CN108034939B - 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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- CN108034939B CN108034939B CN201711284029.7A CN201711284029A CN108034939B CN 108034939 B CN108034939 B CN 108034939B CN 201711284029 A CN201711284029 A CN 201711284029A CN 108034939 B CN108034939 B CN 108034939B
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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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- 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
- 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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- 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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- 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, including transition zone and positioned at the oxygen barrier layers of the transition layer surface, the thermal expansion coefficient 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；Equal static pressure 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 simultaneously, so that Wolfram rhenium heat electric couple antioxidant coating thickness reduces 40% or more, while the oxytolerant ablation ability under 2000 DEG C of coating or more aerobic environment significantly increases, and thus solves the problems, such as long-time contact type temperature measuring in 2000 DEG C or more 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 technique
Measurement for 1600 DEG C or more ultra-high temperatures mostly uses non-contact (infrared, optics etc.) method to measure at present, 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 has apparent advantage compared with other thermocouples:
(1) fusing point is high (> 3000 DEG C), and 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 cannot be 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 project that domestic and international field of pyrometry is paid high attention to.
Use Wolfram rhenium heat electric couple thermometric under aerobic environment at present, generally take two ways: one is disposable measurements
It uses, i.e., each thermometric time is very short, does not use or uses after processing again 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 is used as protection pipe using quartz, corundum, refractory metal and refractory ceramics etc., be packed into after Wolfram rhenium heat electric couple evacuate seal,
Filling with inert gas sealing or filling inertia powder sealing, artificially create non-oxidizing atmosphere in protection pipe for thermocouple, make
It completes thermometric mission, but this anti-oxidant thermocouple of non-removable solid type before oxidation is deteriorated, and has the following problems:
(1) thermocouple use the protected pipe temperature resistant capability of temperature limitation, usually less than 1800 DEG C；
(2) thermocouple armouring protection after volume and weight increase, in the stringenter system of volume requirement use by
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, under the premise of not influencing response speed, thermoelectricity is improved
The even thermometric upper limit in high temperature air and other high temperature oxidative atmospheres extends the thermometric working time, is 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 always
The open report of duration, and put into and actually use without Related product so far in global range.
The invention proposes a kind of novel high-temperature oxidation resistant coating structures and its densification for Wolfram rhenium heat electric couple surface
Change method is allowed to the long-time contact temperature-measuring being able to achieve under 2000 DEG C or more superhigh temperature aerobic environments.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of Wolfram rhenium heat electric couple antioxidant coatings
Densifying method, its object is to by the antioxidant coating being directly in contact with Wolfram rhenium heat electric couple matrix simultaneously or successively
Equal static pressure and heat treatment are carried out, so that Wolfram rhenium heat electric couple antioxidant coating thickness reduces 40~50%, while 2000 DEG C of the coating
Oxytolerant ablation ability under the above aerobic environment significantly increases, and thus solves in 2000 DEG C or more 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 expansion coefficient 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 waiting static pressure and heat treatment.
Preferably, the Wolfram rhenium heat electric couple antioxidant coating is carried out 20~100MPa isostatic pressing 10~30 minutes,
Then under inert gas shielding atmosphere, 1~3 hour isothermal holding is carried out at 750 DEG C~1050 DEG C, is taken after being cooled to room temperature
Out, annealing process is completed.
It is further preferred that heating rate is 3~6 DEG C/min.
Preferably, the Wolfram rhenium heat electric couple antioxidant coating is carried out 20~100MPa isostatic pressing 10~30 minutes,
Then under inert gas shielding atmosphere, 1~3 hour isothermal holding is carried out at 1400~1600 DEG C, 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 are heated to the heating rate of 3~6 DEG C/min, keep the temperature 1~3 hour, is pre-sintered；
(2) 1400~1600 DEG C are heated to the heating rate of 2~4 DEG C/min, keep the temperature 1~3 hour, is sintered；
(3) 300~500 DEG C are cooled to the rate of temperature fall of 2~4 DEG C/min；
(4) it is 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 to the tungsten
Rhenium thermocouple antioxidant coating carries out 1~3 hour isothermal holding, and sample is taken out after pressure release, carries out HIP sintering technique.
It is further preferred that carrying out the sintering of following steps in the case where pressure is the inert gas shielding atmosphere of 10~20MPa
Technique:
(1) 350~450 DEG C are heated to the heating rate of 4~7 DEG C/min, keep the temperature 1~2 hour, is pre-sintered；
(2) 1250~1450 DEG C are heated to the heating rate of 3~4 DEG C/min, keep the temperature 1~3 hour, carry out hot isostatic pressing
Sintering；
(3) 300~500 DEG C are cooled to the rate of temperature fall of 3~4 DEG C/min；
(4) it is 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, tantalum carbide, tungsten silicide or oxidation
Magnesium；The transition zone is preferably 10~100 microns of film layer.
Preferably, the oxygen barrier layers are the multilayered structure not less than 2 layers, layers of material thermal expansion in the oxygen barrier layers
Coefficient is gradually increased to the direction far from the Wolfram rhenium heat electric couple matrix, the oxytolerant ablation energy of layers of material in the oxygen barrier layers
Power is also gradually increased to the direction far from the Wolfram rhenium heat electric couple matrix.
Preferably, the oxygen barrier layers overall 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 blocking or oxytolerant ablation at 2000 DEG C or more
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 by chemical vapour deposition technique, hot spray process or sol-gal process in the transition layer surface
To the oxygen barrier layers.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
1) present invention carries out waiting static pressure and heat treatment by the high-temperature oxidation resistant coating to Wolfram rhenium heat electric couple surface, so that should
Antioxidant coating is finer and close, and micro-crack is less, and porosity is lower；
2) present invention is heat-treated by the antioxidant coating to 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 makes antioxidant coating combine closer, more difficult disengaging, adhesive force
It is greatly improved；
4) treated that coating is more obvious to the barrier effect of oxygen at high temperature for coating densifying method of the present invention, 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
Including transition zone and positioned at the oxygen barrier layers of transition layer surface, transition zone is located immediately at Wolfram rhenium heat electric couple silk table face, with a thickness of 10
~100 microns, setting transition zone makes the adhesive force of Wolfram rhenium heat electric couple surface covering be 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) include in Wolfram rhenium heat electric couple antioxidant coating structure proposed by the present invention multilayered structure oxygen barrier layers, this is more
There are component gradients and concentration gradient for oxygen barrier layers in layer structure, i.e., by adjusting between every layer of material type or material
Proportion, so that the oxygen barrier layers formed are swollen in the oxygen barrier layers material thermal expansion coefficient and matrix heat of close Wolfram rhenium heat electric couple matrix
The absolute value of the difference of swollen coefficient is not more than 6 × 10-6K-1, and layers of material thermal expansion coefficient is warm to separate W-Re in oxygen barrier layers
The direction of galvanic couple matrix is gradually increased, and the oxytolerant ablation ability of layers of material is to far from Wolfram rhenium heat electric couple matrix in oxygen barrier layers
Direction is also gradually increased.In this way, comparing the combination of simple W-Re matrix and single oxygen barrier layers, it is by script thermal expansion coefficient
Big difference has been distributed between layers in the form of gradual change component gradient or concentration gradient so that thermal expansion coefficient by
It is interior and it is outer slowly increase, effectively reduce the thermal stress of Wolfram rhenium heat electric couple high-temperature oxidation resistant coating, while increasing W-Re thermoelectricity
The adhesive force of even high-temperature oxidation resistant coating.
Detailed description of the invention
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 is 1 Wolfram rhenium heat electric couple antioxidant coating of the embodiment of the present invention through equal static pressure+without pressure annealing process densification
Later its thermoelectrical potential with the ablation time variation；
Fig. 3 is 2 Wolfram rhenium heat electric couple antioxidant coating of the embodiment of the present invention through equal static pressure+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 hot isostatic pressing densification through 2500
SEM photograph DEG C after oxy-acetylene flame ablation 35 minutes.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, 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 the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of densifying methods of Wolfram rhenium heat electric couple high-temperature oxidation resistant coating, no with traditional " armouring "
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 being attached to
The oxygen barrier layers of layer surface are crossed, the thermal expansion coefficient of buffer layer material is selected between Wolfram rhenium heat electric couple basis material and oxygen barrier layers
Material between.Densifying method of the present invention its purpose is to enhance Wolfram rhenium heat electric couple antioxidant coating high temperature i.e.
2000 DEG C or more of oxytolerant ablation ability, specific method are to carry out waiting static pressure and heat treatment to Wolfram rhenium heat electric couple antioxidant coating,
The densification degree for enhancing Wolfram rhenium heat electric couple antioxidant coating, to enhance its oxytolerant ablation ability.Specifically, the densification side
Method includes the following three types:
(1) static pressure+without pressure annealing process such as
Wolfram rhenium heat electric couple antioxidant coating is carried out 20~100MPa isostatic pressing 10~30 minutes, then in indifferent gas
Under body protective atmosphere, 1~3 hour isothermal holding is carried out at 750 DEG C~1050 DEG C, is taken out after being cooled to room temperature, complete annealing
Technique.When being warming up to annealing temperature, heating rate is preferably 3~6 DEG C/min.
(2) static pressure+non-pressure sintering technology such as
The Wolfram rhenium heat electric couple antioxidant coating is carried out 20~100MPa isostatic pressing 10~30 minutes, then lazy
Property gas atmosphere under, 1~3 hour isothermal holding is carried out at 1400~1600 DEG C, carries out non-pressure sintering technology.Specifically
Ground, the non-pressure sintering technology include following sub-step:
(1) 400~600 DEG C are heated to the heating rate of 3~6 DEG C/min, keep the temperature 1~3 hour, is pre-sintered；
(2) 1400~1600 DEG C are heated to the heating rate of 2~4 DEG C/min, keep the temperature 1~3 hour, is sintered；
(3) 300~500 DEG C are cooled to the rate of temperature fall of 2~4 DEG C/min；
(4) it is 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 to the Wolfram rhenium heat electric couple
Antioxidant coating carries out 1~3 hour isothermal holding, and sample is taken out after pressure release, carries out HIP sintering technique.Specifically,
The HIP sintering technique includes following sub-step:
(1) 350~450 DEG C are heated to the heating rate of 4~7 DEG C/min, keep the temperature 1~2 hour, is pre-sintered；
(2) 1250~1450 DEG C are heated to the heating rate of 3~4 DEG C/min, keep the temperature 1~3 hour, carry out hot isostatic pressing
Sintering；
(3) 300~500 DEG C are cooled to the rate of temperature fall of 3~4 DEG C/min；
(4) it is 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
For argon gas protection.
In the preferred 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, any the two of transition zone and oxygen barrier layers
Between thermal expansion coefficient absolute value of the difference be no more than 3 × 10-6K-1.General tungsten-rhenium alloy matrix thermal expansion coefficient is minimum, from
It is interior to be sequentially increased to thermal expansion coefficient.Transition zone is selected from titanium nitride, tungsten carbide, tantalum, tantalum carbide, tungsten silicide or magnesia.It crosses
Crossing layer is 10~100 microns of film layer, preferably 10~50 microns.Oxygen barrier layers are the multilayered structure not less than 2 layers, and oxygen stops
Layers of material thermal expansion coefficient is gradually increased to the direction far from Wolfram rhenium heat electric couple matrix in layer, layers of material in oxygen barrier layers
Oxytolerant ablation ability is also gradually increased to the direction far from the Wolfram rhenium heat electric couple matrix, and preferably oxygen barrier layers overall thickness is 200
Within micron.The material that oxygen barrier layers are selected is the refractory metal that can play the role of oxygen blocking or oxytolerant ablation at 2000 DEG C or more
Oxide, boride or nitride.Oxygen barrier layers are silica, hafnium oxide, hafnium boride, hafnium nitride, zirconium oxide, zirconium boride, nitrogen
Change one of zirconium and yttrium oxide or a variety of.There are component gradient or concentration gradients, i.e. oxygen to stop for the oxygen barrier layers of multilayered structure
Different material categories is used for each layer in the multilayered structure of material；Or every layer of material type is identical and at least two kinds of materials
The mixture of material, but the proportion of material is different in each layer.The preferred oxygen barrier material number of plies is 5~10 layers, can also be according to need
Accomplish 5 layers or less or 10 layers or more.
The oxygen barrier layers of transition zone and multilayered structure in Wolfram rhenium heat electric couple antioxidant coating structure of the present invention, material choosing
Select it is most important, when realizing the multilayered structure oxygen barrier layers with concentration gradient or component gradient using different materials, not only
The problem of thermal expansion coefficient is incremented by, realizes stress fine dispersion is met, while also being achieved same compared to relatively under condition of equivalent thickness
A kind of oxygen barrier layers of material, oxytolerant ablation ability, that is, oxidation resistance greatly enhance, and illustrate that the oxygen of heterogeneity type stops
Material or oxygen barrier material between layers have played collaboration facilitation, enhance the anti-oxidant energy of overall antioxidant coating
Power.
Wolfram rhenium heat electric couple antioxidant coating of the invention is carried out isostatic pressing 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 is eliminated in oxide covering, and sintering process can increase granular size in antioxidant coating, densifying method of the invention
The oxytolerant ablation ability and stability of the antioxidant coating are significantly enhanced, so that the coating is in 2000~2500 DEG C of lasting works
Make 30 minutes or more.
The following are embodiments:
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 material, and thermal expansion coefficient is 6 × 10-6K-1, with a thickness of 20 μm；The second layer is HfC-30%ZrC material, with a thickness of 20 μm；Third layer is HfC-50%ZrC, with a thickness of 20 μ
m；4th layer is ZrC, and thermal expansion coefficient is 7.3 × 10-6K-1, with a thickness of 20 μm；Layer 5 is ZrC-10%ZrO2, with a thickness of
20μm；Layer 6 is ZrC-30ZrO2, with a thickness of 20 μm；Layer 7 is ZrC-50ZrO2, with a thickness of 20 μm.The multilayered structure
Oxygen barrier material overall thickness is 140 microns, and thermal expansion coefficient and oxytolerant ablation ability are to far from Wolfram rhenium heat electric couple matrix
Direction is gradually increased.
In the Wolfram rhenium heat electric couple antioxidant coating structure transition zone the preparation method comprises the following steps:
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 the mass ratio of HF acid and Ta powder is about 1.5.Ta powder dissolves rapidly in experimentation, has simultaneously
Gas is emerged.To which TaF5 solution is obtained by filtration after the reaction was completed, places it in 120 DEG C of baking ovens and obtain white powder after drying.
White powder, graphite powder are mixed by 1:1 mass ratio, wrap tungsten-rhenium wire, then be placed in Ar special atmosphere oven and carry out 1800 DEG C
High-temperature heat treatment 1h or so, heating rate are 10 DEG C/min.
In the Wolfram rhenium heat electric couple antioxidant coating structure oxygen barrier material the preparation method comprises the following steps:
It first passes through ball milling and micronization processes is 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
The cladding powder of a%HfC-b%ZrC-c%ZrO2 with heterogeneity accounting is sprayed on transition zone respectively by rate 3kg/h
Seven layers of Wolfram rhenium heat electric couple oxygen barrier layers with component gradient are successively made in outer layer.
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 it is placed in progress 15 clock of 30MPa isostatic pressing in cold isostatic press, it takes out drying and is placed in high-temperature atmosphere furnace, in argon
It take heating rate as the isothermal holding of 5 DEG C/min progress 1 hour at 800 DEG C, after being naturally cooling to room temperature under gas shielded atmosphere
It takes out, completes annealing process.
Laminated coating obtained carries out ablation with 2300 DEG C or more oxy-acetylene flames, Fig. 2 is it after 800 DEG C of annealings
Thermoelectrical potential with the ablation time variation, it is seen that still have thermo-electromotive force generation when 850s, illustrate that Wolfram rhenium heat electric couple is not destroyed, remain to
It works normally, the protection effect of antioxidant coating is significant.
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 expansion coefficient is 4.5 × 10-6K-1, with a thickness of 20 μm；Second
Layer is SiC-20%HfC material, with a thickness of 20 μm；Third layer is SiC-40%HfC, with a thickness of 20 μm；4th layer is SiC-
60%HfC, with a thickness of 20 μm；Layer 5 is SiC-80%HfC, with a thickness of 20 μm；Layer 6 is HfC, thermal expansion coefficient 6.7
×10-6K-1, with a thickness of 20 μm.The oxygen barrier material overall thickness of the multilayered structure is 120 microns, thermal expansion coefficient and resistance to
Oxygen ablation ability is gradually increased to the direction far from Wolfram rhenium heat electric couple matrix.
In the Wolfram rhenium heat electric couple antioxidant coating structure transition zone the preparation method comprises the following steps:
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.
In the Wolfram rhenium heat electric couple antioxidant coating structure oxygen barrier material the preparation method comprises the following steps:
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), adjusts and react by each layer coating composition
The accounting of each gas source 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 layer of ingredient 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 pressing 15 minutes, it takes out drying and is placed in high-temperature atmosphere furnace,
Under argon atmosphere, 500 DEG C first are heated to the heating rate of 5 DEG C/min, 1 hour is kept the temperature, is pre-sintered；Again with 3 DEG C/
The heating rate of min is heated to 1500 DEG C, keeps the temperature 2 hours, is sintered；Then 500 are cooled to the rate of temperature fall of 3 DEG C/min
℃；It is finally taken out after sample is naturally cooling to room temperature, completes non-pressure sintering technology.
SEM photograph of the Fig. 3 for the coating after densification through 2300 DEG C of oxy-acetylene flame ablations after ten minutes.It can by Fig. 3
See, coating surface through a long time thermal-flame is washed away and cracked, but is had 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 material, and thermal expansion coefficient is 4.3 × 10-6K-1, with a thickness of 20 μm；
The second layer is HfO2-10%YSZ (yttrium stable zirconium oxide, molar ratio Y:Zr=6:100) material, with a thickness of 20 μm；Third layer is
HfO2-20%YSZ, with a thickness of 20 μm；4th layer is HfO2- 30%YSZ, with a thickness of 20 μm；Layer 5 is HfO2- 40%YSZ,
With a thickness of 20 μm；Layer 6 is HfO2-50%YSZ, with a thickness of 20 μm；Layer 7 is HfO2- 60%YSZ, with a thickness of 20 μm；The
Eight layers are HfO2- 70%YSZ, with a thickness of 20 μm；9th layer is HfO2- 80%YSZ, with a thickness of 20 μm；Tenth layer is HfO2-
90%YSZ, with a thickness of 20 μm；Eleventh floor is YSZ, and thermal expansion coefficient is 11.5 × 10-6K-1, with a thickness of 20 μm.The multilayer knot
The oxygen barrier material overall thickness of structure is 210 microns, and thermal expansion coefficient and oxytolerant ablation ability are to far from Wolfram rhenium heat electric couple base
The direction of body is gradually increased.
In the Wolfram rhenium heat electric couple antioxidant coating structure transition zone the preparation method comprises the following steps:
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, tungsten-rhenium alloy embedment is closed the lid equipped in the corundum crucible of penetration enhancer.The corundum crucible of embedded Wolfram rhenium heat electric couple is set
In high temperature furnace, 1650 DEG C of high-temperature process 1h are carried out.In order to reliably prevent packet seep during penetration enhancer and alloy oxidation, improve
Quality layer protects packet infiltration process using argon gas.
In the Wolfram rhenium heat electric couple antioxidant coating structure oxygen barrier material the preparation method comprises the following steps:
First with eight hydrations oxychlorination hafnium (10~20wt%), Macrogol 4000 (10~20wt%) and deionized water (60
~80wt%) hafnium colloidal sol is prepared, then adjusting collosol PH value with ammonium hydroxide is 2~3, is taken after the ageing a few days is stable 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 -6% moles yttrium powder of hafnium oxide powder and zirconium oxide
(gross mass account for colloidal sol quality 10~40%) 9:1 in mass ratio 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 -6% moles yttrium powder of zirconium oxide
10~40%) 8:2 in mass ratio is added in colloidal sol, repeat immersion-pull-out-drying steps and third layer be made；Successively class
It pushes away, the Wolfram rhenium heat electric couple antioxidant coating that eleventh floor has component gradient is made.
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 is first heated to 400 DEG C to gas pressurized to 15MPa with the heating rate of 5 DEG C/min, keeps the temperature 1 hour, is pre-sintered；Again
1350 DEG C are heated to the heating rate of 4 DEG C/min, keeps the temperature 2 hours, carries out HIP sintering；Then with the drop of 3 DEG C/min
Warm rate 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.
Fig. 4 is coating through 2500 DEG C of SEM photographs after oxy-acetylene flame ablation 35 minutes.As seen from the figure, coating surface is through length
Time thermal-flame washes away and successively removes, cracks, but WRe thermocouple matrix form remains intact substantially.
Table 1 list Examples 1 to 3 Wolfram rhenium heat electric couple antioxidant coating carry out densification before and after coating layer thickness and
The variation of oxytolerant ablation time.
1 Examples 1 to 3 Wolfram rhenium heat electric couple antioxidant coating of table carries out variation before and after densification
As it can be seen from table 1 the antioxidant coating thickness after isostatic pressing reduces 40% or more, illustrate that coating causes
Degree of densification greatly increases, and wherein oxygen barrier layers structure of the Wolfram rhenium heat electric couple antioxidant coating with eleventh floor in embodiment 3, is adopted
After hip treatment, the oxytolerant ablation time was up to 35 minutes or more；And the antioxidant coating in most thin embodiment 2
Can 2300 DEG C oxytolerant ablation 10 minutes or more.
Each raw material cited by the present invention can realize that the bound value of the present invention and 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, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (8)
1. a kind of densifying method of the Wolfram rhenium heat electric couple antioxidant coating suitable for 2000 DEG C or more aerobic environments, feature exist
In the Wolfram rhenium heat electric couple antioxidant coating is attached to the Wolfram rhenium heat electric couple matrix surface, and the antioxidant coating included
Layer and the oxygen barrier layers positioned at the transition layer surface are crossed, the thermal expansion coefficient of the buffer layer material is between the W-Re warm
Between the material that galvanic couple basis material and the oxygen barrier layers are selected；The densifying method is that the Wolfram rhenium heat electric couple is anti-oxidant
Coating carries out equal static pressure and heat treatment；
The material that the transition zone is selected is selected from titanium nitride, tungsten carbide, tantalum, tantalum carbide, tungsten silicide or magnesia；The transition zone
For 10~100 microns of film layer；
The oxygen barrier layers are multilayered structure not less than 2 layers, and layers of material thermal expansion coefficient is to separate in the oxygen barrier layers
The direction of the Wolfram rhenium heat electric couple matrix is gradually increased, and the oxytolerant ablation ability of layers of material is to far from institute in the oxygen barrier layers
The direction for stating Wolfram rhenium heat electric couple matrix is also gradually increased；
The material that the oxygen barrier layers are selected is the refractory metal that can play the role of oxygen blocking or oxytolerant ablation at 2000 DEG C or more
Oxide, boride or nitride；
The Wolfram rhenium heat electric couple antioxidant coating carry out isostatic pressing the thickness of the antioxidant coating is directly reduced 40~
50%, the densification degree of antioxidant coating is increased, in conjunction with heat treatment, annealing process answers remnants in antioxidant coating
Power is eliminated, and sintering process increases granular size in antioxidant coating；The densifying method significantly enhances the antioxidant coating
Oxytolerant ablation ability and stability so that the coating can continue working 30 minutes or more at 2000~2500 DEG C.
2. densifying method as described in claim 1, which is characterized in that carry out 20 to the Wolfram rhenium heat electric couple antioxidant coating
~100MPa isostatic pressing 10~30 minutes carries out 1~3 at 750 DEG C~1050 DEG C then under inert gas shielding atmosphere
The isothermal holding of hour, takes out after being cooled to room temperature, completes annealing process.
3. densifying method as claimed in claim 2, which is characterized in that heating rate is 3~6 DEG C/min.
4. densifying method as described in claim 1, which is characterized in that carry out 20 to the Wolfram rhenium heat electric couple antioxidant coating
~100MPa isostatic pressing 10~30 minutes carries out 1~3 at 1400~1600 DEG C then under inert gas shielding atmosphere
The isothermal holding of hour carries out non-pressure sintering technology.
5. densifying method as claimed in claim 4, which is characterized in that the non-pressure sintering technology includes following sub-step:
(1) 400~600 DEG C are heated to the heating rate of 3~6 DEG C/min, keep the temperature 1~3 hour, is pre-sintered；
(2) 1400~1600 DEG C are heated to the heating rate of 2~4 DEG C/min, keep the temperature 1~3 hour, is sintered；
(3) 300~500 DEG C are cooled to the rate of temperature fall of 2~4 DEG C/min；
(4) it is taken out after sample is naturally cooling to room temperature.
6. densifying method as described in claim 1, which is characterized in that under inert gas shielding atmosphere, pressure 10~
20MPa, 1250~1450 DEG C of the temperature isothermal holdings to Wolfram rhenium heat electric couple antioxidant coating progress 1~3 hour, after pressure release
Sample is taken out, HIP sintering technique is carried out.
7. densifying method as claimed in claim 6, which is characterized 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 are heated to the heating rate of 4~7 DEG C/min, keep the temperature 1~2 hour, is pre-sintered；
(2) 1250~1450 DEG C are heated to the heating rate of 3~4 DEG C/min, keep the temperature 1~3 hour, carry out hot isostatic pressing burning
Knot；
(3) 300~500 DEG C are cooled to the rate of temperature fall of 3~4 DEG C/min；
(4) it is taken out after sample is naturally cooling to room temperature.
8. densifying method as described in claim 1, which is characterized in that the oxygen barrier layers overall thickness is not more than 200 microns.
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| 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 |
| CN108048839B (en) * | 2017-12-07 | 2019-04-12 | 华中科技大学 | A kind of Wolfram rhenium heat electric couple high-temperature oxidation resistant coating and its application |
| CN109666894B (en) * | 2019-02-27 | 2021-02-09 | 西安方科新材料科技有限公司 | Silver 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 |
| 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 |
| CN114293179B (en) * | 2021-12-08 | 2024-02-06 | 重庆材料研究院有限公司 | Preparation method of hafnium oxide coating for noble metal thermocouple |
| CN114478004B (en) * | 2021-12-31 | 2023-04-07 | 重庆材料研究院有限公司 | Preparation method of hafnium oxide ceramic product |
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| 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 |
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| 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 |
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