CN111534799B - Oxidation-resistant and heat-insulating ceramic coating and preparation method thereof - Google Patents

Oxidation-resistant and heat-insulating ceramic coating and preparation method thereof Download PDF

Info

Publication number
CN111534799B
CN111534799B CN202010473779.4A CN202010473779A CN111534799B CN 111534799 B CN111534799 B CN 111534799B CN 202010473779 A CN202010473779 A CN 202010473779A CN 111534799 B CN111534799 B CN 111534799B
Authority
CN
China
Prior art keywords
coating
workpiece
target
oxidation
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010473779.4A
Other languages
Chinese (zh)
Other versions
CN111534799A (en
Inventor
鲜广
赵海波
鲜丽君
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan University
Original Assignee
Sichuan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan University filed Critical Sichuan University
Priority to CN202010473779.4A priority Critical patent/CN111534799B/en
Publication of CN111534799A publication Critical patent/CN111534799A/en
Application granted granted Critical
Publication of CN111534799B publication Critical patent/CN111534799B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention discloses an anti-oxidation and heat-insulation ceramic coating and a preparation method thereof, belonging to the technical field of surface engineering. The ceramic coating consists of Al-Cr-O surface layer and Cr/Cr2O3The transition layer and the alloy bonding layer are formed; sequentially depositing an alloy bonding layer and Cr/Cr by an arc ion plating process2O3A transition layer and an Al-Cr-O surface layer. The oxidation-resistant and heat-insulating ceramic coating disclosed by the invention is firmly combined with high-temperature alloy and steel workpieces, compact in structure, thin in thickness, simple in preparation process, high in efficiency, easy to implement and good in application prospect in the aspect of high-temperature protection, and has excellent oxidation resistance and heat-insulating property.

Description

Oxidation-resistant and heat-insulating ceramic coating and preparation method thereof
Technical Field
The invention belongs to the technical field of surface engineering, and particularly relates to an antioxidant and heat-insulating ceramic coating and a preparation method thereof.
Background
The oxidation failure is one of the key problems of the service mechanical parts under the high-temperature working condition, and even if the hot end parts are made of high-temperature alloy, the application temperature range has larger limitation. The production of Thermal Barrier Coatings (TBCs) on superalloy surfaces is one of the current effective means to continue to increase the service temperature of superalloys. The thermal barrier coating generally comprises a MCrAlY (M = Ni, Co or Ni-Co) bond coat and a ceramic topcoat. The bonding layer serves to adjust the difference in thermal expansion coefficient between the high gold alloy substrate and the ceramic top layer and to resist oxidation. The ceramic facing is typically yttria stabilized zirconia, which serves as a high temperature shield.
The most common methods for producing thermal barrier coatings are both plasma spray coating (APS) and electron beam physical vapor deposition (EB-PVD). The plasma spraying method has the advantages of simple equipment, high coating preparation speed, high deposition efficiency, low surface roughness of the formed coating, lamellar microstructure, high porosity, a large amount of microcracks and the like, and the defects cause high-temperature oxidation of the coating and reduce the bonding strength of the coating and a matrix. Compared with a plasma spraying method, the coating prepared by the electron beam physical vapor deposition method is more compact and has better oxidation resistance and hot corrosion resistance. However, the microstructure of the prepared coating is columnar crystal, so that the thermal conductivity of the coating is higher than that of the coating prepared by plasma spraying, the electron beam physical vapor deposition process is difficult to control the components of the material, the utilization rate of the raw material is low, and the cost for preparing the coating is higher. From the viewpoint of coating material, the thicker the coating, the stronger the high temperature protection effect of the coating, and the thickness of the MCrAlY bonding layer and the ceramic top layer in the prior art is generally more than 100 μm. However, the thicker the coating, the correspondingly greater the stress generated at the interface of the ceramic layer and the TGO thermally grown layer, and the stress build-up causes the coating to flake off, thereby rendering the thermal barrier coating fail protective. Therefore, the design and development of new high-temperature protective coatings become an important direction for the development of the current high-temperature protection technology.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and firstly provides an oxidation-resistant and heat-insulating ceramic coating.
It is another object of the present invention to provide a method for preparing the above oxidation-resistant and heat-insulating ceramic coating.
In order to achieve the first purpose, the invention provides an oxidation-resistant and heat-insulating ceramic coating which is composed of an Al-Cr-O surface layer and Cr/Cr2O3The transition layer and the alloy bonding layer are formed, the chemical components of the Al-Cr-O surface layer are Al, Cr and O, the atomic percentage of Al/Cr is more than 1, the coating structure is a non-directional compact amorphous structure, and the thickness of the coating is 0.5-10 mu m.
Wherein, in the ceramic coating, Cr/Cr2O3The thickness of the transition layer is 50-100 nm, Cr is connected with the alloy bonding layer, and Cr is connected with the Al-Cr-O surface layer2O3。
Wherein, in the ceramic coating, the alloy bonding layer is M a b c d1----Cr a Al b Si c Y d Wherein M is one or more of Ni, Co and Fe, and is not less than 0.2a≤0.4，0.05≤b≤0.15，c≤0.05，dLess than or equal to 0.02, and the thickness of the alloy bonding layer is 5-20 mu m.
The invention provides a method for preparing the oxidation-resistant and heat-insulating ceramic coating, which comprises the following steps:
A. pre-treating a workpiece before coating;
B. depositing an alloy bonding layer by adopting an arc ion plating process;
C. deposition of Cr/Cr2O3A transition layer;
D. depositing an Al-Cr-O surface layer.
Wherein, the pretreatment of the workpiece before the film coating in the step A in the method is to clean the workpieceAfter the workpiece to be plated is loaded into the film plating chamber, the vacuum-pumping system is started to vacuumize the film plating chamber, and when the back bottom vacuum reaches 3.5 multiplied by 10-3When the pressure is lower than Pa, introducing argon into the coating chamber, heating the workpiece by using the bombardment heat effect of the electron beam and an auxiliary heating device, wherein the vacuum pressure is 0.1-1 Pa, the workpiece rotates along with the workpiece frame in the coating chamber at the rotation speed of 1-4 rpm until the workpiece is heated to 350-450 ℃; then introducing hydrogen into the film coating chamber, adjusting the flow of the argon, controlling the vacuum pressure to be 0.2-0.5 Pa, applying a bias voltage of-300 to-800V to the workpiece, and utilizing Ar+And H+And (3) etching the workpiece to remove surface adsorption and pollution for 30-90 min.
Wherein, the step B of depositing the alloy bonding layer by adopting the arc ion plating process in the method refers to adjusting the flow of argon to ensure that the indoor pressure is 2-10 Pa, and opening M a b c d1----Cr a Al b Si c Y d Arc target power supply, M a b c d1----Cr a Al b Si c Y d The atomic percentage of the target satisfies: 0.2-0.2 ≤a≤0.4，0.05≤b≤0.15，c≤0.05，dLess than or equal to 0.02, M is one or more of Ni, Co and Fe, arc current is set to be 80-120A, workpiece bias voltage is adjusted to be-200-600V, and total coating time is 4-20 h.
Wherein, the step C of the method deposits Cr/Cr2O3The transition layer is used for adjusting the flow of argon gas, controlling the pressure to be 0.1-5 Pa and enabling the working arc target to be driven to move from M a b c d1----Cr a Al b Si c Y d Switching the target to a Cr target, adjusting the current of the Cr target to be 70-120A, adjusting the bias voltage of the workpiece to be-50 to-200V, and depositing for 5-10 min; and then introducing oxygen into the coating chamber, slowly increasing the oxygen flow, and increasing the oxygen flow to 0.5-1 time of argon flow within the time range of 2-5 min.
Wherein, the step D of depositing the Al-Cr-O ceramic coating in the method refers to switching the working arc target from a Cr target to Al x Cr x1-Target (A)x0.6 to 0.98) of Al x Cr x1-The target current is 70-120A, the workpiece bias voltage is-50 to-150V, and the film coating is finished after the deposition is continued for 0.5-12 h.
In the above method, the step A, B, C, D may be performed sequentially (one-step deposition method), or the plating may be finished after the steps a and B are performed sequentially, and then the step A, C, D is performed sequentially, that is, the plating is performed sequentially according to A, B, A, C, D (two-step deposition method).
Compared with the prior art, the invention has the following advantages:
1) the oxidation-resistant and heat-insulating ceramic coating provided by the invention is composed of an Al-Cr-O surface layer and Cr/Cr2O3The transition layer and the alloy bonding layer form a whole. The Al-Cr-O surface layer has compact structure, excellent antioxidation and heat insulation effects, and the compact structure can also prevent oxygen from rapidly entering the coating, thereby greatly reducing the growth rate of TGO; a small amount of Cr element is beneficial to promoting amorphous alumina to be converted into an alpha-type crystal structure with a compact structure under a high-temperature condition, and the Cr element can also increase the phase structure stability of the alumina. Cr/Cr2O3The transition layer skillfully realizes the organic transition from the alloy bonding layer to the ceramic surface layer, relieves the interface mutation of metal/ceramic, and Cr2O3The template can be used for inducing the surface layer alumina to grow according to an alpha type crystal structure. The alloy bonding layer effectively improves the bonding condition between the ceramic surface layer and the high-temperature alloy and steel workpiece, the bonding grade between the coating and the workpiece reaches HF1, the Si and Y elements in the alloy bonding layer have synergistic effect, so that the alloy bonding layer has good oxidation resistance, the strength of the alloy bonding layer is improved, the alloy bonding layer obtained through interstitial deposition has the characteristic of short columnar crystals, and the pores in the structure enable the coating to have larger strain tolerance and heat insulation effect. Therefore, the oxidation-resistant and heat-insulating ceramic coating provided by the invention can realize good protection on a substrate material within 30 mu m of the total thickness, and the thickness is far lower than the use thickness of a thermal barrier coating.
2) The preparation method of the oxidation-resistant and heat-insulating ceramic coating provided by the invention is different from the conventional method adopted by a thermal barrier coating, and the combination of a compact oxide ceramic surface layer and a columnar structure alloy bonding layer is realized by using an arc ion plating method and different deposition processes, so that the ceramic layer prepared by a plasma spraying method is prevented from being in a layered structure containing a plurality of transverse cracks, and the ceramic layer prepared by an electron beam physical vapor deposition method is prevented from being in a penetrating columnar shape. The arc ion plating process has good controllability, and the prepared ceramic layer is a non-directional compact structure without cracks and gaps in the structure and has a barrier effect on inward diffusion of oxygen atoms. In addition, the alloy bonding layer prepared by the arc ion plating process has controllable transverse and longitudinal gaps, so that the strain tolerance and the heat insulation effect of the coating are increased, the process for preparing the alloy bonding layer with complex components by the arc ion plating process is more flexible, and the controllability of the components is better.
Drawings
Fig. 1 is a cross-sectional texture of the oxidation-resistant and heat-insulating ceramic coating prepared in example 1 of the present invention, the left image is 2000 times magnified, the scale is 10 μm, the right image is 5000 times magnified, and the scale is 5 μm.
FIG. 2 is a graph showing the elemental composition and content of the oxidation-resistant and heat-insulating ceramic coating top layer prepared in example 1 of the present invention.
Fig. 3 is a graph showing the elemental composition and content of the oxidation-resistant and heat-insulating ceramic coating alloy adhesion layer prepared in example 1 of the present invention.
Fig. 4 is an X-ray diffraction pattern of the oxidation-resistant and heat-insulating ceramic coating prepared in example 1 of the present invention before oxidation treatment.
FIG. 5 is a graph showing the change in appearance of the ceramic coating for oxidation resistance and thermal insulation prepared in example 1 of the present invention after being oxidized for 10 hours under the condition of 1100 ℃ in static air.
FIG. 6 is the change in appearance of K418 superalloy without any coating protection after oxidation for 10 hours in static air at 1100 ℃.
FIG. 7 is an X-ray diffraction pattern of the oxidation-resistant and thermal-insulating ceramic coating prepared in example 1 of the present invention after being oxidized for 10 hours under the condition of 1100 ℃ in static air.
Fig. 8 is a graph showing the results of a thermal insulation performance test of the oxidation-resistant and thermal-insulating ceramic coating prepared in example 1 of the present invention at 1100 ℃.
Detailed Description
The present invention is further illustrated by the following specific examples, but the present invention is not limited to the following examples, and any non-inventive modifications made by those skilled in the art based on the present invention are within the scope of the present invention.
It should be noted that the cross-sectional structure morphology of the oxidation-resistant and heat-insulating ceramic coating provided in the following examples was observed by using a scanning electron microscope of hitachi model S4800, and the elemental composition and content of the coating were detected by an X-ray energy spectrometer attached thereto; detecting the phase composition of the coating before and after oxidation by adopting a D8 advanced X-ray diffractometer of Bruker company; the static air oxidation experiment is completed in an SX2-10-12 box type resistance furnace, and the appearance after oxidation is photographed by a mobile phone; the test for the thermal insulation performance was carried out in a self-made apparatus using an SX2-10-12 box-type resistance furnace, a K-type thermocouple and an AT4508 multichannel temperature recorder, and the data of the test results were obtained by Origin mapping.
Example 1
After the cleaned K418 high-temperature alloy workpiece is loaded into the coating chamber, the vacuum-pumping system is started to vacuumize the coating chamber, and when the back bottom vacuum reaches 3.5 multiplied by 10-3When the pressure is lower than Pa, introducing argon into the coating chamber, heating the workpiece by using the bombardment heat effect of the electron beam and an auxiliary heating device, wherein the vacuum pressure is 0.2Pa, the workpiece rotates in the coating chamber at the rotation speed of 1rpm until the workpiece is heated to 400 ℃; introducing hydrogen into the coating chamber, adjusting the flow of the argon, controlling the vacuum pressure to be 0.2Pa, applying a bias voltage of-600V to the workpiece, and applying Ar+And H+And etching the workpiece to remove surface adsorption and pollution for 70 min. Adjusting the flow of argon gas to make the pressure in the chamber 9Pa, and opening Ni0.47Cr0.35Al0.15Si0.02Y0.01Setting arc current of 100A for an arc target power supply, adjusting workpiece bias voltage to-400V, total coating time to 16h, and finishing coating. Starting the vacuum-pumping system again to vacuumize the film coating chamber until the back bottom vacuum reaches 3.5 multiplied by 10-3When the pressure is lower than Pa, introducing argon into the coating chamber, heating the workpiece by using the bombardment heat effect of the electron beam and an auxiliary heating device, wherein the vacuum pressure is 0.2Pa, the workpiece rotates in the coating chamber at the rotation speed of 1rpm until the workpiece is heated to 400 ℃; introducing hydrogen into the coating chamber, adjusting the flow of the argon, controlling the vacuum pressure to be 0.2Pa, applying a bias voltage of-600V to the workpiece, and applying Ar+And H+And etching the workpiece to remove surface adsorption and pollution for 70 min. Regulating argon flow, controlling pressure to be 2Pa, and making working arc target from Ni0.47Cr0.35Al0.15Si0.02Y0.01Switching the target to a Cr target, adjusting the current of the Cr target to be 90A, adjusting the bias voltage of the workpiece to be-90V, and depositing for 5 min; and then introducing oxygen into the coating chamber, slowly increasing the oxygen flow, and increasing the oxygen flow to 0.6 time of argon flow within the time range of 2 min. Switching the working arc target from Cr target to Al0.95Cr0.05Target, Al0.95Cr0.05The target current is 100A, the workpiece bias voltage is-60V, and the film coating is finished after the deposition is continued for 1 h. The total thickness of the obtained ceramic coating is about 22.7 mu m, the thickness of the bonding layer is 22 mu m, and the thickness of the Al-Cr-O ceramic surface layer is 0.7 mu m. The bonding layer is a short column-shaped structure, and a gap is formed in the tissue; the ceramic surface layer is a non-directional compact amorphous structure. The ratio of the total atomic percent of metallic atoms Al and Cr to the atomic percent of O is about 2: 3, the atomic percentage ratio of Al to Cr is more than 3. The coating is still complete after being oxidized for 10 hours at 1100 ℃, has no peeling, and plays a good role in protecting workpiece materials. The heat insulation of the coating reaches more than 43.6 ℃ after heat preservation for one hour at 1100 ℃.
Example 2
After the cleaned K418 high-temperature alloy workpiece is loaded into the coating chamber, the vacuum-pumping system is started to vacuumize the coating chamber, and when the back bottom vacuum reaches 3.5 multiplied by 10-3When the pressure is lower than Pa, introducing argon into the coating chamber, heating the workpiece by using the bombardment heat effect of the electron beam and the auxiliary heating device, wherein the vacuum pressure is 0.5Pa, the workpiece rotates in the coating chamber at the rotation speed of 2rpm until the workpiece is heated to the temperature of 2rpm400 ℃; introducing hydrogen into the coating chamber, adjusting the flow of the argon, controlling the vacuum pressure to be 0.35Pa, applying a bias voltage of-600V to the workpiece, and applying Ar+And H+And etching the workpiece to remove surface adsorption and pollution for 60 min. Adjusting the flow of argon gas to make the pressure in the chamber 5Pa, and opening Ni0.40Co0.20Cr0.28Al0.10Si0.01Y0.01An arc target power supply sets arc current of 100A, adjusts the bias voltage of a workpiece to-400V, and the total coating time is 16 h. Regulating argon flow, controlling pressure to be 2Pa, and making working arc target from Ni0.40Co0.20Cr0.28Al0.10Si0.01Y0.01Switching the target to a Cr target, adjusting the current of the Cr target to be 90A, adjusting the bias voltage of the workpiece to be-90V, and depositing for 5 min; and then introducing oxygen into the coating chamber, slowly increasing the oxygen flow, and increasing the oxygen flow to 0.6 time of argon flow within the time range of 2 min. Switching the working arc target from Cr target to Al0.95Cr0.05Target, Al0.95Cr0.05The target current is 100A, the workpiece bias voltage is-60V, and the film coating is finished after the deposition is continued for 1 h. The total thickness of the obtained oxidation-resistant and heat-insulating ceramic coating is about 22.8 mu m, the thickness of the bonding layer is 22 mu m, and the thickness of the Al-Cr-O ceramic surface layer is 0.8 mu m. The bonding layer is a short column-shaped structure, and a gap is formed in the tissue; the ceramic surface layer is a non-directional compact amorphous structure. The ratio of the total atomic percent of metallic atoms Al and Cr to the atomic percent of O is about 2: 3, the atomic percentage ratio of Al to Cr is more than 3. The coating is still complete after being oxidized for 10 hours at 1100 ℃, has no peeling, and plays a good role in protecting workpiece materials. The heat insulation of the coating reaches more than 42.3 ℃ after heat preservation for one hour at 850 ℃.
Example 3
After the cleaned 304 stainless steel workpiece is loaded into the coating chamber, the vacuum-pumping system is started to vacuumize the coating chamber, and when the back bottom vacuum reaches 3.5 multiplied by 10-3When the pressure is lower than Pa, introducing argon into the coating chamber, heating the workpiece by using the bombardment heat effect of the electron beam and an auxiliary heating device, wherein the vacuum pressure is 0.5Pa, the workpiece rotates in the coating chamber at the rotation speed of 2rpm until the workpiece is heated to 350 ℃; then communicated with the coating chamberIntroducing hydrogen, adjusting argon flow, controlling vacuum pressure to be 0.5Pa, applying-600V bias voltage to the workpiece, and utilizing Ar+And H+And etching the workpiece to remove surface adsorption and pollution for 90 min. Adjusting the flow of argon gas to make the pressure in the chamber 5Pa, and opening Fe0.40Ni0.15Cr0.3Al0.15Si0.04Y0.01An arc target power supply sets arc current of 100A, adjusts the bias voltage of a workpiece to-400V, and the total coating time is 4 h. Adjusting the flow of argon gas, controlling the pressure to be 2Pa, and making the working arc target be Fe0.40Ni0.15Cr0.3Al0.15Si0.04Y0.01Switching the target to a Cr target, adjusting the current of the Cr target to be 100A, adjusting the bias voltage of the workpiece to be-90V, and depositing for 10 min; and then introducing oxygen into the coating chamber, slowly increasing the oxygen flow, and increasing the oxygen flow to 0.5 time of argon flow within the time range of 5 min. Switching the working arc target from Cr target to Al0.67Cr0.33Target, Al0.67Cr0.33The target current is 120A, the workpiece bias voltage is-60V, and the film coating is finished after the deposition is continued for 1 h. The total thickness of the obtained oxidation-resistant and heat-insulating ceramic coating is about 6.8 mu m, the thickness of the bonding layer is 6 mu m, and the thickness of the Al-Cr-O ceramic surface layer is 0.8 mu m. The bonding layer is a short column-shaped structure, and a gap is formed in the tissue; the ceramic surface layer is a non-directional compact amorphous structure. The ratio of the total atomic percent of metallic atoms Al and Cr to the atomic percent of O is about 2: 3, the atomic percentage ratio of Al to Cr is more than 3. The coating is still complete after being oxidized for 10 hours at 1100 ℃, has no peeling, and plays a good role in protecting workpiece materials. The heat insulation of the coating reaches more than 40.7 ℃ after heat preservation for one hour at 850 ℃.
In order to examine the structure and performance of the obtained oxidation-resistant and heat-insulating ceramic coating of the above examples, the present invention examined it as follows:
1) coating microstructure
The fracture morphology of the coating obtained in example 1 of the present invention was observed using a S4800 scanning electron microscope, and the results are shown in fig. 1. As can be seen, the oxidation-resistant and heat-insulating ceramic coating is approximately two-layer, and the detection surface is detected by using a spectrum device attached to a scanning electron microscopeThe composition of the layer is three elements of Al, Cr, O (see fig. 2), and the ratio of the metal to non-metal atom contents is about 2: 3, therefore, the surface layer is determined to be (Al, Cr)2O3(ii) a The compositions of the inner layer are detected to be five elements of Ni, Cr, Al, Si and Y (see figure 3), which is consistent with the designed composition of the alloy bonding layer. It is observed that a very thin thickness of the transition layer structure is also present between the two layers. Most notably, the oxide ceramic top layer has a thickness of 0.7 μm and is a non-directional dense structure, which is typically an amorphous structure. The phase structure of the coating was examined by X-ray diffractometer and the results are shown in FIG. 4, with the diffraction peak being Ni3The Al phase is main and is accompanied by a small amount of NiAl phase, the two phases are derived from the alloy bonding layer, and no diffraction peak of oxide appears in the diffraction peak, which confirms that the oxide ceramic surface layer exists in an amorphous state. This structure has no grain boundary and no void as between columnar crystals, and thus prevents oxygen atoms from diffusing by short circuit via the interface and void. Because oxygen atoms are difficult to enter the coating, the time for the alloy bonding layer to be oxidized is delayed, and the service life of the coating is prolonged.
2) High-temperature oxidation resistance and heat insulation performance of coating
After the coated superalloy workpiece obtained in example 1 of the present invention was put into a box-type resistance furnace and subjected to oxidation treatment for 10 hours, the appearance of the workpiece was photographed and recorded, and compared with the appearance before oxidation, as shown in fig. 5, it can be seen from the figure that the coated workpiece was still intact, no crack was present on the surface of the workpiece, no peeling of the coating occurred, and it was confirmed that the coating had a good high temperature protection effect. For comparison, the superalloy workpieces not protected by the coating of the present invention were also placed in a box-type resistance furnace for oxidation treatment for 10 hours, and the appearance of the workpieces was also recorded by photographing and compared with the appearance before oxidation, as shown in fig. 6, the surface of the superalloy workpiece before oxidation showed metallic luster, the surface of the superalloy workpiece after oxidation completely lost metallic luster, and the surface was entirely blackened, i.e., a large amount of black scale was formed on the surface of the workpiece, and a portion of the scale was peeled off because the scale had grownThicker, stress buildup causes it to flake off. It can be seen that the workpieces which are not coated with the coating of the present invention cannot withstand high temperature corrosion of 1100 ℃ at all. The phase structure of the coated superalloy workpiece obtained in example 1 of the present invention after being oxidized for 10 hours was examined by an X-ray diffractometer, and the results are shown in fig. 7, in which a large amount of Ni is still present in the diffraction peak3Al phase, which shows that the structure of the alloy bonding layer is not obviously changed; in addition, the diffraction peak shows lower intensity of alpha- (Al, Cr)2O3And alpha-Al2O3The peak positions of the two phases are very close and difficult to distinguish, which shows that the surface layer structure of the oxide ceramic in the amorphous state is partially crystallized and transformed into alpha- (Al, Cr)2O3And alpha-Al2O3Because the alpha-structure alumina and the alumina chromium are the most compact, the protective effect is still good. The heat insulation performance test of the high-temperature alloy workpiece with the coating obtained in the embodiment 1 of the invention is carried out, and the result is shown in fig. 8, and the temperature difference between the surface of the workpiece and the temperature in the hole of the workpiece is more than 40 ℃ in the heat insulation process under the 1100 ℃ condition, which indicates that the coating plays a good heat insulation role.

Claims (3)

1. An oxidation-resistant and thermal-insulating ceramic coating, characterized by: with Al-Cr-O surface layer, Cr/Cr2O3The transition layer and the alloy bonding layer are formed, the chemical components of the Al-Cr-O surface layer comprise three elements of Al, Cr and O, the atomic percent of Al/Cr is more than 1, the surface layer structure is a non-directional compact amorphous structure, and the thickness of the surface layer is 0.5-10 mu m; Cr/Cr2O3The thickness of the transition layer is 50-100 nm, Cr is connected with the alloy bonding layer, and Cr is connected with the Al-Cr-O surface layer2O3(ii) a The alloy bonding layer is M a b c1---- d Cr a Al b Si c Y d Wherein M is one or more of Ni, Co and Fe, and is not less than 0.2a≤0.4，0.05≤b≤0.15，c≤0.05，dLess than or equal to 0.02, and the thickness of the alloy bonding layer is 5-20 mu m.
2. A method of preparing the oxidation-resistant and thermal-insulating ceramic coating of claim 1, characterized by the steps of:
A. pre-treating the workpiece before coating, loading the cleaned workpiece to be coated into a coating chamber, starting a vacuum-pumping system to vacuumize the coating chamber until the vacuum of the back bottom reaches 3.5 multiplied by 10-3When the pressure is lower than Pa, introducing argon into the coating chamber, heating the workpiece by using the bombardment heat effect of the electron beam and an auxiliary heating device, wherein the vacuum pressure is 0.1-1 Pa, the workpiece rotates along with the workpiece frame in the coating chamber at the rotation speed of 1-4 rpm until the workpiece is heated to 350-450 ℃; then introducing hydrogen into the film coating chamber, adjusting the flow of the argon, controlling the vacuum pressure to be 0.2-0.5 Pa, applying a bias voltage of-300 to-800V to the workpiece, and utilizing Ar+And H+Etching the workpiece to remove surface adsorption and pollution for 30-90 min;
B. depositing an alloy bonding layer by adopting an arc ion plating process, adjusting the flow of argon gas to ensure that the indoor pressure is 2-10 Pa, and opening M a b c d1----Cr a Al b Si c Y d Arc target power supply, M a b c d1----Cr a Al b Si c Y d The atomic percentage of the target satisfies: 0.2-0.2 ≤a≤0.4，0.05≤b≤0.15，c≤0.05，dLess than or equal to 0.02, M is one or more of Ni, Co and Fe, arc current is set to be 80-120A, workpiece bias voltage is adjusted to be-200-600V, and total coating time is 4-20 h;
C. deposition of Cr/Cr2O3A transition layer for adjusting the flow of argon gas, controlling the pressure to be 0.1-5 Pa and controlling the working arc target to be M a b c d1----Cr a Al b Si c Y d Switching the target to a Cr target, adjusting the current of the Cr target to be 70-120A, adjusting the bias voltage of the workpiece to be-50 to-200V, and depositing for 5-10 min; then introducing oxygen into the coating chamber, slowly increasing the oxygen flow, and increasing the oxygen flow to 0.5-1 time of the argon flow within the time range of 2-5 min;
D. depositing an Al-Cr-O surface layerThe arc target is switched from Cr target to Al x Cr x1-Target, whereinx0.6 to 0.98 of Al x Cr x1-The target current is 70-120A, the workpiece bias voltage is-50 to-150V, and the film coating is finished after the deposition is continued for 0.5-12 h.
3. The method of oxidation-resistant and thermal-insulating ceramic coating of claim 2, characterized in that: the step A, B, C, D can be performed sequentially, or the coating can be finished after the steps a and B are performed sequentially, and then the step A, C, D is performed sequentially, that is, the coating is performed in the order of A, B, A, C, D.
CN202010473779.4A 2020-05-29 2020-05-29 Oxidation-resistant and heat-insulating ceramic coating and preparation method thereof Active CN111534799B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010473779.4A CN111534799B (en) 2020-05-29 2020-05-29 Oxidation-resistant and heat-insulating ceramic coating and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010473779.4A CN111534799B (en) 2020-05-29 2020-05-29 Oxidation-resistant and heat-insulating ceramic coating and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111534799A CN111534799A (en) 2020-08-14
CN111534799B true CN111534799B (en) 2021-11-12

Family

ID=71974118

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010473779.4A Active CN111534799B (en) 2020-05-29 2020-05-29 Oxidation-resistant and heat-insulating ceramic coating and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111534799B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115679263B (en) * 2022-10-11 2023-12-01 中国核动力研究设计院 Corrosion-resistant coating and cladding material for nuclear reactor and preparation method thereof
CN116497330B (en) * 2023-04-28 2024-01-05 华中科技大学 High-strength and high-toughness titanium alloy and magnetron sputtering-based titanium alloy component screening method

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101430004B (en) * 2008-12-12 2010-06-02 武汉大学 PVD chromium based ceramic composite coating piston ring and method for producing the same
EP2363509A1 (en) * 2010-02-28 2011-09-07 Oerlikon Trading AG, Trübbach Synthesis of metal oxides by reactive cathodic arc evaporation
US10001021B2 (en) * 2013-05-23 2018-06-19 Oerlikon Surface Solutions Ag, Pfäffikon Barrier layer for a turbocharger
CN104278234B (en) * 2013-07-02 2017-02-22 中国科学院兰州化学物理研究所 Preparation technology for self-lubricating coating with wide temperature range of room temperature to 800 DEG C
DE102016212874A1 (en) * 2016-07-14 2018-01-18 Oerlikon Surface Solutions Ag, Pfäffikon Protective coating for a thermally stressed structure
CN109082641B (en) * 2018-08-28 2020-05-22 华南理工大学 Three-layer film structure coating and preparation method thereof
CN111074216A (en) * 2018-10-22 2020-04-28 海门市源美美术图案设计有限公司 α - (Al, Cr)2O3Method for producing film

Also Published As

Publication number Publication date
CN111534799A (en) 2020-08-14

Similar Documents

Publication Publication Date Title
Zhang et al. Plasma spray of Ti2AlC MAX phase powders: Effects of process parameters on coatings' properties
CN111424242B (en) CMAS-resistant double-layer structure protective coating, thermal barrier coating multilayer structure and preparation method thereof
CN111534799B (en) Oxidation-resistant and heat-insulating ceramic coating and preparation method thereof
CN108468028B (en) Periodic multilayer structure AlTiYN/AlCrSiN hard coating and preparation method and application thereof
CN112813399B (en) High-entropy metal glass protective coating and preparation method thereof
CN103160773A (en) Method for prolonging service life of engine thermal barrier coating by controlling components of thermal growth oxide layer
Singh et al. Architecture of thermal barrier coatings produced by electron beam-physical vapor deposition (EB-PVD)
CN101845609A (en) Method for preparing diffusion-resistant coating for single-crystal high-temperature alloy
CN110158035B (en) Metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion and preparation method thereof
US20080292873A1 (en) Method for Providing a Thermal Barrier Coating and Substrate Having Such Coating
CN106435489A (en) Preparation method for oxidation resisting self-healing Cr/NiCr coatings on niobium-based surface
CN111378935B (en) Al/NiCrAlY/Al2O3Composite coating, preparation method and application thereof
CN109338303B (en) Amorphous and nanocrystalline composite coating for zirconium alloy protection and preparation method thereof
CN112853288A (en) Fe-Cr-Al-based protective coating with long-time high-temperature steam oxidation resistance and preparation method thereof
CN111020497A (en) Periodic multilayer structure AlTiN/AlCrO coating and preparation method thereof
CN109252137B (en) Preparation method of zirconium alloy surface coating
CN110484883A (en) A kind of synthetic method and application of hard Zr-B-O nano compound film
CN114959584A (en) TaNbTi-based refractory intermediate-entropy amorphous alloy coating and preparation method thereof
CN108070859A (en) Refractory metal surfaces lamellar composite Ir/W high-temperature oxidation resistant coatings and preparation method thereof
CN113174571A (en) Ultra-microcrystalline titanium diboride composite coating and preparation method and application thereof
Peng et al. Oxidation behavior at 1100° C of NiCrAlY coatings deposited by various PVD techniques
CN112553580A (en) Diboride composite coating and preparation method and application thereof
CN110670020B (en) Zirconium-aluminum-nitrogen-aluminum oxide multilayer composite coating firmly combined with metal ceramic and preparation method thereof
CN114717516B (en) Strongly-combined high corrosion-resistant TiAl/Ti2Preparation method of AlC coating
CN109338289A (en) A kind of preparation method of Oxidation Resistant Coatings for Carbon/Carbon Composites

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant