use and compare, demonstrate the heat insulating coating film material of higher coefficient of thermal expansion and lower thermal conductivity.
And then, according to the present invention, by containing above-mentioned ceramic composition reciprocally or with known zirconium white based material is carried out the compound material that forms, can provide above-mentioned coefficient of thermal expansion and thermal conductivity further are controlled at heat-proof coating material in the optimum range.
Description of drawings
Fig. 1 is the synoptic diagram of the tissue of heat insulating coat.
Fig. 2 is MgO-SiO 2The state graph of system.
Fig. 3 is FeO-SiO 2The state graph of system.
Fig. 4 is MnO-SiO 2The state graph of system.
Fig. 5 is NiO-SiO 2The state graph of system.
Fig. 6 is CoO-SiO 2The state graph of system.
Fig. 7 is FeO-MgO-SiO 2The state graph of system.
Fig. 8 is CaO-MgO-SiO 2The state graph of system.
Fig. 9 is FeO-MnO-SiO 2The state graph of system.
Figure 10 is MgO-MnO-SiO 2The state graph of system.
Figure 11 is Mg 2SiO 4-Ni 2SiO 4The state graph of system.
Embodiment
Embodiments of the present invention are described with reference to the accompanying drawings.
[embodiment 1]
Knownly find the solution the condition of quantum-mechanical fundamental equation, can obtain nano level various physics value by change.This method is not adopt any test-results to carry out non-empirical calculating as parameters calculated, obtains the research method of required information, is called " calculating of first principle ".In the present invention, adopt this first principle to calculate and infer coefficient of thermal expansion α and thermal conductivity λ from crystalline texture.
(come from; Http:// www.nistep.go.jp/achiev/ftx/jpn/stfc/stt009j/feature3.ht ml#4-0" scientific and technical trend " December calendar year 2001 number, policies of science and technology institute of Japanese MEXT science and technology trend research centre)
At first, present inventors calculate principle according to first, study for coefficient of thermal expansion α that is inferred by crystalline texture and thermal conductivity λ, have selected by composition formula Nd 2Ti 2O 7, La 2Si 2O 7, La 2Ti 2O 7, Sr 2Nb 2O 7, Sr 2Ta 2O 7, Sr 3Ti 2O 7, La 2NiO 4, LaTaO 4The composition of expression.
Then, select the oxide compound of these components or carbonate as starting raw material, weighing reaches the regulation ratio, uses the ball mill solid phase mixing.Behind the dry mixed powder, 1200 ℃ of following pre-burnings.Identify the pre-burning powder that obtains by powder x-ray diffraction, confirming does not have the unreacting material composition residual, and all test portions all become single-phase.
Then at 1400 ℃ of above-mentioned each test portions of roasting, downcut the bar-shaped test portion of 4 * 4 * 15mm from its sintered compact, measure coefficient of thermal expansion.The value of the coefficient of thermal expansion under 1000 ℃ is as shown in table 1.Also put down in writing comparative material 3YSZ (3mol%Y in addition in this table 2O 3-ZrO 2: the value of the coefficient of thermal expansion zirconium white of partially stabilizedization of yttrium oxide).
Table 1
The material name Coefficient of thermal expansion [* 10 -6/℃]
3YSZ (comparative material) 9.92
Nd 2Ti 2O 7 10.01
La 2Si 2O 7 7.97
La 2Ti 2O 7 9.60
Sr 2Nb 2O 7 10.77
Sr 2Ta 2O 7 7.93
Sr 3Ti 2O 7 11.99
La 2NiO 4 13.98
LaTaO 4 5.33
In the material of making, Nd 2Ti 2O 7, Sr 2Nb 2O 7, Sr 3Ti 2O 7, La 2NiO 4Demonstrate coefficient of thermal expansion greater than 3YSZ.This explanation is when these materials are used as heat insulating coat, and the possibility that produces tensile stress between the metal member made on basis is less than the zirconium white that uses at present.
Then for Nd 2Ti 2O 7, La 2Si 2O 7, La 2Ti 2O 7, Sr 2Nb 2O 7, Sr 2Ta 2O 7, Sr 3Ti 2O 7, La 2NiO 4, LaTaO 4,,,, measure thermal conductivity by laser flash method from the discoid test portion of its sintered compact cutting-out diameter 10mm φ, thick 1mm 1400 ℃ of following roastings.The value of thermal conductivity at room temperature is as shown in table 2.Also put down in writing the value (1000 ℃, literature value) of the coefficient of thermal expansion of comparative material 3YSZ in addition in this table.
Table 2
The material name Thermal conductivity [W/m.K]
3YSZ (comparative material) (2.2 1000 ℃, literature value)
Nd 2Ti 2O 7 2.57
La 2Si 2O 7 1.68
La 2Ti 2O 7 2.28
Sr 2Nb 2O 7 1.74
Sr 2Ta 2O 7 2.99
Sr 3Ti 2O 7 5.64
La 2NiO 4 2.66
LaTaO 4 2.11
Existence between the mean free path L of the thermal conductivity λ of material and specific heat C, heat-transfer medium (phonon), its movement velocity v is as shown in the formula the relation of (1) expression.Because mean free path L and the absolute temperature T of phonon are inversely proportional to (L ∝ (1/T)), therefore under the situation of pottery, formula (1) is as following formula (2) (wherein A is a rate constant), the tendency of thermal conductivity minimizing when demonstrating temperature and rise.
λ∝C·L·v .......(1)
λ＝A·(C·L·v)/T .......(2)
Nd in the table 2 2Ti 2O 7, La 2Si 2O 7, La 2Ti 2O 7, Sr 2Nb 2O 7, Sr 2Ta 2O 7, Sr 3Ti 2O 7, La 2NiO 4Thermal conductivity be in the room temperature (～value 300K) measured down.According to formula (2), can infer about 1/4 of value when thermal conductivity under these materials 1000 ℃ (1273K) is room temperature.Under its 1000 ℃ to infer heat conductivity value as shown in table 3.
As shown in table 3, can infer that these materials any one in 1000 ℃ thermal conductivity is all little than zirconium white, think that it can be suitable as heat-proof coating material.
Table 3
The material name Supposition thermal conductivity [W/m.K] under 1000 ℃
3YSZ (comparative material) (2.2 1000 ℃, literature value)
Nd 2Ti 2O 7 0.643
La 2Si 2O 7 0.420
La 2Ti 2O 7 0.570
Sr 2Nb 2O 7 0.435
Sr 2Ta 2O 7 0.748
Sr 3Ti 2O 7 1.41
La 2NiO 4 0.665
LaTaO 4 0.528
[embodiment 2]
In the present embodiment, the compound of material of having measured coefficient of thermal expansion, thermal conductivity in the foregoing description 1 studied.
According to embodiment 1, La 2Si 2O 7, La 2Ti 2O 7, Sr 2Ta 2O 7And LaTaO 4Because the coefficient of thermal expansion of itself less than zirconium white, may produce tensile stress when therefore being used for heat-proof coating material.Therefore, for low heat conductivity and the high coefficient of thermal expansionization of keeping these materials, study for the compound of other high coefficient of thermal expansion material of record in itself and the table 1.
2 kinds of big potteries of thermal expansion rate variance are being carried out compound tense, the coefficient of thermal expansion (α of its matrix material c) by shown in the following formula (3) that is called Tener (Turner) formula.In the formula (3), α is a coefficient of thermal expansion, and K is a volumetric modulus of elasticity, and V is a volume fraction, and subscript m is a matrix, the phase of subscript p for adding.
α c＝(α pV pK p+α mV mK m)/(V pK p+V mK m)···(3)
The thermal conductivity of matrix material (λ) is by shown in the following formula (4) that is called Mike Si Weier-Ou Ken (Maxwell-Eucken) formula in addition.In the formula (4), λ is a thermal conductivity, and V is a volume fraction, and subscript m is a matrix, the phase of subscript p for adding.
λ c＝λ m{1+2V p(1-λ m/λ p)/(2λ m/λ p+1)}/{1-V p(1-λ m/λ p)/(λ m/λ p+1)}
···(4)
For example, with the low heat expansion property shown in the table 1 (low heat conductivity) material LaTaO 4(α=5.33, λ=2.11) and high thermal expansivity (high thermal conductivity) material Sr 3Ti 2O 7(α=11.99, λ=5.64) carry out compound.That is, with Sr 3Ti 2O 7As matrix, LaTaO 4As the phase of adding.If add 10vol%LaTaO 4, V then p=0.1, Sr in addition 3Ti 2O 7And LaTaO 4Volumetric modulus of elasticity be respectively K m=146.7, K p=213.6.
With these numerical value substitution formulas (3), formula (4),
According to formula (3), α c=11.06
According to formula (4), λ c=5.11
Because λ c=5.11 is the room temperature thermal conductivity, is about 1/4 supposition according to the thermal conductivity under 1000 ℃, λ=1.28.It all is to make in the favourable value of heat insulating coat that its coefficient of thermal expansion, thermal conductivity are compared with the zirconium white based material of present use.
By compound 2 kinds of materials like this, coefficient of thermal expansion and thermal conductivity can be got both intermediary values, by suitably determining volume fraction, can control its value.Though be here to Sr 3Ti 2O 7And LaTaO 4The compound situation is calculated, but can easily infer, also carries out same research by other material of putting down in writing in the his-and-hers watches, also can control its coefficient of thermal expansion and thermal conductivity.
Therefore, think that 2 kinds of record in his-and-hers watches 1 and the table 2 or more material carry out compound and material that form enough is suitable as heat-proof coating material.
[embodiment 3]
Though Mg 2SiO 4Being used as insulating material in electronics, electric installations such as IC substrate and assembly, is the example of the high-temperature structural material of representative but also be not used in the heat insulating coat.Present inventors are conceived to Mg 2SiO 4The high thermal expansivity and the low heat conductivity that are had are considered the application aspect heat insulating coat, at first to Mg 2SiO 4And similar compound is studied.
Mg 2SiO 4The mineral name be forsterite, belong to iris, have according to spacer Pmnb and be categorized as M 2SiO 4The material of the olivine-type structure of (M is the divalent metallic element).Belong to this iris, have according to spacer Pmnb and be categorized as M 2SiO 4The material of the olivine-type structure of (M is the divalent metallic element) also has Fe 2SiO 4(mineral name fayalite), Mn 2SiO 4(mineral name tephroite), Ni 2SiO 4(mineral name nickel peridotites), Co 2SiO 4Deng.
The divalent metallic element that M represents in the above-mentioned composition formula needs not to be a kind, for example also has (M, M ') 2SiO 4Form, promptly (Fe, Mg) 2SiO 4(mineral name peridotites), (Ca, Mg) 2SiO 4(mineral name monticellite), (Fe, Mn) 2SiO 4(mineral name knebelite), (Ca, Mn) 2SiO 4(mineral name glaucochroite), (Ca, Fe) 25iO 4Materials such as (mineral name kirschsteinites).Though the part of this divalent metallic element represents that with this form of (M, M ') it must be 1: 1 that M and M ' are not limited to, and can be any ratio.
To these by M 2SiO 4Or (M, M ') 2SiO 4The thermostability of the material of expression is studied.The state graph of each material such as Fig. 2 are to shown in Figure 11.The fusing point of reading from each state graph (or decomposition temperature) is as shown in table 4 in addition.In addition, the source of each state graph of Fig. 2 to Figure 11 is documented in the table 9.
Table 4
The material name Fusing point (or decomposition temperature) [℃]
Mg 2SiO 4 1890
Fe 2SiO 4 1205
Mn 2SiO 4 1345
Ni 2SiO 4 1545
Co 2SiO 4 1420
(Fe，Mg) 2SiO 4 1205～1890
(Ca，Mg) 2SiO 4 1430～1490
(Fe，Mn) 2SiO 4 1205～1250
(Mg，Mn) 2SiO 4 1345～1890
(Mg，Ni) 2SiO 4 1630～1890
CaMnSiO 4 1355
CaFeSiO 4 1230
If consider that fusing point wherein is lower than 1400 ℃ Fe as heat insulating coat 2SiO 4, Mn 2SiO 4, (Fe, Mn) 2SiO 4, CaMnSiO 4, CafeSiO 4Obviously be unaccommodated.Yet for example (Fe, Mg) 2SiO 4Situation under as can be known, by with dystectic Mg 2SiO 4With low-melting Fe 2SiO 4Compound, can make have its intermediary fusing point (Fe, Mg) 2SiO 4And, can control the FeO-MgO-SiO of its fusing point this point from Fig. 7 by the ratio of Fe and Mg 2Be to read in the state graph.Thereby can easily infer, for the situation beyond Fe and the Mg, by selecting (M, M ') 2SiO 4M and element combinations and the ratio thereof of M ', can obtain having the material of desirable fusing point.
Then, for by composition formula Mg 2SiO 4, Ni 2SiO 4, Co 2SiO 4, (Ca, Mg) 2SiO 4, (Mg, Co) 2SiO 4, (Mg, Ni) 2SiO 4, (Ni, Co) 2SiO 4The composition of expression, the oxide powder of each component of weighing are to reach the ratio of regulation, and after the ball mill solid phase mixing, the pre-burning powder is made 1200 ℃ of following pre-burnings in dry back.Identify the pre-burning powder that obtains by powder x-ray diffraction, confirm not have SiO 2Residual Deng the unreacting material composition, all test portions all become single-phase.
The theoretical density of the material of record is as shown in table 5 in the table 4.But omitted in these materials owing to fusing point is lower than 1400 ℃ of materials that are not suitable for use in heat insulating coat.In addition, for the Mg that more than 1400 ℃ of following roastings, makes 2SiO 4, Ni 2SiO 4, Co 2SiO 4, (Ca, Mg) 2SiO 4, (Mg, Co) 2SiO 4, (Mg, Ni) 2SiO 4, (Ni, Co) 2SiO 4Each pre-burning powder, the measurement result of the density of its sintered compact also is shown in Table 5.But Co wherein 2SiO 4Owing to the sintered compact partial melting is excluded outside determination object.Also put down in writing comparative material 3YSZ (3mol%Y in addition in this table 2O 3-ZrO 2: the value of the density zirconium white of partially stabilizedization of yttrium oxide).
Table 5
The material name Theoretical density [g/cm 3] Measuring density [g/cm 3] Relative density [%]
3YSZ (comparative material) ～6.00 5.844 ～97.4
Mg 2SiO 4 3.222 2.538 78.22
Ni 2SiO 4 4.923 4.040 82.06
Co 2SiO 4 4.708 - -
(Ca，Mg) 2SiO 4 3.057 2.374 89.43
(Mg，Co) 2SiO 4 ～3.97 3.722 ～93.8
(Mg，Ni) 2SiO 4 ～4.07 3.088 ～75.9
(Ni，Co) 2SiO 4 ～4.82 4.249 ～88.2
The relative density of the 3YSZ of material proposition is 97% as a comparison, almost is DB, and by comparison, other material demonstrates 75～94% relatively low density value.Can infer M thus 2SiO 4(MM ') 2SiO 4It is hard-to-sinter all that the material of system is compared with zirconium white.During as heat insulating coat, it is organized becomes the state with a large amount of pores as shown in Figure 1 on spraying to metal parts.Owing to there are these a large amount of pores, think that the thermal resistance performance of material is guaranteed, compare with the zirconium white of present use and be difficult to become fine and close.Thereby think that these have M 2SiO 4Or (MM ') 2SiO 4The material of olivine-type structure can be suitable as heat insulating coat.
The theoretical density of any material is zirconic about 1/2～about 5/6 in addition, can alleviate the weight that heat insulating coating film adds man-hour, can expect the efficient of internal combustion turbine etc. is produced desirable influence,, think that these materials also are suitable for practical application therefore from this point.
[embodiment 4]
1400 ℃ of following roastings, make by composition formula Mg 2SiO 4, Ni 2SiO 4, (Ca, Mg) 2SiO 4, (Mg, Co) 2SiO 4, (Mg, Ni) 2SiO 4, (Ni, Co) 2SiO 4The composition of expression downcuts the bar-shaped test portion of 4 * 4 * 15mm from each sintered compact that obtains, and measures coefficient of thermal expansion.Coefficient of thermal expansion under 1000 ℃ is as shown in table 6.The value of the coefficient of thermal expansion of comparative material 3YSZ also is shown in this table in addition.
Table 6
The material name Coefficient of thermal expansion [* 10 -6/℃]
3YSZ (comparative material) 9.92
Mg 2SiO 4 11.59
Ni 2SiO 4 12.59
(Ca，Mg) 2SiO 4 11.89
(Mg，Co) 2SiO 4 11.40
(Mg，Ni) 2SiO 4 10.97
(Ni，Co) 2SiO 4 10.42
As shown in table 6, the coefficient of thermal expansion of any test portion of making all demonstrates the value greater than 3YSZ.This expression, when being used for heat insulating coat, the possibility that produces tensile stress between the metal member made of matrix is also less than the zirconium white that uses at present.Therefore from this point, think to have M 2SiO 4Or (MM ') 2SiO 4The material of olivine-type structure go for heat insulating coat.
Calcine down at 1400 ℃ then and make by composition formula Mg 2SiO 4, Ni 2SiO 4, (Ca, Mg) 2SiO 4, (Mg, Co) 2SiO 4The composition of expression downcuts the discoid test portion of diameter 10mm φ, thick 1mm from each sintered compact that obtains, and by laser flash method, measures thermal conductivity.The value of thermal conductivity at room temperature is as shown in table 7.Also put down in writing the value (1000 ℃, literature value) of the coefficient of thermal expansion of comparative material 3YSZ in addition in this table.
Table 7
The material name Thermal conductivity [W/m.K]
3YSZ (comparative material) (2.2 1000 ℃, literature value)
Mg 2SiO 4 4.00
Ni 2SiO 4 8.52
(Ca，Mg) 2SiO 4 3.85
(Mg，Co) 2SiO 4 3.29
Carry out and same experiment described in before the embodiment 1, can infer with table 7 in the Mg of record 2SiO 4, Ni 2SiO 4, (Ca, Mg) 2SiO 4, (Mg, Co) 2SiO 4The heat conductivity value of measuring down in room temperature (～300 ℃) compare about 1/4 of the value the when thermal conductivity under 1000 ℃ (1273K) is its room temperature.1000 ℃ supposition heat conductivity value is as shown in table 8.
Table 8
The material name 1000 ℃ supposition thermal conductivity [W/m.K]
3YSZ (comparative material) (2.2 1000 ℃, literature value)
Mg 2SiO 4 1.00
Ni 2SiO 4 2.13
(Ca，Mg) 2SiO 4 0.963
(Mg，Co) 2SiO 4 0.823
As shown in table 8, can infer that any one thinks that all less than zirconium white it is enough to be applicable to heat insulating coat to these materials in 1000 ℃ thermal conductivity.
Table 9
Publisher: AMERICAN CERAMIC SOCIETY
Title: " PHASE DIAGRAMS FOR CERAMISTS " vol.1～6
Author: Ernst M.Levin, Carl R.Robbins, Howard F.McMurdie
Edition year: Vol.1 1964
Vol.2 1969
Figure number Composition formula Reel number Number of pages Reference drawing
Fig. 2 MgO-SiO 2System Vol.1 112 pages Fig.266
Fig. 3 Fe-Si-O system Vol.1 59 pages Fig.8
Fig. 4 Mn-Si-O system Vol.1 65 pages Fig.101
Fig. 5 NiO-SiO 2System Vol.2 90 pages Fig.2324
Fig. 6 Co-Si-O system Vol.2 23 pages Fig.2120
Fig. 7 FeO-MgO-SiO 2System Vol.1 236 pages Fig.682
Fig. 8 CaO-MgO-SiO 2System Vol.1 210 pages Fig.598
Fig. 9 FeO-MnO-SiO 2System Vol.1 239 pages Fig.689
Figure 10 MgO-MnO-SiO 2System Vol.1 242 pages Fig.699
Figure 11 MgO-NiO-SiO 2System Vol.1 243 pages Fig.702
[embodiment 5]
Owing in embodiment 1 before, can infer Sr 2Nb 2O 7Coefficient of thermal expansion greater than zirconium white, and thermal conductivity is less than zirconium white, thereby is applicable to heat-proof coating material, based on this, in this example, for other the research that the Nb oxide compound similarly carries out coefficient of thermal expansion α, thermal conductivity λ that contains.In addition, similarly based on embodiment 1 described La 2NiO 4, for using other rare earth element, for example Pr, Nd, Eu etc. and La are similarly the rare earth element displacement La of 3 valencys and the oxide compound that obtains, and based on the La described in the embodiment 1 2NiO 4Metallic element with other 3 valency, for example Al, V, Cr, Fe, Ga, Y, Rh, In, Ce, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu displacement La and the oxide compound that obtains also has other oxide compound that contains Ta similarly to carry out the research of coefficient of thermal expansion α, thermal conductivity λ.Here the material of Xuan Zeing is, changes the Sr of the ratio of Sr and Nb 4Nb 2O 9, Sr 5Nb 4O 15, replace the Ca of Sr with the Ca that is all alkaline-earth metal 2Nb 2O 7, replace the YNbO of Sr with rare earth element 4, LaNbO 4Deng the oxide compound that contains Nb, replace La with Nd 2NiO 4In La and the Nd that obtains 2NiO 4, replace LaTaO with Nd 4In La and the NdTaO that obtains 4, and Ca 4Ta 2O 9, BaTa 2O 6These materials are as shown in table 10.
Table 10
The material name Fusing point [℃]
Sr 4Nb 2O 9 1700
Sr 5Nb 4O 15 1475
Ca 2Nb 2O 7 1571
YNbO 4 2000
LaNbO 4 1620
Nd 2NiO 4 1900
NdTaO 4 1900
Ca 4Ta 2O 9 1990
BaTa 2O 6 1875
As shown in table 10, the fusing point of these materials thinks that all at 1400 ℃ or higher it can not have problems aspect the thermostability in the temperature range of heat insulating coat.
For the material of record in synthetic table 10, oxide compound, oxyhydroxide or the carbonate of choosing each component are as starting raw material, and weighing reaches the regulation ratio, uses the ball mill solid phase mixing.Behind the dry mixed powder, 1400 ℃ of following pre-burnings.Identify the pre-burning powder that obtains by powder x-ray diffraction, confirming does not have the unreacting material composition residual, and all test portions all become single-phase.Then at 1500 ℃ of above-mentioned each test portions of roasting, downcut the bar-shaped test portion of 4 * 4 * 15mm from its sintered compact, measure coefficient of thermal expansion.The value of the coefficient of thermal expansion under 1000 ℃ is as shown in table 11.Also put down in writing the coefficient of thermal expansion of comparative material 3YSZ in addition in this table.
Table 11
The material name Coefficient of thermal expansion [* 10 -6/℃]
3YSZ (comparative material) 9.92
Sr 4Nb 2O 9 14.47
Sr 5Nb 4O 15 11.27
Ca 2Nb 2O 7 12.06
YNbO 4 9.22
LaNbO 4 12.64
Nd 2NiO 4 14.05
NdTaO 4 9.87
Ca 4Ta 2O 9 7.38
BaTa 2O 6 7.79
In the material of making, Sr 4Nb 2O 9, Sr 5Nb 4O 15, Ca 2Nb 2O 7, LaNbO 4Coefficient of thermal expansion all demonstrates the value greater than 3YSZ.This expression, when these materials were used for heat insulating coat, the possibility that produces tensile stress between the metal member made of matrix was also less than the zirconium white that uses at present.Though YNbO in addition 4Coefficient of thermal expansion less than zirconium white, but also suitable substantially with it, can infer that when being used for heat insulating coat producing tensile stress between the metal member made of matrix also is same degree with the zirconium white that uses at present.Think its as heat-proof coating material no problem aspect the thermal expansion.
In addition, present embodiment only in 9 kinds of test portions of his-and-hers watches 11 record carried out the mensuration of coefficient of thermal expansion, but can easily infer, for the rare earth element beyond the Nd, for example Pr, Eu displacement La 2NiO 4In La and the oxide compound that obtains, and with the metallic element of 3 valencys beyond the Nd, for example Al, V, Cr, Fe, Ga, Y, Rh, In, Ce, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu replace LaTaO 4In La and the oxide compound that obtains because it has and Nd 2NiO 4, NdTaO 4Same crystalline texture, thereby the coefficient of thermal expansion that also has the same degree size.
Then at 1500 ℃ of following roasting Sr 4Nb 2O 9, Ca 2Nb 2O 7, YNbO 4, Nd 2NiO 4, NdTaO 4, Ca 4Ta 2O 9, BaTa 2O 6,,, measure thermal conductivity by laser flash method from the discoid test portion of sintered compact cutting-out diameter 10mm φ, thick 1mm.The value of thermal conductivity at room temperature is as shown in table 12.Also put down in writing the value (1000 ℃, literature value) of the coefficient of thermal expansion of comparative material 3YSZ in addition in this table.
Table 12
The material name Thermal conductivity [W/m.K]
3YSZ (comparative material) (2.2 1000 ℃ of literature values)
Sr 4Nb 2O 9 1.02
Ca 2Nb 2O 7 2.10
YNbO4 1.95
Nd 2NiO 4 1.84
NdTaO 4 2.15
Ca 4Ta 2O 9 2.18
BaTa 2O 6 1.60
Carry out and same research described in the embodiment 1, according to the thermal conductivity of formula (2) supposition of representing before 1000 ℃ (1273K), as shown in table 13.
Table 13
The material name Infer thermal conductivity [W/m.K] under 1000 ℃
3YSZ (comparative material) (2.2 1000 ℃ of literature values)
Sr 4Nb 2O 9 0.255
Ca 2Nb 2O 7 0.525
YNbO 4 0.488
Nd 2NiO 4 0.460
NdTaO 4 0.538
Ca 4Ta 2O 9 0.545
BaTa 2O 6 0.400
As shown in table 13, can infer these materials 1000 ℃ thermal conductivity all less than zirconic this value, think that it goes for heat-proof coating material.
Therefore in addition,, can control coefficient of thermal expansion and thermal conductivity, can think 2 kinds or more as table 11 and 12 materials of representing are compound and material formation also is enough to be applicable to heat-proof coating material by formula (3) and (4) of explanation among the utilization embodiment 2.Similarly, can think that also material formation also is enough to be applicable to heat-proof coating material with the material of table 1 among the embodiment 1 and table 2 record is compound with the table 11 in 2 kinds or the more present embodiment and the material of table 12 expression.
In addition, present embodiment only in 7 kinds of test portions of his-and-hers watches 12 record carried out the mensuration of coefficient of thermal expansion, but can easily infer, for the rare earth element beyond the Nd, for example Pr, Eu displacement La 2NiO 4In La and the oxide compound that obtains, and with the metallic element of 3 valencys beyond the Nd, for example Al, V, Cr, Fe, Ga, Y, Rh, In, Ce, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu replace LaTaO 4In La and the oxide compound that obtains because it has and Nd 2NiO 4, NdTaO 4Same crystalline texture, thereby the coefficient of thermal expansion that also has the same degree size.
[embodiment 6]
Because in embodiment 1 before, the coefficient of thermal expansion that can infer the sosoloid that the described Sr-Nb that is applicable to heat-proof coating material is an oxide compound is greater than zirconium white, and thermal conductivity is less than zirconium white, based on this, in this example, for BaTa 2O 6Sosoloid and LaNiO 4Sosoloid and other similar compound similarly carry out the research of coefficient of thermal expansion α, thermal conductivity λ.Here the material of Xuan Zeing is Ca 4Nb 2O 9, Ca 11Nb 4O 21, BaTa 1.8Ti 0.2O 6, BaTa 1.8Zr 0.2O 6, Sr 2Nb 1.8Ti 0.2O 7, Sr 2Nb 2-XZr XO 7, Sr 4Nb 2-XTi XO 9, Sr 4Nb 1.8Zr 0.2O 9, La 3NbO 7, DyNbO 4, La 1.8Ca 0.2NiO 4, La 6WO 12, Ce 6WO 12, Dy 6WO 12, Sm 6WO 12, Yb 6WO 12, Y 6WO 12, Dy 2WO 6, Yb 2WO 6, SrYb 2O 4, La 6WO 12, Dy 2WO 6These materials are as shown in table 14.
Table 14
The material name Fusing point (℃)
Ca 4Nb 2O 9 1700
Ca 11Nb 4O 21 2005
BaTa 1.8Ti 0.2O 6 1880
BaTa 1.8Zr 0.2O 6 1890
Sr 2Nb 1.8Ti 0.2O 7 1705
Sr 2Nb 1.8Zr 0.2O 7 1702
Sr 4Nb 1.8Ti 0.2O 9 1710
Sr 4Nb 1.8Zr 0.2O 9 1700
La 3NbO 7 1900
DyNbO 4 1950
La 1.8Ca 0.2NiO 4 1857
La 6WO 12 2150
Ce 6WO 12 2030
Dy 6WO 12 2300
Sm 6WO 12 2240
Yb 6WO 12 2525
Y 6WO 12 2400
Dy 2WO 6 2200
Yb 2WO 6 2200
As shown in table 14, the fusing point of these materials is all at 1700 ℃ or higher, wherein also there is the fusing point material of above 2500 ℃ of zirconic fusing point of yttrium oxide that surpassed solid solution, thinks not have problems aspect its thermostability in the temperature range that can be used for heat insulating coat.
The material of synthetic above-mentioned then table 15 record.When synthesizing these materials, oxide compound, oxyhydroxide or the carbonate of choosing each component are as starting raw material, and weighing reaches the regulation ratio, uses the ball mill solid phase mixing.Behind the dry mixed powder, 1400 ℃ of following pre-burnings.Identify the pre-burning powder that obtains by powder x-ray diffraction, confirmation does not have the unreacting material composition residual, all test portions all become single-phase, for material at the displacement solid solution, studied each peak in great detail, find the peak drift of certain orientation, confirmed that the solid solution composition that adds is solid-solubilized in the crystallization definitely.Then at 1500 ℃ of above-mentioned each test portions of roasting, downcut the bar-shaped test portion of 4 * 4 * 15mm from its sintered compact, measure coefficient of thermal expansion.In addition, though generally be similar compound, similar crystalline texture, the situation that the difference that its delicate difference causes thermal conductivity is bigger is also very common, but coefficient of thermal expansion seldom has so big difference.That is, can know Ca 4Nb 2O 9, Ca 11Nb 4O 21With Ca 2Nb 2O 7, BaTa 2-XTi XO 6, BaTa 2-XZr XO 6With BaTa 2O 6, Sr 2Nb 2-XTi XO 7, Sr 2Nb 2-XZr XO 7With Sr 2Nb 2O 7, Sr 4Nb 2-XTi XO 9, Sr 4Nb 2-XZr XO 9With Sr 4Nb 2O 9, La 3NbO 7, DyNbO 4With LaNbO 4, La 2-XCa XNiO 4With LaNiO 4, Ce 6WO 12, Dy 6WO 12, Sm 6WO 12, Yb 6WO 12, Y 6WO 12With La 6WO 12, Yb 2WO 6With Dy 2WO 6Have equal coefficient of thermal expansion value, omitted wherein some here, SrYb 2O 4, La 6WO 12, Dy 2WO 6Coefficient of thermal expansion value under 1000 ℃ is shown in Table 15.Also put down in writing the coefficient of thermal expansion of comparative material 3YSZ in addition in this table.
Table 15
The material name Coefficient of thermal expansion [* 10 -6/℃]
3YSZ (comparative material) 9.92
SrYb 2O 4 10.85
La 6WO 12 10.92
Dy 2WO 6 10.60
As shown in Table 15, in the material of making, SrYb 2O 4, La 6WO 12, Dy 2WO 6Coefficient of thermal expansion all demonstrate value greater than 3YSZ.This expression, when being used for heat insulating coat, the possibility that produces tensile stress between the metal member made (mother metal) of matrix is also less than the zirconium white that uses at present.
Then at 1500 ℃ of following roasting Ca 4Nb 2O 9, Ca 11Nb 4O 21, BaTa 1.8Ti 0.2O 6, BaTa 1.8Zr 0.2O 6, Sr 2Nb 1.8Ti 0.2O 7, Sr 2Nb 2-XZr XO 7, Sr 4Nb 2-XTi XO 9, Sr 4Nb 1.8Zr 0.2O 9, La 3NbO 7, DyNbO 4, La 1.8Ca 0.2NiO 4, La 6WO 12, Ce 6WO 12, Dy 6WO 12, Sm 6WO 12, Yb 6WO 12, Y 6WO 12, Dy 2WO 6, Yb 2WO 6,,, measure thermal conductivity by laser flash method from the discoid test portion of sintered compact cutting-out diameter 10mm φ, thick 1mm.The value of thermal conductivity at room temperature is shown in table 16.Also put down in writing the value (1000 ℃, literature value) of the coefficient of thermal expansion of comparative material 3YSZ in addition in this table.
Table 16
The material name Thermal conductivity [W/m.K]
3YSZ (comparative material) (2.2 1000 ℃, literature value)
Ca 4Nb 2O 9 2.06
Ca 11Nb 4O 21 2.01
BaTa 1.8Ti 0.2O 6 1.54
BaTa 1.8Zr 0.2O 6 1.58
Sr 2Nb 1.8Ti 0.2O 7 1.49
Sr 2Nb 1.8Zr 0.2O 7 1.50
Sr 4Nb 1.8Ti 0.2O 9 1.58
Sr 4Nb 1.8Zr 0.2O 9 1.53
La 3NbO 7 1.91
DyNbO 4 1.84
La 1.8Ca 0.2NiO 4 1.83
La 6WO 12 1.83
Ce 6WO 12 1.92
Dy 6WO 12 1.84
Sm 6WO 12 1.88
Yb 6WO 12 1.92
Y 6WO 12 1.91
Dy 2WO 6 1.89
Yb 2WO 6 1.82
According to the above result who obtains, carry out 1 described same research with embodiment, infer thermal conductivity under 1000 ℃ (1273K) according to the formula (2) of expression before, shown in table 17.
Table 17
The material name Infer thermal conductivity [W/m.K] under 1000 ℃
3YSZ (comparative material) (2.2 1000 ℃, literature value)
Ca 4Nb 2O 9 0.515
Ca 11Nb 4O 21 0.503
BaTa 1.8Ti 0.2O 6 0.385
BaTa 1.8Zr 0.2O 6 0.395
Sr 2Nb 1.8Ti 0.2O 7 0.373
Sr 2Nb 1.8Zr 0.2O 7 0.375
Sr 4Nb 1.8Ti 0.2O 9 0.395
Sr 4Nb 1.8Zr 0.2O 9 0.383
DyNbO 4 0.460
La 1.8Ca 0.2NiO 4 0.458
La 6WO 12 0.458
Ce 6WO 12 0.480
Dy 6WO 12 0.460
Sm 6WO 12 0.470
Yb 6WO 12 0.480
Y 6WO 12 0.488
Dy 2WO 6 0.473
Yb 2WO 6 0.455
Shown in table 16,17, can infer these materials in room temperature, 1000 ℃ thermal conductivity all less than zirconic this value, think that it goes for heat-proof coating material.
Therefore in addition,, can control coefficient of thermal expansion and thermal conductivity, can think 2 kinds or more as table 15 and 16 materials of representing are compound and material formation also is enough to be applicable to heat-proof coating material by formula (3) and (4) of explanation among the utilization embodiment 2.Similarly, also can think the material of the material of table 15 in 2 kinds or the more present embodiments and table 16 expression and table 1 among the embodiment 1 and table 2 expression is compound and material that form also is enough to be applicable to heat-proof coating material.
In addition, present embodiment only in 19 kinds of test portions of his-and-hers watches 16 record carried out the mensuration of coefficient of thermal expansion, but can infer easily that for use other rare earth element, for example Pr, Nd, Eu, Gd, Er etc. replace La 6WO 12, Dy 2WO 6In La and the oxide compound that obtains because it has and La 6WO 12And Dy 2WO 6Same crystalline texture, thereby the coefficient of thermal expansion that also has the same degree size.
[embodiment 7]
In this example, thermal conductivity is suitable as the heat-proof coating material this point less than zirconic material and carries out proof test greater than zirconium white for infer coefficient of thermal expansion in embodiment 1 before.In checking, at first suppose the operational situation of applied internal combustion turbine, consider startup under adding the state of maximum stress, the thermal stresses of being loaded when stopping, carrying out from studying the thermal cycling test of the fatigue phenomenon that causes by this thermal stresses in essence.
At first, the Ni based heat resistant alloy that will consist of Ni-16Cr-8.5Co-1.7Mo-2.6W-1.7T-0.9Nb-3.4Al-3.4Ti (at%) is cut into discoid, as the test film base material.With this substrate surface Al 2O 3After powder carries out sandblasting, the bonding coat that the CoNiCrAlY alloy that utilizes the formation of low-voltage plasma spraying method to be made up of Co-32Ni-21Cr-8Al-0.5Y (at%) is in the above constituted is as metal bonding layer, on the bonding coat of this CoNiCrAlY alloy, utilize atmos plasma spraying method laminated ceramic layer (film that forms by heat-proof coating material), form heat insulating coating film, as test film.
In addition, the thickness of bonding coat (CoNiCrAlY alloy film) is 0.1mm, and ceramic layer thickness is 0.5mm.
Then, with large-scale infrared(ray)lamp the heat insulating coating film side surface of this test film is carried out the optically focused heating, heating makes its surface temperature reach specified temperature, Optic gate blocking-up light cools off, open the optical gate heating once more after being cooled to specified temperature then, as above heating is repeatedly carried out thermal cycling test.
In addition,, adopt following acceleration environment, promptly-20 ℃ cooling air approximately, the integral body of refrigeration test sheet are sprayed in the heated reverse side of test film surface from spout in order in the short cycle, to finish test.Thus, test film is that the center is cooled to 0 ℃ substantially with the surface of the reverse side of heat insulating coating film, keeps the whole state that is cooled when heating with infrared(ray)lamp beyond the surface of heat insulating coating film side always.By paying this temperature head wittingly, the very large thermal stresses that has been central concentrated load with the membrane interface on the test film.This test is performed until can be by till the peeling off on the heat insulation coated side of Visual Confirmation.
To by Sr 2Nb 2O 7The test portion that the heat insulating coating film that forms coats carries out above-mentioned thermal cycling test.The condition of thermal cycling test is, the top temperature of test film hot face (heat insulating coating film surface) is 1450 ℃, and the highest interface temperature (temperature at the interface between heat insulating coating film and the base material) is 850 ℃, repeats heating.At this moment, be set 1 minute heat-up time, the circulation of 1 minute cooling time.The result of this thermal cycling test is shown in table 18.In addition, also put down in writing the situation of the heat insulating coating film of the 3YSZ that is used for comparison in the lump.
Table 18
The material name Reach the number of times that peeling off appears in the heat insulating coating film surface
3YSZ (comparative material) 80
Sr 2Nb 2O 7 600
Can confirm Sr by table 18 2Nb 2O 7Have as the excellent effect of heat insulating coat with material.Think that this is to compare the high and low thermal conductivity of high coefficient of thermal expansion with comparative material because this material has, thereby can easily infer, also can obtain equal effect for other material.
Industrial applicibility
By heat-proof coating material of the present invention, can form the heat insulating coating film of high coefficient of thermal expansion and lower thermal conductivity. If this is filmed for the heat-resisting protective film of gas turbine lamp, can obtain having good heat resistance and durability, and can deal with easily the high performance gas-turbine engine of the high temperature of burning gases.

Claims (2)

1. go for the heat-proof coating material at the heat insulating coating film of mother metal surface coverage, wherein, described heat-proof coating material comprises Sr 2Nb 2-XZr xO 7As main body, 0＜x≤2 wherein.
2. heat-proof coating material, contain will record in the claim 1 oxide compound and zirconium white based material carry out the composition of compound and formation as main body.
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