CN107698255A - Rare earth ion tantalates of Eu Gd Dy tri- and preparation method and application - Google Patents

Rare earth ion tantalates of Eu Gd Dy tri- and preparation method and application Download PDF

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CN107698255A
CN107698255A CN201710761079.3A CN201710761079A CN107698255A CN 107698255 A CN107698255 A CN 107698255A CN 201710761079 A CN201710761079 A CN 201710761079A CN 107698255 A CN107698255 A CN 107698255A
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rare earth
tri
earth ion
tantalates
ion tantalates
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CN107698255B (en
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冯晶
宋鹏
胡志辉
周颖
陈琳
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Shaanxi Tianxuan Coating Technology Co ltd
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Kunming Craftsman Coating Technology Co Ltd
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Abstract

The invention discloses a kind of rare earth ion tantalates of Eu Gd Dy tri- and preparation method and application, the chemical general formula of the rare earth ion tantalates of Eu Gd Dy tri- is EuaGdbDycTaO7, wherein, a+b+c=3, a, b, c=0.8~1.2.Its preparation method comprises the following steps：1) Europium chloride, gadolinium nitrate, dysprosium nitrate and tantalum oxalate are stoichiometrically weighed, and mechanical mixture is carried out under heat-retaining condition with the citric acid of set amount, in mixed process add concentrated ammonia liquor in and solution, then under heat-retaining condition carry out mechanical mixture promote reaction progress.2) resulting solution is dried, then calcining removes carbon impurity at high temperature, produces the rare earth ion tantalic acid salt powders of Eu Gd Dy tri-.The rare earth ion tantalates of Eu Gd Dy tri-, high high-temp stability is good, and thermal conductivity coefficient is low, can be applied as heat barrier coat material.

Description

Rare earth ion tantalates of Eu-Gd-Dy tri- and preparation method and application
Technical field
The present invention relates to a kind of tantalates, particularly relates to a kind of rare earth ion tantalates of Eu-Gd-Dy tri- and preparation method thereof With application.
Background technology
With the development of Aeronautics and Astronautics and civilian technology, the temperature in use of hot-end component requires more and more higher, has reached high The extreme condition of temperature alloy and monocrystal material.By taking the heating part of gas turbine such as nozzle, blade, combustion chamber as an example, at them In the adverse circumstances such as high-temperature oxydation and high temperature gas flow erosion, bearing temperature is up to 1100 DEG C, and having exceeded high temperature nickel alloy makes Limiting temperature (1075 DEG C).The high intensity of metal, high tenacity are combined with the resistant to elevated temperatures advantage of ceramics prepared The thermal barrier coating gone out can solve the above problems, and it can play heat-insulated, anti-oxidant, etch-proof effect, be sent out in steam turbine, diesel oil Certain application is obtained on the material of the hot junction such as motor, jet engine, and extends the service life of hot-end component.
At present, being most suitable as the ceramic material of thermal barrier coating mainly has yttria-stabilized zirconia (YSZ), rare earth zirconic acid Salt (RE2Zr2O7), rare earth silicate (RE2SiO5), RE phosphate (REPO4), rare earth cerate (RE2Ce2O7) and rare earth Stannate (RE2Sn2O7) etc..Wherein most widely used is yttria-stabilized zirconia (YSZ), and it has high-melting-point, low-heat Lead, high thermal expansion coefficient and good mechanical property, but temperature in use is relatively low, and only 1200 DEG C, this is due at 1200 DEG C Above YSZ, which can be undergone phase transition, to be caused Volume Changes and causes coating failure.In addition to YSZ, the thermal barrier coating material applied at present Material has La2Zr2O7, belong to one kind of rare earth zirconate, it has lower thermal conductivity compared to YSZ, and temperature in use is up to 1600 DEG C, this is due to that rare earth zirconate is burnt green stone and defect fluorite type structure, has substantial amounts of crystal defect can be effective Phonon is scattered, so as to reduce thermal conductivity, and the problems such as phase transformation is not present at high temperature.It follows that finding new thermal boundary The low thermal conducting material with good high temperature phase stability can be explored during coating material from crystal structure.
Rare earth tantalate RE3TaO7It is that the research of new heat barrier coat material, Yoshiyuki et al. a kind of shows (Yoshiyuki Yokogawa,Masahiro Yoshimura and Shigeyuki Somiya；Order-disorder in R3TaO7(R=rare earth) Phases, Solid State ionics:28-30 (1988) 1250-1253), in RE3TaO7 In with the change of ionic radius of rare earth occur to be changed by Jiao Lvshi to defect fluorite structure it is orderly -- unordered change, this with it is dilute Native zirconates (RE2Zr2O7) similar.Therefore it can guess that the two oxides ceramics with analogous crystalline structure may be with phase Same characteristic, such as high-melting-point, lower thermal conductivity, high thermal expansion coefficient etc., and RE is shown according to previous investigation3TaO7For Ferroelasticity material, this is identical with YSZ, therefore has good mechanical property at high temperature.
The content of the invention
It is an object of the invention to provide the rare earth ion tantalic acids of Eu-Gd-Dy tri- that a kind of thermal conductivity coefficient is low, heat endurance is good Salt and preparation method and application.
To achieve the above object, the rare earth ion tantalates of Eu-Gd-Dy tri- provided by the present invention, its chemical general formula are EuaGdbDycTaO7, wherein, a+b+c=3, a, b, c=0.8~1.2.Preferably, a=b=c=1, now, the Eu-Gd-Dy The chemical formula of three rare earth ion tantalates is EuGdDyTaO7。
Preferably, the rare earth ion tantalates of Eu-Gd-Dy tri- has following property：1) average grain size is 2~10 μ m；2) at 100~800 DEG C of temperature, thermal conductivity is 1.4~1.8Wm-1·K-1, and reduced as temperature raises；3) XRD In spectrum, diffraction maximum by relative intensity successively decrease arrangement where angle be：30 ± 1 °, 49 ± 1 °, 34.5 ± 1 °, 58 ± 1 °, 61 ± 1°。
Invention also provides a kind of preparation method of the above-mentioned rare earth ion tantalates of Eu-Gd-Dy tri-, including following step Suddenly：
1) Europium chloride, gadolinium nitrate, dysprosium nitrate and tantalum oxalate are stoichiometrically weighed, and is being protected with the citric acid of set amount Carry out mechanical mixture under the conditions of temperature, added in mixed process in concentrated ammonia liquor and solution, then mechanical mixture is carried out under heat-retaining condition Promote the progress of chemical reaction：
In reacting above, the amount sum of the material of three kinds of rare earth elements: tantalum oxalate: citric acid=6: 1: 8, each rare earth element Material amount stoichiometrically coefficient determine；Citric acid then can be calcined out, therefore can be somewhat excessive；Ammoniacal liquor addition with Solution is reached near neutral is advisable.
2) resulting solution is dried, then at high temperature calcining remove carbon impurity, produce the rare earths of Eu-Gd-Dy tri- from Sub- tantalic acid salt powder.
Preferably, in step 1), during first time mechanical mixture, temperature is 135 ± 10 DEG C, 50 ± 10min of time；Second During mechanical mixture, temperature is 180 ± 20 DEG C, 30 ± 10min of time.
Preferably, in step 2), drying temperature is 300 ± 10 DEG C, 10 ± 1h of drying time；Calcining heat is 800 ± 10 DEG C, 10 ± 1h of calcination time.
The above-mentioned rare earth ion tantalates of Eu-Gd-Dy tri- has the low and higher thermal coefficient of expansion of low thermal conductivity coefficient, can make Applied for heat barrier coat material.It is as a kind of application mode of heat barrier coat material：The Eu-Gd-Dy tri- is dilute Native ion tantalates is sent into atmospheric plasma spraying equipment with powder morphology, and air plasma spraying is carried out to matrix surface, Prepare high-temp heat barrier coating.Atmospheric plasma spraying (APS) and electron beam-physical vapour deposition (PVD) (EB-PVD) are to use at present In the main method for preparing thermal barrier coating.Compared with air plasma spraying, its deposition efficiency of EB-PVD thermal barrier coatings is relatively low, applies Thickness degree is uncontrollable, and surface clean complexity, equipment complex and expensive, sedimentation rate is relatively low, technological process is cumbersome, and sample Size can not be too big, therefore prepares high-temperature ceramic coating using air plasma spraying mode in the present invention.
Preferably, atmospheric plasma spraying equipment is re-fed into after the rare earth ion tantalates of Eu-Gd-Dy tri- is granulated Sprayed；The step of granulation, includes：1) binding agent is mixed into the rare earth ion tantalic acid salt powders of Eu-Gd-Dy tri-, It is made pureed liquid, 2) it is re-fed into spray drier and is sprayed, spherical prilling powder, the powder obtained after sieving is made Granularity is 40~50 μm.The binding agent is preferably high viscosity agar solution of the viscosity in 900~1200MPaS.
Preferably, when carrying out atmospheric plasma spraying, the ionized gas that uses is Ar and He, and the flow of Ar gases For 50~100L/min, the flow of He gases is 6~20L/min；Arc voltage is 50~80V, arc current is 500~ 800A；Powder feed rate is 20~110g/min, and powder feeding angle is 60~90 °, and spray distance is 90~130mm.
Beneficial effects of the present invention are as follows：
1) the rare earth ion tantalates Eu of Eu-Gd-Dy tri-aGdbDycTaO7It can obtain than existing rare earth tantalate RE3TaO7More preferable thermal property, such as more preferable high high-temp stability (use is without phase transformation at 1600 DEG C), lower thermal conductivity The thermal coefficient of expansion (~12.8 × 10 of coefficient and Geng Gao-6K-1, 1200 DEG C), the thermal mismatching with alloy substrate can be effectively reduced. With double rare earth ion tantalates (number of patent applications：CN201610597143.4) compare, the present invention in the rare earths of Eu-Gd-Dy tri- from Sub- tantalates is defect fluorite type crystal structure, and oxygen vacancy concentration is big, can effectively reduce thermal conductivity, and at high temperature without phase Become；And double rare earth ion tantalates are monoclinic phase (m) structure, there is m-t phase transformations in it, Volume Changes are big at high temperature, in reality Failure of coating etc. may be caused in.
2) its preparation method uses liquid-phase reaction system, is sufficiently mixed three kinds of rare earth ions, and mixed by being incubated machinery Conjunction and the addition of concentrated ammonia liquor, promote the abundant reaction between raw material., can be by reacting and calcining using citric acid and ammoniacal liquor The removal of impurity is gone, the impurity for being difficult to remove can be produced in the product with other acid or alkaline solution.Obtained Eu-Gd-Dy tri- Rare earth ion tantalic acid purity salt is high, and impurity content is few, and consistency is high, and crystallite dimension is small, few the defects of stomata, crackle, has good Good mechanical property.
3) the rare earth ion tantalates of Eu-Gd-Dy tri- is tested, as a result shown, its crystallite dimension is 2~10 μm； At 100~800 DEG C of temperature, thermal conductivity is 1.4~1.8Wm-1·K-1, and reduced as temperature raises；In XRD spectrum, spread out Penetrate peak by relative intensity successively decrease arrangement where angle be：30 ± 1 °, 49 ± 1 °, 34.5 ± 1 °, 58 ± 1 °, 61 ± 1 °.
5) the rare earth ion tantalates of Eu-Gd-Dy tri- has a good high temperature phase stability, and larger hardness is relatively low Thermal conductivity, higher thermal coefficient of expansion, used as new heat barrier coat material, there is good effect of heat insulation.
Brief description of the drawings
Fig. 1 is the rare earth ion tantalates EuGdDyTaO of Eu-Gd-Dy tri- that embodiment 1 is provided7Refractory ceramics block X-ray diffractogram (XRD spectrum)；
Fig. 2 is the rare earth ion tantalates EuGdDyTaO of Eu-Gd-Dy tri- that embodiment 1 is provided7Refractory ceramics block Picture in kind；
Fig. 3 is the rare earth ion tantalates EuGdDyTaO of Eu-Gd-Dy tri- that embodiment 1 is provided7Refractory ceramics block Electron scanning micrograph (SEM)；
Fig. 4 is the rare earth ion tantalates EuGdDyTaO of Eu-Gd-Dy tri- that embodiment 1 is provided7Refractory ceramics block Thermal conductivity and yttria-stabilized zirconia (7YSZ), rare earth zirconate (La2Zr2O7) and tantalic acid europium (Eu3TaO7) comparison diagram.
Embodiment
The present invention is described in further detail with specific embodiment 1~7 below in conjunction with the accompanying drawings.
The rare earth ion tantalates of Eu-Gd-Dy tri- provided by the present invention, its chemical general formula are EuaGdbDycTaO7, wherein, A+b+c=3, a, b, c=0.8~1.2.In each embodiment, Eu, Gd, Dy coefficient refer to table 1.
The preparation process of the above-mentioned rare earth ion tantalates of Eu-Gd-Dy tri- is as follows：
(1) Europium chloride (EuCl is stoichiometrically weighed3), gadolinium nitrate (Gd (NO3)3), dysprosium nitrate (Dy (NO3)3) and grass Sour tantalum (Ta2(C2O4)5), it is added to citric acid (C6H8O7) in, each specific addition of embodiment is shown in Table 1 and (needs to convert when weighing Into quality, for convenience of representing stoichiometric proportion therefore use mole to be measured in the present invention).50min is incubated at 135 DEG C to go forward side by side The violent mechanical agitation of row is sufficiently mixed it, is added dropwise in whipping process with 1mL/min speed in concentrated ammonia liquor and solution is (with guarantor Warm time consistency 50min, is added dropwise to neutrality), 30min is then incubated at 180 DEG C and vigorous mechanical agitation promotes entering for reaction OK.
2) obtained solution is heated to 300 DEG C, insulation is dried for 10 hours.Obtained solid powder is placed in sintering 800 DEG C are heated in stove, 10 hours is incubated and carries out carbon removal treatment.
3) powder obtained to step 2) carries out tabletting.Dwell pressure 4MPa, dwell time 2min, finally at 1680 DEG C Sintering obtains the rare earth ion tantalates ceramic blocks of Eu-Gd-Dy tri- of densification for 8 hours, and its photo is as shown in Figure 2, it can be seen that Block surface pore-free, crackle, surface quality are good.
Each embodiment raw material proportioning of table 1 and test data
4) X-ray diffraction is carried out to obtained ceramic block, as shown in Figure 1 the EuGdDyTaO obtained by embodiment 17 The XRD spectrum of block, diffraction maximum by relative intensity successively decrease arrangement where angle be：30 ± 1 °, 49 ± 1 °, 34.5 ± 1 °, 58 ± 1 °, 61 ± 1 °.The XRD spectrum of other embodiment is substantially the same manner as Example 1, and only the intensity of part diffraction maximum is different.With Dy3TaO7Standard PDF card PDF Number：38-1406 is compared, the densification of the rare earth ion tantalates of Eu-Gd-Dy tri- The diffraction maximum that ceramic X-ray diffraction result is shown is consistent with the quantity of standard PDF cards, and is corresponded with it, this explanation institute Be made sample crystal structure types and standard card it is consistent, and dephasign is not present.The thing of gained sample is mutually orthorhombic phase, The angle of the axles of abc tri- is 90 degree in crystal structure, and in crystal structure a, b, c length it is unequal, its space group is C2221.In addition, all diffraction maximums of gained sample are all offset to the right compared with standard card, this is due to the rare earth ion Eu of doping3 +、Gd3+With than Dy3+Bigger ionic radius causes the mean radius of rare earth ion to increase, cause lattice constant increase and The extension of atomic distance.
5) ceramic block is made to each embodiment using SEM (SEM) to shoot, is illustrated in figure 3 reality Apply the EuGdDyTaO obtained by example 17The SEM photograph of block, it can be seen that the rare earths of Eu-Gd-Dy tri- being prepared Ion tantalates ceramic structure is fine and close, and crystal grain is tiny (2~5 μm), and flawless has only micro stomata, and test result shows it Consistency reaches 94%.The average grain size scope that each embodiment measures refers to table 1.
6) EuGdDyTaO obtained by embodiment 1 is continuously measured using laser reflecting method (LFA 457)7Block 100~ Thermal conductivity at 800 DEG C, as a result draw in Fig. 4, give the thermal barrier coating being widely used at present simultaneously in figure as a comparison Material 7YSZ, La2Zr2O7And Eu3TaO7Thermal conductivity.It will be seen from figure 1 that the EuGdDyTaO obtained by embodiment 17Block Thermal conductivity in 100~800 DEG C of temperature is 1.4~1.7Wm-1·K-1, far below 7YSZ, La2Zr2O7And Eu3TaO7, and Main function of the effect of heat insulation as thermal barrier coating, lower thermal conductivity is exactly the performance of its most critical, it may thus be appreciated that SmEuGdTaO7 Ceramics can be used as heat barrier coat material popularization and application.The thermal conductivity scope that each embodiment measures refers to table 1, smaller value 100 DEG C measured value, higher value is 800 DEG C of measured values.
One application examples of the rare earth ion tantalates of Eu-Gd-Dy tri- given below.
In the application example, the rare earth ion tantalates of Eu-Gd-Dy tri- is sprayed to by Ni-based conjunction using atmospheric plasma spraying Golden steel matrix surface, it is comprised the following steps that：
1) by preparation process 2) obtained rare earth ion tantalic acid salt powders of Eu-Gd-Dy tri- add dissolved adhesiveness and are in concentration It is 1200MPaS high viscosity agar solution when 2%, 60 DEG C are nearby incubated, and are stirred simultaneously, pureed liquid is made.
2) pureed liquid is carried out using the spray drier of 25000rpm, 160 DEG C of inlet temperature, 78 DEG C of outlet temperature Spraying, 30~60 μm of spherical prilling powder is made.
3) it is rearmounted again by the grinding of spherical prilling powder (if necessary, as obtained powder diameter properly can directly sieve) In 50 μm and 40 μm of the upper and lower sieve being disposed vertically, middle powder is taken, you can obtain 40~50 μm of particle.
4) sprayed using air plasma spraying equipment (SluzerMetco UniCoat), spray gun type 9MB.Spray Painting gaseous environment is Ar/He：Ar flows are that 80L/min, He flow are 12L/min；Arc voltage is 80V, arc current is 500A, powder feed rate 110g/min, powder feeding angle are 90 °, spray distance 130mm.In spraying process, using recirculated water Cooling method cools down matrix, and the flow for cooling down current is 200L/min.Room temperature is cooled to, that is, obtains required refractory ceramics thermal boundary and applies Layer (thermal conductivity：1.4~1.8W.m-1.K-1)。

Claims (10)

  1. A kind of 1. rare earth ion tantalates of Eu-Gd-Dy tri-, it is characterised in that：The chemical general formula of the tantalates is EuaGdbDycTaO7, wherein, a+b+c=3, a, b, c=0.8~1.2.
  2. 2. the rare earth ion tantalates of Eu-Gd-Dy tri- according to claim 1, it is characterised in that：A=b=c=1.
  3. 3. the rare earth ion tantalates of Eu-Gd-Dy tri- according to claim 1, it is characterised in that：The rare earths of Eu-Gd-Dy tri- Ion tantalates has following property：1) its crystallite dimension is 2~10 μm；2) at 100~800 DEG C of temperature, thermal conductivity be 1.4~ 1.8W·m-1·K-1, and reduced as temperature raises；3) in XRD spectrum, diffraction maximum is successively decreased by relative intensity arranges place Angle is：30 ± 1 °, 49 ± 1 °, 34.5 ± 1 °, 58 ± 1 °, 61 ± 1 °.
  4. It is 4. a kind of such as the preparation method of the rare earth ion tantalates of Eu-Gd-Dy tri- according to any one of claims 1 to 3, its spy Sign is：Comprise the following steps：
    1) Europium chloride, gadolinium nitrate, dysprosium nitrate and tantalum oxalate are stoichiometrically weighed, and with the citric acid of set amount in heat preservation strip Carry out mechanical mixture under part, added in mixed process in concentrated ammonia liquor and solution, then mechanical mixture promotion is carried out under heat-retaining condition The progress of chemical reaction.
    2) resulting solution is dried, then calcining removes carbon impurity at high temperature, produces the rare earth ion tantalums of Eu-Gd-Dy tri- Hydrochlorate.
  5. 5. the preparation method of the rare earth ion tantalates of Eu-Gd-Dy tri- according to claim 4, it is characterised in that：Step 1) In, during first time mechanical mixture, temperature is 135 ± 10 DEG C, 50 ± 10min of time；During second of mechanical mixture, temperature 180 ± 20 DEG C, 30 ± 10min of time；In step 2), drying temperature is 300 ± 10 DEG C, 10 ± 1h of drying time；Calcining heat is 800 ± 10 DEG C, 10 ± 1h of calcination time.
  6. 6. the preparation method of the rare earth ion tantalates of Eu-Gd-Dy tri- according to claim 4, it is characterised in that：Step 1) In, the amount sum of the material of three kinds of rare earth elements: tantalum oxalate: citric acid=6: 1: 8.
  7. It is 7. a kind of if the rare earth ion tantalates of Eu-Gd-Dy tri- according to any one of claims 1 to 3 is as thermal barrier coating material The application of material.
  8. 8. application of the rare earth ion tantalates of Eu-Gd-Dy tri- according to claim 7 as heat barrier coat material, it is special Sign is：The rare earth ion tantalates of Eu-Gd-Dy tri- is sent into atmospheric plasma spraying equipment with powder morphology, to base Body surface face carries out air plasma spraying, prepares the thermal barrier coating that thermal conductivity is low, thermal coefficient of expansion is high.
  9. 9. application of the rare earth ion tantalates of Eu-Gd-Dy tri- according to claim 8 as heat barrier coat material, it is special Sign is：Atmospheric plasma spraying equipment is re-fed into after the rare earth ion tantalates of Eu-Gd-Dy tri- is granulated to be sprayed Apply；The step of granulation, includes：1) binding agent is mixed into the rare earth ion tantalic acid salt powders of Eu-Gd-Dy tri-, mud is made Shape liquid, 2) it is re-fed into spray drier and is sprayed, spherical prilling powder is made, the powder size obtained after sieving is 40~50 μm.
  10. 10. application of the rare earth ion tantalates of Eu-Gd-Dy tri- as heat barrier coat material according to claim 8 or claim 9, It is characterized in that：When carrying out atmospheric plasma spraying, the ionized gas used is Ar and He, and the flow of Ar gases is 50 The flow of~100L/min, He gas is 6~20L/min；Arc voltage is 50~80V, and arc current is 500~800A；Send Powder speed is 20~110g/min, and powder feeding angle is 60~90 °, and spray distance is 90~130mm.
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