CN108034939A - A kind of densifying method of Wolfram rhenium heat electric couple high-temperature oxidation resistant coating - Google Patents
A kind of densifying method of Wolfram rhenium heat electric couple high-temperature oxidation resistant coating Download PDFInfo
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- CN108034939A CN108034939A CN201711284029.7A CN201711284029A CN108034939A CN 108034939 A CN108034939 A CN 108034939A CN 201711284029 A CN201711284029 A CN 201711284029A CN 108034939 A CN108034939 A CN 108034939A
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- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
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- 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
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- 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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- 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
- C23C4/18—After-treatment
Abstract
The invention belongs to technical field of temperature measurement, more particularly, to a kind of densifying method of Wolfram rhenium heat electric couple antioxidant coating.The Wolfram rhenium heat electric couple antioxidant coating is attached to Wolfram rhenium heat electric couple matrix surface, oxygen barrier layers including transition zone and positioned at the transition layer surface, the thermal coefficient of expansion of the buffer layer material is between the material that the Wolfram rhenium heat electric couple basis material and the oxygen barrier layers are selected；Isostatic pressed and heat treatment are carried out to the Wolfram rhenium heat electric couple antioxidant coating, so that the antioxidant coating is finer and close, micro-crack is less, porosity is lower, thermal stress is released at the same time, so that Wolfram rhenium heat electric couple antioxidant coating thickness reduces more than 40%, while the oxytolerant ablation ability under more than 2000 DEG C aerobic environments of the coating significantly increases, and thus solves the problems, such as long-time contact type temperature measuring in more than 2000 DEG C superhigh temperature aerobic environments.
Description
Technical field
The invention belongs to technical field of temperature measurement, more particularly, to a kind of cause of Wolfram rhenium heat electric couple antioxidant coating
Densification method.
Background technology
Measurement for more than 1600 DEG C ultra-high temperatures, it is more at present to be measured using non-contact (infrared, optics etc.) method, but
Not only response speed is slow for non-contact method, but also temperature measurement accuracy can not show a candle to carry out direct contact type thermometric using thermocouple.Platinum rhodium
(Pt-Rh) thermocouple, nickel chromium-nickel silicon thermocouple, iron-constantan thermocouple and W-Re (W-Re) thermocouple are relatively common several
Pyrometer couple, wherein Wolfram rhenium heat electric couple have obvious advantage compared with other thermocouples：
(1) fusing point it is high (>3000 DEG C), intensity is big, good thermal shock, and chemical property is stablized；
(2) thermo-electromotive force is big (about 2~3 times of platinum rhodium thermocouple), high sensitivity；
(3) temperature-measuring range is big, and the operating temperature upper limit is up to 2800 DEG C；
(4) cheap (about 1/10th of platinum rhodium thermocouple).
However, Wolfram rhenium heat electric couple under aerobic environment since 300 DEG C or so i.e. aoxidize, be only applicable to reduction, inertia, very
The high temperature measurement of the environment such as sky, it is impossible to applied in high temperature oxidation stability atmosphere.Therefore, the anti-oxidant energy of Wolfram rhenium heat electric couple how is improved
Power, is always the problem that domestic and international field of pyrometry is paid high attention to.
Wolfram rhenium heat electric couple thermometric is used under aerobic environment at present, generally takes two ways：One kind is disposably to measure
Use, i.e., each thermometric time is very short, does not use or is used again after processing after thermocouple oxidation deactivation, another
Mode is to take anti-oxidant treatment to thermocouple.Current commercialized Wolfram rhenium heat electric couple anti-oxidation technology is mainly armouring protection
Method, i.e., be used as protection pipe using quartz, corundum, refractory metal and refractory ceramics etc., load evacuation after Wolfram rhenium heat electric couple seal,
Filling with inert gas seals or the powder sealing of filling inertia, artificially creates non-oxidizing atmosphere for thermocouple in protection pipe, makes
It completes thermometric mission, but this anti-oxidant thermocouple of non-removable solid type before oxidation is deteriorated, and there are problems with：
(1) limitation of the protected pipe temperature resistant capability of thermocouple temperature in use, usually less than 1800 DEG C；
(2) volume and weight increases after the protection of thermocouple armouring, using being subject in the stringenter system of volume requirement
Limitation；
(3) after using casing and filler protection, the response speed of thermocouple is greatly affected.
By coating antioxidant coating on Wolfram rhenium heat electric couple surface, on the premise of response speed is not influenced, thermoelectricity is improved
Occasionally the thermometric upper limit in high temperature air and other high temperature oxidative atmospheres, extension thermometric working time, are to solve problem above
More satisfactory method.In fact, the research of this respect has just been carried out from the sixties in last century both at home and abroad, but have no all the time
The open report of continuation, and so far without Related product input actual use in global range.
The present invention proposes a kind of new high-temperature oxidation resistant coating structure and its densification for Wolfram rhenium heat electric couple surface
Change method, makes it to realize the long-time contact temperature-measuring under more than 2000 DEG C superhigh temperature aerobic environments.
The content of the invention
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides a kind of Wolfram rhenium heat electric couple antioxidant coating
Densifying method, its object is to by pair antioxidant coating being directly in contact with Wolfram rhenium heat electric couple matrix simultaneously or successively
Carry out isostatic pressed and heat treatment so that Wolfram rhenium heat electric couple antioxidant coating thickness reduces 40~50%, while 2000 DEG C of the coating
Oxytolerant ablation ability under above aerobic environment significantly increases, and thus solves in more than 2000 DEG C superhigh temperature aerobic environments for a long time
The problem of contact type temperature measuring.
To achieve the above object, it is proposed, according to the invention, a kind of densifying method of Wolfram rhenium heat electric couple antioxidant coating is provided,
The Wolfram rhenium heat electric couple antioxidant coating is attached to the Wolfram rhenium heat electric couple matrix surface, and the antioxidant coating includes transition zone
And the oxygen barrier layers positioned at the transition layer surface, the thermal coefficient of expansion of the buffer layer material is between the Wolfram rhenium heat electric couple
Between the material that basis material and the oxygen barrier layers are selected；The densifying method is by the anti-oxidant painting of the Wolfram rhenium heat electric couple
Layer carries out isostatic pressed and heat treatment.
Preferably, 20~100MPa isostatic presseds are carried out to the Wolfram rhenium heat electric couple antioxidant coating to handle 10~30 minutes,
Then under inert gas shielding atmosphere, the isothermal holding when 750 DEG C~1050 DEG C progress 1~3 are small, takes after being cooled to room temperature
Go out, complete annealing process.
It is further preferred that heating rate is 3~6 DEG C/min.
Preferably, 20~100MPa isostatic presseds are carried out to the Wolfram rhenium heat electric couple antioxidant coating to handle 10~30 minutes,
Then under inert gas shielding atmosphere, the isothermal holding when 1400~1600 DEG C of progress 1~3 are small, carries out pressureless sintering work
Skill.
It is further preferred that the non-pressure sintering technology includes following sub-step：
(1) 400~600 DEG C, when insulation 1~3 is small are heated to the heating rate of 3~6 DEG C/min, carried out pre-sintered；
(2) 1400~1600 DEG C are heated to the heating rate of 2~4 DEG C/min, when insulation 1~3 is small, be sintered；
(3) 300~500 DEG C are cooled to the rate of temperature fall of 2~4 DEG C/min；
(4) taken out after sample is naturally cooling to room temperature.
Preferably, under inert gas shielding atmosphere, in 10~20MPa of pressure, 1250~1450 DEG C of temperature is to the tungsten
Isothermal holding when rhenium thermocouple antioxidant coating progress 1~3 is small, takes out sample after pressure release, carry out HIP sintering technique.
It is further preferred that in the case where pressure is the inert gas shielding atmosphere of 10~20MPa, the sintering of following steps is carried out
Technique：
(1) 350~450 DEG C, when insulation 1~2 is small are heated to the heating rate of 4~7 DEG C/min, carried out pre-sintered；
(2) 1250~1450 DEG C, when insulation 1~3 is small are heated to the heating rate of 3~4 DEG C/min, carry out high temperature insostatic pressing (HIP)
Sintering；
(3) 300~500 DEG C are cooled to the rate of temperature fall of 3~4 DEG C/min；
(4) taken out after sample is naturally cooling to room temperature.
Preferably, the material that the transition zone is selected is selected from titanium nitride, tungsten carbide, tantalum, ramet, tungsten silicide or oxidation
Magnesium；The transition zone is preferably 10~100 microns of film layer.
Preferably, the oxygen barrier layers are sandwich construction not less than 2 layers, layers of material thermal expansion in the oxygen barrier layers
Coefficient gradually increases to the direction away from the Wolfram rhenium heat electric couple matrix, the oxytolerant ablation energy of layers of material in the oxygen barrier layers
Power also gradually increases to the direction away from the Wolfram rhenium heat electric couple matrix.
Preferably, the oxygen barrier layers gross thickness is not more than 200 microns.
Preferably, the material that the oxygen barrier layers are selected is that can play the role of oxygen stop or oxytolerant ablation more than 2000 DEG C
Refractory metal oxide, boride or nitride.
Preferably, by magnetron sputtering method, hot spray process, chemical vapour deposition technique or investment in the Wolfram rhenium heat electric couple
The transition zone is prepared in matrix surface.
Preferably, it is prepared into by chemical vapour deposition technique, hot spray process or sol-gal process in the transition layer surface
To the oxygen barrier layers.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect：
1) present invention to the high-temperature oxidation resistant coating on Wolfram rhenium heat electric couple surface by carrying out isostatic pressed and heat treatment so that should
Antioxidant coating is finer and close, and micro-crack is less, and porosity is lower；
2) present invention is by being heat-treated the antioxidant coating on Wolfram rhenium heat electric couple surface so that its coating stress obtains
Part discharges, and is used for the service life and plays large increase；
3) densifying method proposed by the present invention make it that antioxidant coating combination is closer, more difficult disengaging, adhesive force
It is greatly improved；
4) coating after coating densifying method processing of the present invention is more obvious to the barrier effect of oxygen at high temperature, high temperature
Oxidation resistance obtains larger raising；
5) Wolfram rhenium heat electric couple antioxidant coating of the present invention is attached directly to Wolfram rhenium heat electric couple matrix surface, the antioxidant coating
Oxygen barrier layers including transition zone and positioned at transition layer surface, transition zone is located immediately at Wolfram rhenium heat electric couple silk table face, thickness 10
~100 microns, set transition zone that the adhesive force of Wolfram rhenium heat electric couple face coat is greatly improved；The heat of buffer layer material
Between Wolfram rhenium heat electric couple matrix and oxygen barrier layers material, the thermal stress of coating at high temperature greatly reduces the coefficient of expansion；
6) oxygen barrier layers of sandwich construction are included in Wolfram rhenium heat electric couple antioxidant coating structure proposed by the present invention, this is more
Oxygen barrier layers in Rotating fields are there are component gradient and concentration gradient, i.e., by adjusting between every layer of material species or material
Proportioning so that the oxygen barrier layers of formation are swollen in the oxygen barrier layers material thermal expansion coefficient close to Wolfram rhenium heat electric couple matrix and matrix heat
The absolute value of the difference of swollen coefficient is not more than 6 × 10-6K-1, and layers of material thermal coefficient of expansion is warm to remote W-Re in oxygen barrier layers
The direction of galvanic couple matrix gradually increases, and the oxytolerant ablation ability of layers of material is to away from Wolfram rhenium heat electric couple matrix in oxygen barrier layers
Direction also gradually increases.In this way, compared to the combination of simple W-Re matrix and single oxygen barrier layers, it is by script thermal coefficient of expansion
Big difference has been distributed between layers by component gradient or concentration gradient in the form of gradual change so that thermal coefficient of expansion by
The interior and outer thermal stress for slowly increasing, effectively reducing Wolfram rhenium heat electric couple high-temperature oxidation resistant coating, while increase W-Re thermoelectricity
The adhesive force of even high-temperature oxidation resistant coating.
Brief description of the drawings
Fig. 1 is 1 Wolfram rhenium heat electric couple antioxidant coating of the embodiment of the present invention i.e. Wolfram rhenium heat electric couple matrix-transition zone-multilayer knot
The cross section structure schematic diagram of the oxygen barrier material of structure；
Fig. 2 be 1 Wolfram rhenium heat electric couple antioxidant coating of the embodiment of the present invention through isostatic pressed+without pressure annealing process densification
Afterwards its thermoelectrical potential with the ablation time change；
Fig. 3 is 2 Wolfram rhenium heat electric couple antioxidant coating of the embodiment of the present invention through isostatic pressed+non-pressure sintering technology densification
SEM photograph of the coating afterwards through 2300 DEG C of oxy-acetylene flame ablations after ten minutes；
Fig. 4 be 3 Wolfram rhenium heat electric couple antioxidant coating of the embodiment of the present invention after high temperature insostatic pressing (HIP) densification through 2500
SEM photograph after DEG C oxy-acetylene flame ablation 35 minutes.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Not forming conflict each other can be mutually combined.
The present invention provides a kind of densifying method of Wolfram rhenium heat electric couple high-temperature oxidation resistant coating, with traditional " armouring " no
Together, antioxidant coating proposed by the present invention includes being attached directly to the transition zone of Wolfram rhenium heat electric couple matrix surface and was attached to
The oxygen barrier layers of layer surface are crossed, the thermal coefficient of expansion of buffer layer material is selected between Wolfram rhenium heat electric couple basis material and oxygen barrier layers
Material between.Its purpose is to strengthen Wolfram rhenium heat electric couple antioxidant coating in high temperature i.e. for densifying method of the present invention
More than 2000 DEG C of oxytolerant ablation ability, specific method are to carry out isostatic pressed and heat treatment to Wolfram rhenium heat electric couple antioxidant coating,
Strengthen the densification degree of Wolfram rhenium heat electric couple antioxidant coating, so as to strengthen its oxytolerant ablation ability.Specifically, the densification side
Method includes following three kinds：
(1) isostatic pressed+without pressure annealing process
20~100MPa isostatic presseds are carried out to Wolfram rhenium heat electric couple antioxidant coating to handle 10~30 minutes, then in indifferent gas
Under body protective atmosphere, the isothermal holding when 750 DEG C~1050 DEG C progress 1~3 are small, takes out after being cooled to room temperature, completes annealing
Technique.When being warming up to annealing temperature, heating rate is preferably 3~6 DEG C/min.
(2) isostatic pressed+non-pressure sintering technology
20~100MPa isostatic presseds are carried out to the Wolfram rhenium heat electric couple antioxidant coating to handle 10~30 minutes, then lazy
Property gas atmosphere under, 1400~1600 DEG C carry out 1~3 it is small when isothermal holding, carry out non-pressure sintering technology.Specifically
Ground, the non-pressure sintering technology include following sub-step：
(1) 400~600 DEG C, when insulation 1~3 is small are heated to the heating rate of 3~6 DEG C/min, carried out pre-sintered；
(2) 1400~1600 DEG C are heated to the heating rate of 2~4 DEG C/min, when insulation 1~3 is small, be sintered；
(3) 300~500 DEG C are cooled to the rate of temperature fall of 2~4 DEG C/min；
(4) taken out after sample is naturally cooling to room temperature.
(3) HIP sintering technique
Under inert gas shielding atmosphere, in 10~20MPa of pressure, 1250~1450 DEG C of temperature is to the Wolfram rhenium heat electric couple
Isothermal holding when antioxidant coating progress 1~3 is small, takes out sample after pressure release, carry out HIP sintering technique.Specifically,
The HIP sintering technique includes following sub-step：
(1) 350~450 DEG C, when insulation 1~2 is small are heated to the heating rate of 4~7 DEG C/min, carried out pre-sintered；
(2) 1250~1450 DEG C, when insulation 1~3 is small are heated to the heating rate of 3~4 DEG C/min, carry out high temperature insostatic pressing (HIP)
Sintering；
(3) 300~500 DEG C are cooled to the rate of temperature fall of 3~4 DEG C/min；
(4) taken out after sample is naturally cooling to room temperature.
Room temperature, that is, room temperature in densifying method of the present invention, general temperature range are 10~40 DEG C, and inert gas shielding is preferred
Protected for argon gas.
In the preferable coating structure of Wolfram rhenium heat electric couple antioxidant coating of the present invention transition zone select material 2000 DEG C with
On do not react with the Wolfram rhenium heat electric couple matrix, and Wolfram rhenium heat electric couple matrix, transition zone and oxygen barrier layers it is any both it
Between thermal coefficient of expansion difference absolute value be no more than 3 × 10-6K-1.General tungsten-rhenium alloy matrix thermal coefficient of expansion is minimum, from
It is interior to be sequentially increased to thermal expansion coefficient.Transition zone is selected from titanium nitride, tungsten carbide, tantalum, ramet, tungsten silicide or magnesia.Cross
Layer is crossed as 10~100 microns of film layer, preferably 10~50 microns.Oxygen barrier layers are the sandwich construction not less than 2 layers, and oxygen stops
Layers of material thermal coefficient of expansion gradually increases to the direction away from Wolfram rhenium heat electric couple matrix in layer, layers of material in oxygen barrier layers
Oxytolerant ablation ability also gradually increases to the direction away from the Wolfram rhenium heat electric couple matrix, and preferably oxygen barrier layers gross thickness is 200
Within micron.The material that oxygen barrier layers are selected is the refractory metal that can play the role of oxygen stop or oxytolerant ablation more than 2000 DEG C
Oxide, boride or nitride.Oxygen barrier layers are silica, hafnium oxide, hafnium boride, hafnium nitride, zirconium oxide, zirconium boride, nitrogen
Change the one or more in zirconium and yittrium oxide.There are component gradient or concentration gradient, i.e. oxygen stop for the oxygen barrier layers of sandwich construction
The different material category of each layer of use in the sandwich construction of material；Or identical and at least two kinds of materials per layer of material species
The mixture of material, but the proportioning of material is different in each layer.The preferable oxygen barrier material number of plies is 5~10 layers, also can be according to need
Accomplish less than 5 layers or more than 10 layers.
The oxygen barrier layers of transition zone and sandwich construction in Wolfram rhenium heat electric couple antioxidant coating structure of the present invention, material choosing
Select it is most important, when realizing the sandwich construction oxygen barrier layers with concentration gradient or component gradient using different materials, not only
The problem of meeting thermal coefficient of expansion to be incremented by, realizing stress fine dispersion, while also achieve under condition of equivalent thickness compared to more same
A kind of oxygen barrier layers of material, oxytolerant ablation ability, that is, oxidation resistance greatly enhance, and illustrate that the oxygen of heterogeneity species stops
Material or oxygen barrier material between layers have played collaboration facilitation, enhance the anti-oxidant energy of overall antioxidant coating
Power.
The Wolfram rhenium heat electric couple antioxidant coating of the present invention is carried out isostatic pressed processing can be directly by the antioxidant coating
Thickness reduces 40~50%, considerably increases the densification degree of antioxidant coating, in conjunction with heat treatment, annealing process to resist
Residual stress eliminates in oxide covering, and sintering process can increase granular size in antioxidant coating, densifying method of the invention
Significantly enhance the oxytolerant ablation ability and stability of the antioxidant coating so that the coating is in 2000~2500 DEG C of lasting works
Make more than 30 minutes.
It is embodiment below：
Embodiment 1
A kind of Wolfram rhenium heat electric couple high-temperature oxidation resistant coating structure, including transition zone and oxygen barrier layers.Oxygen barrier material and tungsten
There is the TaC transition of one layer of 20 μm of left and right thickness between the Wolfram rhenium heat electric couple silk table face that rhenium thermocouple matrix, that is, diameter is about 0.5mm
Layer, as shown in Figure 1, oxygen barrier layers one share seven layers, first layer is HfC-10%ZrC materials, and thermal coefficient of expansion is 6 × 10-6K-1, thickness is 20 μm；The second layer is HfC-30%ZrC materials, and thickness is 20 μm；Third layer is HfC-50%ZrC, and thickness is 20 μ
m；4th layer is ZrC, and thermal coefficient of expansion is 7.3 × 10-6K-1, thickness is 20 μm；Layer 5 is ZrC-10%ZrO2, and thickness is
20μm；Layer 6 is ZrC-30ZrO2, thickness is 20 μm；Layer 7 is ZrC-50ZrO2, thickness is 20 μm.The sandwich construction
Oxygen barrier material gross thickness is 140 microns, its thermal coefficient of expansion and oxytolerant ablation ability are to away from Wolfram rhenium heat electric couple matrix
Direction gradually increases.
The preparation method of transition zone is in the Wolfram rhenium heat electric couple antioxidant coating structure：
Ta powder is added fill in the plastic containers of HF (concentration about 40%) solution in the closed bin for have exhaust equipment with
80 DEG C or so heating water baths, wherein HF acid and the mass ratio of Ta powder are about 1.5.Ta powder dissolves rapidly in experimentation, has at the same time
Gas is emerged.TaF5 solution is obtained by filtration after the completion of question response, is placed in 120 DEG C of baking ovens and obtains white powder after drying.
White powder, graphite powder are pressed 1:1 mass ratio mixes, and wraps tungsten-rhenium wire, then is placed in Ar special atmosphere ovens and carries out 1800 DEG C
High-temperature heat treatment 1h or so, heating rate are 10 DEG C/min.
The preparation method of oxygen barrier material is in the Wolfram rhenium heat electric couple antioxidant coating structure：
First pass through ball milling and micronization processes are carried out respectively to hafnium carbide, zirconium carbide and Zirconium oxide powder, according to mentioned component
Content adjusts their mass ratio, then controls spray distance 150mm, spray power 30kW, powder feeding by plasma spraying machine
Speed 3kg/h, is sprayed on transition zone by the cladding powder of the a%HfC-b%ZrC-c%ZrO2 with heterogeneity accounting respectively
Outer layer, is made seven layers of Wolfram rhenium heat electric couple oxygen barrier layers with component gradient successively.
Annealing process is used again after the antioxidant coating is carried out isostatic cool pressing processing, is specifically carried out as follows：
Cated Wolfram rhenium heat electric couple surface will be wrapped up in be soaked with deionized water, be then placed in polybag and do at exhaust sealing
Reason, then be placed in cold isostatic press and carry out 30MPa isostatic presseds 15 clocks of processing, take out drying and is placed in high-temperature atmosphere furnace, in argon
Under gas shielded atmosphere, using isothermal holding of the heating rate as 5 DEG C/min when 800 DEG C of progress 1 are small, after room temperature is naturally cooling to
Take out, complete annealing process.
Obtained laminated coating carries out ablation, Fig. 2 is it after 800 DEG C of annealings with more than 2300 DEG C oxy-acetylene flames
Thermoelectrical potential with the ablation time change, it is seen that still have thermo-electromotive force generation during 850s, illustrate that Wolfram rhenium heat electric couple is not destroyed, remain to
Normal work, the protection effect of antioxidant coating are notable.
Embodiment 2
A kind of Wolfram rhenium heat electric couple high-temperature oxidation resistant coating structure, including transition zone and oxygen barrier layers.Oxygen barrier material and tungsten
There is the Ta transition of one layer of 15 μm of left and right thickness between the Wolfram rhenium heat electric couple silk table face that rhenium thermocouple matrix, that is, diameter is about 0.5mm
Layer.Oxygen barrier layers one share six layers, and first layer is SiC material, and thermal coefficient of expansion is 4.5 × 10-6K-1, thickness is 20 μm；Second
Layer is SiC-20%HfC materials, and thickness is 20 μm；Third layer is SiC-40%HfC, and thickness is 20 μm；4th layer is SiC-
60%HfC, thickness are 20 μm；Layer 5 is SiC-80%HfC, and thickness is 20 μm；Layer 6 is HfC, thermal coefficient of expansion 6.7
×10-6K-1, thickness is 20 μm.The oxygen barrier material gross thickness of the sandwich construction is 120 microns, its thermal coefficient of expansion and resistance to
Oxygen ablation ability gradually increases to the direction away from Wolfram rhenium heat electric couple matrix.
The preparation method of transition zone is in the Wolfram rhenium heat electric couple antioxidant coating structure：
Using tungsten-carbide powder as reaction raw materials, by superhigh temperature atomising device to W-Re after 3000 DEG C of superhigh temperature meltings
Matrix surface carries out thermal spraying, controls spray distance 150mm, spray power 30kW, controls flow, makes coating uniform and cause
Close, thickness is about 15 μm.
The preparation method of oxygen barrier material is in the Wolfram rhenium heat electric couple antioxidant coating structure：
With hydrogen (flow velocity is about 750sccm), methyl trichlorosilane (flow velocity is about 200sccm) and hafnium tetrachloride (flow velocity
About 100sccm) as reaction gas phase, using argon gas as carrier (flow velocity is about 350sccm), adjust and react by each layer coating composition
The accounting of each source of the gas in gas phase, passes through the side of low-pressure chemical vapor deposition under 850mTorr or so low pressure, 900 DEG C or so high temperature
The multilayer x%SiC-y%HfC thin layers of component accounting gradual change can be made in method, and deposition velocity is about 3 μm/h.
It is sintered after the antioxidant coating is carried out isostatic cool pressing processing, specifically carries out as follows again：
Cated Wolfram rhenium heat electric couple surface will be wrapped up in be soaked with deionized water, be then placed in polybag and do at exhaust sealing
Reason, then be placed in cold isostatic press and carry out 30MPa isostatic presseds processing 15 minutes, take out drying and is placed in high-temperature atmosphere furnace,
Under argon atmosphere, 500 DEG C, when insulation 1 is small first are heated to the heating rate of 5 DEG C/min, is carried out pre-sintered；Again with 3 DEG C/
The heating rate of min is heated to 1500 DEG C, when insulation 2 is small, is sintered；Then 500 are cooled to the rate of temperature fall of 3 DEG C/min
℃；Finally taken out after sample is naturally cooling to room temperature, complete non-pressure sintering technology.
Fig. 3 is SEM photograph of the coating after densification through 2300 DEG C of oxy-acetylene flame ablations after ten minutes.Can by Fig. 3
See, coating surface through a long time thermal-flame washes away and cracking, but has no significant through crackle.
Embodiment 3
A kind of Wolfram rhenium heat electric couple high-temperature oxidation resistant coating structure, including transition zone and oxygen barrier layers.Oxygen barrier material and tungsten
There is the WSi2 transition of one layer of 20 μm of left and right thickness between the Wolfram rhenium heat electric couple silk table face that rhenium thermocouple matrix, that is, diameter is about 0.5mm
Layer.Oxygen barrier layers one share eleventh floor, and first layer is HfO2 materials, and thermal coefficient of expansion is 4.3 × 10-6K-1, thickness is 20 μm；
The second layer is HfO2-10%YSZ (yttrium stable zirconium oxide, molar ratio Y：Zr=6：100) material, thickness are 20 μm；Third layer is
HfO2-20%YSZ, thickness are 20 μm；4th layer is HfO2- 30%YSZ, thickness are 20 μm；Layer 5 is HfO2- 40%YSZ,
Thickness is 20 μm；Layer 6 is HfO2-50%YSZ, and thickness is 20 μm；Layer 7 is HfO2- 60%YSZ, thickness are 20 μm；The
Eight layers are HfO2- 70%YSZ, thickness are 20 μm；9th layer is HfO2- 80%YSZ, thickness are 20 μm；Tenth layer is HfO2-
90%YSZ, thickness are 20 μm；Eleventh floor is YSZ, and thermal coefficient of expansion is 11.5 × 10-6K-1, thickness is 20 μm.The multilayer knot
The oxygen barrier material gross thickness of structure is 210 microns, its thermal coefficient of expansion and oxytolerant ablation ability are to away from Wolfram rhenium heat electric couple base
The direction of body gradually increases.
The preparation method of transition zone is in the Wolfram rhenium heat electric couple antioxidant coating structure：
Will penetrate into element powders, filler, activator according to (high-purity silicon powder) 25wt%, (silicon carbide powder) 70wt%,
The ratio of (sodium fluoride powder) 5wt% weighs, and the penetration enhancer of certain mass is weighed according to the size of corundum crucible.It is uniformly mixed
Afterwards, by corundum crucible of the tungsten-rhenium alloy embedment equipped with penetration enhancer, close the lid.The corundum crucible of embedded Wolfram rhenium heat electric couple is put
In high temperature furnace, 1650 DEG C of high-temperature process 1h are carried out.In order to reliably prevent the oxidation of penetration enhancer and alloy during bag oozes, improve
Quality layer, oozes process using argon gas protection bag.
The preparation method of oxygen barrier material is in the Wolfram rhenium heat electric couple antioxidant coating structure：
First with eight hydration oxychlorination hafniums (10~20wt%), Macrogol 4000 (10~20wt%) and deionized water (60
~80wt%) hafnium colloidal sol is prepared, it is 2~3 then to adjust collosol PH value with ammonium hydroxide, is taken after ageing a few days stabilization a certain amount of in beaker
Suspension is made in middle incorporation hafnium oxide powder (the 10~40% of colloidal sol quality), uniform stirring, then using pulling machine that W-Re is warm
First layer is made in galvanic couple immersion-pull-out-drying；Equivalent colloidal sol is taken, by hafnium oxide powder and the moles yttrium powder of zirconium oxide -6%
(gross mass accounts for the 10~40% of colloidal sol quality) in mass ratio 9：1 is added in colloidal sol, repeats immersion-pull-out-drying steps
The second layer is made；Equivalent colloidal sol separately is taken, (gross mass accounts for colloidal sol quality by hafnium oxide powder and the moles of zirconium oxide -6% yttrium powder
10~40%) in mass ratio 8：2 are added in colloidal sol, repeat immersion-pull-out-drying steps and third layer is made；Class successively
Push away, eleventh floor, which is made, has the Wolfram rhenium heat electric couple antioxidant coating of component gradient.
The antioxidant coating is directly subjected to HIP sintering processing, is specifically carried out as follows：
Cated Wolfram rhenium heat electric couple will be wrapped up in be placed in hot isostatic pressure stove, pass to the inert gases such as argon gas as protection
Gas, to gas pressurized to 15MPa, is first heated to 400 DEG C, when insulation 1 is small with the heating rate of 5 DEG C/min, carries out pre-sintered；Again
1350 DEG C, when insulation 2 is small are heated to the heating rate of 4 DEG C/min, carries out HIP sintering；Then with the drop of 3 DEG C/min
Warm speed is cooled to 400 DEG C；Finally pressure release and sample is taken out after furnace body is naturally cooling to room temperature, completed at HIP sintering
Reason.
The SEM photograph that Fig. 4 is coating after 2500 DEG C of oxy-acetylene flame ablations 35 minutes.As seen from the figure, coating surface is through length
Time thermal-flame washes away and successively peels off, cracks, but WRe thermocouple matrix forms remain intact substantially.
Table 1 list 1~3 Wolfram rhenium heat electric couple antioxidant coating of embodiment carry out densification before and after coating layer thickness and
The change of oxytolerant ablation time.
1 embodiment of table, 1~3 Wolfram rhenium heat electric couple antioxidant coating carries out the front and rear change of densification
As it can be seen from table 1 the antioxidant coating thickness after isostatic pressed is handled reduces more than 40%, illustrate that coating causes
Degree of densification greatly increases, and Wolfram rhenium heat electric couple antioxidant coating has the oxygen barrier layers structure of eleventh floor wherein in embodiment 3, adopts
After hip treatment, its oxytolerant ablation time was up to more than 35 minutes；And the antioxidant coating in most thin embodiment 2
Can be more than 10 minutes in 2300 DEG C of oxytolerant ablations.
Each raw material cited by the present invention can realize the present invention, and the bound value of each raw material, interval value can
Realize the present invention, the bound value of technological parameter (such as pressure, temperature, time, heating rate) of the invention and section
Value can realize the present invention, embodiment numerous to list herein.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., should all include
Within protection scope of the present invention.
Claims (10)
- A kind of 1. densifying method of Wolfram rhenium heat electric couple antioxidant coating, it is characterised in that the anti-oxidant painting of Wolfram rhenium heat electric couple Layer is attached to the Wolfram rhenium heat electric couple matrix surface, and the antioxidant coating includes transition zone and positioned at the transition layer surface Oxygen barrier layers, the thermal coefficient of expansion of the buffer layer material is between the Wolfram rhenium heat electric couple basis material and the oxygen barrier layers Between the material of selection；The densifying method is that the Wolfram rhenium heat electric couple antioxidant coating is carried out isostatic pressed and heat treatment.
- 2. densifying method as claimed in claim 1, it is characterised in that 20 are carried out to the Wolfram rhenium heat electric couple antioxidant coating ~100MPa isostatic presseds are handled 10~30 minutes, and then under inert gas shielding atmosphere, 1~3 is carried out at 750 DEG C~1050 DEG C The isothermal holding of hour, takes out after being cooled to room temperature, completes annealing process.
- 3. densifying method as claimed in claim 2, it is characterised in that heating rate is 3~6 DEG C/min.
- 4. densifying method as claimed in claim 1, it is characterised in that 20 are carried out to the Wolfram rhenium heat electric couple antioxidant coating ~100MPa isostatic presseds are handled 10~30 minutes, and then under inert gas shielding atmosphere, 1~3 is carried out at 1400~1600 DEG C The isothermal holding of hour, carries out non-pressure sintering technology.
- 5. densifying method as claimed in claim 4, it is characterised in that the non-pressure sintering technology includes following sub-step：(1) 400~600 DEG C, when insulation 1~3 is small are heated to the heating rate of 3~6 DEG C/min, carried out pre-sintered；(2) 1400~1600 DEG C are heated to the heating rate of 2~4 DEG C/min, when insulation 1~3 is small, be sintered；(3) 300~500 DEG C are cooled to the rate of temperature fall of 2~4 DEG C/min；(4) taken out after sample is naturally cooling to room temperature.
- 6. densifying method as claimed in claim 1, it is characterised in that under inert gas shielding atmosphere, pressure 10~ 20MPa, isothermal holding when temperature is 1250~1450 DEG C small to Wolfram rhenium heat electric couple antioxidant coating progress 1~3, after pressure release Sample is taken out, carries out HIP sintering technique.
- 7. densifying method as claimed in claim 6, it is characterised in that in the inert gas shielding that pressure is 10~20MPa Under atmosphere, the sintering process of following steps is carried out：(1) 350~450 DEG C, when insulation 1~2 is small are heated to the heating rate of 4~7 DEG C/min, carried out pre-sintered；(2) 1250~1450 DEG C, when insulation 1~3 is small are heated to the heating rate of 3~4 DEG C/min, carry out high temperature insostatic pressing (HIP) burning Knot；(3) 300~500 DEG C are cooled to the rate of temperature fall of 3~4 DEG C/min；(4) taken out after sample is naturally cooling to room temperature.
- 8. densifying method as claimed in claim 1, it is characterised in that the material that the transition zone is selected be selected from titanium nitride, Tungsten carbide, tantalum, ramet, tungsten silicide or magnesia；The transition zone is preferably 10~100 microns of film layer.
- 9. densifying method as claimed in claim 1, it is characterised in that the oxygen barrier layers are the multilayer knot not less than 2 layers Structure, layers of material thermal coefficient of expansion gradually increases to the direction away from the Wolfram rhenium heat electric couple matrix in the oxygen barrier layers, institute The oxytolerant ablation ability for stating layers of material in oxygen barrier layers also gradually increases to the direction away from the Wolfram rhenium heat electric couple matrix, excellent The oxygen barrier layers gross thickness is selected to be not more than 200 microns.
- 10. densifying method as claimed in claim 1, it is characterised in that the material that the oxygen barrier layers are selected is 2000 It can play the role of refractory metal oxide, boride or the nitride of oxygen stop or oxytolerant ablation more than DEG C.
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| PCT/CN2018/108521 WO2019109717A1 (en) | 2017-12-07 | 2018-09-29 | Method of densifying high temperature anti-oxidation coating for tungsten-rhenium thermocouple |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109666894A (en) * | 2019-02-27 | 2019-04-23 | 西安方科新材料科技有限公司 | A kind of siller tin oxide composite coating and preparation method thereof |
| WO2019109717A1 (en) * | 2017-12-07 | 2019-06-13 | 华中科技大学 | Method of densifying high temperature anti-oxidation coating for tungsten-rhenium thermocouple |
| WO2019109718A1 (en) * | 2017-12-07 | 2019-06-13 | 华中科技大学 | Oxygen barrier material in anti-oxidation coating structure for tungsten-rhenium thermocouple and application thereof |
| WO2019109752A1 (en) * | 2017-12-07 | 2019-06-13 | 华中科技大学 | High temperature anti-oxidation coating for tungsten-rhenium thermocouple and application thereof |
| CN110863167A (en) * | 2019-12-06 | 2020-03-06 | 华中科技大学 | Niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating structure and preparation method thereof |
| CN114293179A (en) * | 2021-12-08 | 2022-04-08 | 重庆材料研究院有限公司 | Preparation method of hafnium oxide coating for noble metal thermocouple |
| CN114351074A (en) * | 2021-12-08 | 2022-04-15 | 重庆材料研究院有限公司 | Method for coating high-temperature-resistant coating on noble metal thermocouple wire |
| CN114478004A (en) * | 2021-12-31 | 2022-05-13 | 重庆材料研究院有限公司 | Preparation method of hafnium oxide ceramic product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579958A (en) * | 2009-06-29 | 2009-11-18 | 中国科学院等离子体物理研究所 | Steel-based multifunctional ceramic composite coating and preparation method thereof |
| CN102095517A (en) * | 2010-11-26 | 2011-06-15 | 中国航空工业集团公司北京长城计量测试技术研究所 | High-temperature temperature sensor based on surface-modified tungsten-rhenium thermocouple |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106498355B (en) * | 2016-10-20 | 2018-08-21 | 电子科技大学 | A kind of high temperature film sensor anti-oxidant composite armor and its manufacturing method |
| CN107012425B (en) * | 2017-03-09 | 2020-02-14 | 电子科技大学 | Composite insulating layer for thin film sensor and preparation method thereof |
| CN107201502A (en) * | 2017-05-05 | 2017-09-26 | 电子科技大学 | A kind of high temperature film sensor with self-healing composite armor and preparation method thereof |
| CN108034939B (en) * | 2017-12-07 | 2019-07-19 | 华中科技大学 | A kind of densifying method of Wolfram rhenium heat electric couple high-temperature oxidation resistant coating |
-
2017
- 2017-12-07 CN CN201711284029.7A patent/CN108034939B/en active Active
-
2018
- 2018-09-29 WO PCT/CN2018/108521 patent/WO2019109717A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579958A (en) * | 2009-06-29 | 2009-11-18 | 中国科学院等离子体物理研究所 | Steel-based multifunctional ceramic composite coating and preparation method thereof |
| CN102095517A (en) * | 2010-11-26 | 2011-06-15 | 中国航空工业集团公司北京长城计量测试技术研究所 | High-temperature temperature sensor based on surface-modified tungsten-rhenium thermocouple |
Non-Patent Citations (3)
| Title |
|---|
| 现代材料腐蚀与防护: "《现代材料腐蚀与防护》", 30 September 2012, 上海交通大学出版社 * |
| 罗蜜: "以硅化物涂层为过渡层的钨铼热电偶抗氧化膜的研制", 《华中科技大学硕士学位论文》 * |
| 郦振声等: "《现代表面工程技术》", 30 June 2007, 机械工业出版社 * |
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| WO2019109718A1 (en) * | 2017-12-07 | 2019-06-13 | 华中科技大学 | Oxygen barrier material in anti-oxidation coating structure for tungsten-rhenium thermocouple and application thereof |
| WO2019109752A1 (en) * | 2017-12-07 | 2019-06-13 | 华中科技大学 | High temperature anti-oxidation coating for tungsten-rhenium thermocouple and application thereof |
| CN109666894A (en) * | 2019-02-27 | 2019-04-23 | 西安方科新材料科技有限公司 | A kind of siller tin oxide composite coating and preparation method thereof |
| CN110863167A (en) * | 2019-12-06 | 2020-03-06 | 华中科技大学 | Niobium-tungsten alloy ultrahigh-temperature oxidation-resistant coating structure and preparation method thereof |
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| CN114478004A (en) * | 2021-12-31 | 2022-05-13 | 重庆材料研究院有限公司 | Preparation method of hafnium oxide ceramic product |
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