CN116516309A - Single-layer Cr-enriched N-doped coating on surface of zirconium alloy for nuclear and preparation method thereof - Google Patents
Single-layer Cr-enriched N-doped coating on surface of zirconium alloy for nuclear and preparation method thereof Download PDFInfo
- Publication number
- CN116516309A CN116516309A CN202310520440.9A CN202310520440A CN116516309A CN 116516309 A CN116516309 A CN 116516309A CN 202310520440 A CN202310520440 A CN 202310520440A CN 116516309 A CN116516309 A CN 116516309A
- Authority
- CN
- China
- Prior art keywords
- coating
- zirconium alloy
- layer
- enriched
- doped
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 156
- 239000011248 coating agent Substances 0.000 title claims abstract description 150
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 54
- 239000002356 single layer Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 17
- 238000004544 sputter deposition Methods 0.000 claims abstract description 25
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 21
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 18
- 239000000956 alloy Substances 0.000 claims abstract description 18
- 238000005477 sputtering target Methods 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims description 40
- 230000008021 deposition Effects 0.000 claims description 39
- 238000005498 polishing Methods 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 15
- 244000137852 Petrea volubilis Species 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 229910003460 diamond Inorganic materials 0.000 claims description 9
- 239000010432 diamond Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 abstract description 27
- 238000007254 oxidation reaction Methods 0.000 abstract description 27
- 239000013078 crystal Substances 0.000 abstract description 20
- 230000004584 weight gain Effects 0.000 abstract description 11
- 235000019786 weight gain Nutrition 0.000 abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000005253 cladding Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005524 ceramic coating Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003758 nuclear fuel Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 1
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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
-
- 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
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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)
Abstract
A single-layer Cr-enriched N-doped coating on the surface of a zirconium alloy for nuclear, wherein the doping amount of N in the single-layer Cr-enriched N-doped coating is 8-15 at%, specifically, by magnetron sputtering, a Cr target is used as a sputtering target, and N is introduced during sputtering 2 Is prepared. According to the invention, the single-layer Cr-enriched N-doped coating is prepared by magnetron sputtering, so that the mechanical property of the coating is improved, the hardness of the coating is enhanced, and the maximum hardness reaches 25.16Gpa, thereby improving the wear resistance of the coating; the morphology and microstructure of the coating are improved by doping a small amount of N atoms, the grain structure of the coating is a nanocrystalline structure without columnar crystal characteristics, the high-temperature oxidation resistance is effectively improved, and the oxidation weight gain is only 15.63mg/m 2 At the same time, the failure of the coating is slowed down, and in addition, the nanocrystalline structure is favorable for the interface between alloy and coating in the high-temperature steam environmentThe surface forms continuous and compact twin crystals, and effectively blocks the interdiffusion of Zr and Cr.
Description
Technical Field
The invention relates to the technical field of preparation of nuclear fuel cladding zirconium alloy protective coatings, in particular to a single-layer Cr-enriched N-doped zirconium alloy surface coating for a nuclear and a preparation method thereof.
Background
Zirconium alloys have been selected as cladding materials for pressurized water reactors and boiling water reactor fuel pellets and reactor core structural materials since the beginning of the 60 th century because of their excellent combination of properties, and are therefore also referred to as "first metals in the atomic age". However, among other advantages, zirconium alloys currently suffer from a number of drawbacks. The most fatal is that under Loss of coolant Account (LOCA), the service environment of cladding materials in the reactor becomes high-temperature steam with the temperature of up to 1200 ℃. A large amount of hydrogen and heat can be released in the high-temperature steam oxidation process of the zirconium alloy, hydrogen explosion occurs, the process of melting and burning of the reactor core is accelerated, and finally a nuclear leakage accident occurs. Therefore, an Accident-resistant fuel (ATF) concept is provided to solve the safety problem of the zirconium alloy cladding-uranium dioxide fuel pellet system of the existing water-cooled reactor.
The ATF material design which is most likely to realize industrial application at first can not only improve the strength and oxidation resistance of the ATF material by performing element proportioning regulation based on the current commercial zirconium alloy, but also improve the performance of the coated zirconium alloy by a surface modification method. The method can not only greatly improve the oxidation resistance of the zirconium alloy in high-temperature steam, but also effectively solve the problem of cladding failure caused by fretting wear under normal operation working conditions, and can greatly improve the safety of a reactor.
The surface modification of zirconium alloy is mainly two types of metal coating and ceramic coating. The metal coating mainly comprises pure Cr, crAl, feCrAl and the like, and the ceramic coating mainly comprises a MAX phase coating, an oxide coating, a nitride coating, a carbide coating and the like. The CrN coating in the ceramic coating has a mature preparation process and abundant industrialized experience, the coating structure is good after oxidation in air at 1160 ℃, and the oxidation weight gain of the surface coating zirconium alloy after oxidation is reduced by about 97.7 percent relative to that of an uncoated zirconium alloy, which shows that the CrN coating also has excellent oxidation resistance and potential as an ATF material. However, the nitrogen diffusion and release behavior of CrN coatings during decomposition and oxidation at high temperatures can affect the structural integrity of the coating, affecting the oxidation behavior and long-term stability of the coating.
Disclosure of Invention
The invention aims to provide a single-layer Cr-enriched N-doped coating on the surface of a zirconium alloy for nuclear use.
The invention also aims to provide a preparation method of the monolayer Cr-rich N-doped coating on the surface of the zirconium alloy for the nuclear. A small amount of N-doped Cr-rich single-layer coating is prepared by magnetron sputtering, so that the high-temperature oxidation resistance of the coating is effectively improved, and the purpose of inhibiting the failure of the coating is achieved.
The invention aims at realizing the following technical scheme:
a single-layer Cr-enriched N-doped coating on the surface of a zirconium alloy for nuclear use is characterized in that the doping amount of N in the single-layer Cr-enriched N-doped coating is 8-15 at%, specifically, a Cr target is used as a sputtering target by magnetron sputtering, and N is introduced during sputtering 2 Is prepared.
Further, the substrate bias voltage of the magnetron sputtering is-5 to-20V, the deposition air pressure is 0.3 to 0.6Pa, and the deposition time is 8 to 12 hours.
Further, the driving power of the Cr target is a direct current power, and the sputtering power is 300W and N 2 The amount of the mixture to be introduced is 3-10 sccm.
Preferably, the substrate bias of the magnetron sputtering is-10V, and the deposition air pressure is 0.4Pa.
A preparation method of a single-layer Cr-enriched N-doped coating on the surface of a zirconium alloy for a core is characterized by comprising the following steps: specifically, a Cr target is used as a sputtering target, and N is introduced at the same time 2 And (3) performing magnetron sputtering, wherein the base bias voltage of the magnetron sputtering is-5 to-20V.
Further, in the magnetron sputtering process, the deposition air pressure is 0.3-0.6 Pa, and the deposition time is 8-12 h.
Further, the driving power of the Cr target is a DC power supply, and the sputtering power is 300W.
Further, the N is 2 The amount of the mixture to be introduced is 3-10 sccm.
The technical difficulties faced in preparing the Cr coating by adopting the magnetron sputtering are that the magnetron sputtering coating grows in situ due to the short deposition time and the short atomic diffusion distance, so that columnar crystal structures exist in the coating, defects and cracks of the coating are increased due to the existence of the columnar crystal structures, the compactness is reduced, and the oxidation resistance is correspondingly reduced. Generally, the field will enhance the compactness of the coating by increasing the substrate bias, but the increase of the substrate bias only reduces the columnar crystal structure, and cannot completely eliminate the columnar crystal structure, and also increases the residual stress of the coating, so that the performance of the coating is affected to a certain extent.
According to the invention, the doping amount of N is regulated to be 8-15at% under an extremely low substrate bias environment, so that the coating forms a single-layer coating rich in Cr and doped with a small amount of N, the morphology and microstructure of the Cr coating are changed by doping a specific amount of N element, the grain structure of the Cr coating is changed from an original columnar crystal structure to a columnar-free nanocrystalline structure, meanwhile, the internal stress of the coating is smaller, the inward diffusion of N in the coating is facilitated when the coating with the nanocrystalline structure is oxidized at a high temperature, an in-situ continuous twin crystal ZrN layer is formed between a zirconium alloy interface and Zr, and the mutual diffusion of Zr and Cr in a substrate is effectively prevented.
The preparation method of the single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy for the nuclear is characterized by comprising the following steps of:
(1) Sequentially polishing the surface of the zirconium alloy by using 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper, and sequentially polishing the polished zirconium alloy substrate by using diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m. After determining that the polished sample has no scratches, burrs and the like, sequentially ultrasonically cleaning the sample for 10 minutes by using acetone and absolute ethyl alcohol, and drying the sample for later use;
(2) During the sputtering process of the coating, the back vacuum is 8 multiplied by 10 -4 Pa, the deposition temperature is 250-350 ℃, the bias voltage of the zirconium alloy matrix is minus 5-minus 20V, the deposition air pressure is 0.3-0.6 Pa, the deposition time is 8-12 h, a Direct Current (DC) power supply is used for driving a Cr target, the sputtering power of the Cr target is fixed to 300W, and the high-purity N is obtained 2 The introducing amount is 3-10 sccm, the N content of the coating is controlled to be 8-15 at%And (3) the room(s).
The invention has the following technical effects:
according to the invention, the single-layer Cr-enriched N-doped coating is prepared by magnetron sputtering, so that the mechanical property of the coating is improved, the hardness of the coating is enhanced, and the maximum hardness reaches 25.16Gpa, thereby improving the wear resistance of the coating; the morphology and microstructure of the coating are improved by doping a small amount of N atoms, the grain structure of the coating is a nanocrystalline structure without columnar crystal characteristics, the high-temperature oxidation resistance is effectively improved, and the oxidation weight gain is only 15.63mg/m 2 Meanwhile, the failure of the coating is slowed down, in addition, the nanocrystalline structure is favorable for forming continuous and compact twin crystals at the interface of the alloy and the coating in a high-temperature steam environment, and the interdiffusion of Zr and Cr is effectively blocked.
Drawings
Fig. 1: XRD patterns of as-deposited monolayer Cr-rich N-doped coatings prepared in example 1 of the present invention.
Fig. 2: scanning electron microscope image of the surface of the as-deposited monolayer Cr-rich N-doped coating prepared in the embodiment 1 of the invention.
Fig. 3: cross-sectional morphology diagram of a single-layer Cr-rich N-doped coating in a deposition state prepared in the invention example 1.
Fig. 4: the as-deposited monolayer Cr-rich N-doped coating prepared in the embodiment 1 of the invention is a transmission electron microscope image.
Fig. 5: surface and cross-sectional morphology of the as-deposited monolayer Cr-rich N-doped coating prepared in comparative example 2.
Fig. 6: the oxidation weight gain curve of the as-deposited monolayer Cr-rich N-doped coating prepared by the invention at different temperatures.
Fig. 7: the cross-sectional morphology and element distribution diagram of the as-deposited monolayer Cr-rich N-doped coating prepared by the invention are oxidized under 1200 ℃ water vapor.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be to those skilled in the art in light of the foregoing disclosure.
Example 1
The preparation method of the single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy for the nuclear comprises the following steps:
(1) Sequentially polishing the surface of the zirconium alloy by using 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper, and sequentially polishing the polished zirconium alloy substrate by using diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m. After determining that the polished sample has no scratches, burrs and the like, sequentially ultrasonically cleaning the sample for 10 minutes by using acetone and absolute ethyl alcohol, and drying the sample for later use;
(2) During the sputtering process of the coating, the back vacuum is 8 multiplied by 10 -4 Pa, deposition temperature of 300 ℃, substrate bias of-10V, deposition pressure of 0.4Pa, deposition time of 10h, and driving Cr target with Direct Current (DC) power supply, wherein sputtering power of the Cr target is fixed to 300W, and high purity N is obtained 2 The inlet amount is as follows: 5sccm, the N content of the prepared coating was 9.89at.%.
FIG. 1 shows the XRD patterns of the as-deposited Cr-rich N-doped coating prepared in this example, showing the shape of the XRD diffraction peak slightly different from the diffraction peak of the common Cr (110), the intensity of the peak being lower and slightly shifted to the left, and showing a state between crystal and amorphous similar to the amorphous "steamed bread peak".
Fig. 2 is a surface morphology diagram of the as-deposited Cr-rich N-doped coating prepared in this example, and it can be seen from the figure that the coating surface structure is compact, and has no defects such as cracks and holes. Wherein the doping amount of N is 9.89at.%.
FIG. 3 is a cross-sectional morphology of a as-deposited Cr-Rich N-doped coating prepared in this example, showing that the coating (Rich Cr-CrN coating) has good adhesion to the zirconium alloy substrate, a dense coating structure, and a coating thickness of 15.13 μm.
The transmission electron microscope of the deposited Cr-rich N-doped coating prepared in the embodiment is shown in Table 4, and the crystal is long-shuttle, the crystal size is about 5-40 nm, and the coating is a typical nano crystal structure.
The pure Cr coating is prepared according to the magnetron sputtering method, and the coating is found to have an obvious columnar crystal structure and larger pores and cracks.
Comparative example 1:
the preparation method of the single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy for the nuclear comprises the following steps:
(1) Sequentially polishing the surface of the Zr-4 alloy by using 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper, and sequentially polishing the polished Zr-4 alloy substrate by using diamond polishing liquid with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m. After determining that the polished sample has no scratches, burrs and the like, sequentially ultrasonically cleaning the sample for 10 minutes by using acetone and absolute ethyl alcohol, and drying the sample for later use;
(2) During the sputtering process of the coating, the back vacuum is 8 multiplied by 10 -4 Pa, deposition temperature 300 ℃, substrate bias voltage-60V, deposition air pressure 0.4Pa, deposition time length 10h, and a Direct Current (DC) power supply to drive a Cr target, wherein the sputtering power of the Cr target is fixed to 300W, so as to prepare the Cr coating with the thickness of 14.92 mu m.
Compared with the embodiment 1, in the magnetron sputtering process, the substrate bias voltage is increased from-10V to-60V, and compared with the pure Cr coating prepared at-10V, the prepared pure Cr coating has the advantages that the columnar crystal structure is reduced, and defects such as pores, cracks and the like in the coating are also reduced.
Comparative example 2:
the preparation method of the single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy for the nuclear comprises the following steps:
(1) Sequentially polishing the surface of the Zr-4 alloy by using 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper, and sequentially polishing the polished Zr-4 alloy substrate by using diamond polishing liquid with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m. After determining that the polished sample has no scratches, burrs and the like, sequentially ultrasonically cleaning the sample for 10 minutes by using acetone and absolute ethyl alcohol, and drying the sample for later use;
(2) During the sputtering process of the coating, the back vacuum is 8 multiplied by 10 -4 Pa, the deposition temperature is 300 ℃, the bias voltage of a Zr-4 alloy matrix is-60V, the deposition air pressure is 0.4Pa, the deposition time period is 10 hours, a Direct Current (DC) power supply is used for driving a Cr target, the sputtering power of the Cr target is fixed to 300W, and the high-purity N is obtained 2 The inlet amount is as follows: 5sccm, the N content of the prepared coating was 12.57at.%.
In the preparation process, it is found that in the process of preparing the N-doped Cr coating by magnetron sputtering, the substrate bias voltage is increased, the ion density of the substrate surface is increased, the doping amount of N deviates from the original setting, no nanocrystalline structure is formed in the prepared coating, but only the columnar crystal structure is reduced to a certain extent, even if the doping amount of N is increased, the defects such as pores and cracks are slightly reduced, but obvious defects still exist, as shown in fig. 5, obvious cracks are generated from the surface morphology (left graph) in fig. 5, and obvious pores and cracks still exist on the surface of the coating from the cross-sectional morphology (right graph).
Example 2
The preparation method of the single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy for the nuclear comprises the following steps:
(1) Sequentially polishing the surface of the Zr-4 alloy by using 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper, and sequentially polishing the polished Zr-4 alloy substrate by using diamond polishing liquid with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m. After determining that the polished sample has no scratches, burrs and the like, sequentially ultrasonically cleaning the sample for 10 minutes by using acetone and absolute ethyl alcohol, and drying the sample for later use;
(2) During the sputtering process of the coating, the back vacuum is 8 multiplied by 10 -4 Pa, the deposition temperature is 250-350 ℃, the substrate bias voltage is-10V, the deposition air pressure is 0.4Pa, the deposition time is 10h, a Direct Current (DC) power supply is used for driving a Cr target, the sputtering power of the Cr target is fixed to 300W, and the high-purity N is obtained 2 The inlet amount is as follows: 3sccm, the coating N content was controlled at 8.61at.%.
Example 3
The preparation method of the single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy for the nuclear comprises the following steps:
(1) Sequentially polishing the surface of the zirconium alloy by using 100# abrasive paper, 400# abrasive paper, 1000# abrasive paper and 2000# abrasive paper, and sequentially polishing the polished zirconium alloy substrate by using diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m. After determining that the polished sample has no scratches, burrs and the like, sequentially ultrasonically cleaning the sample for 10 minutes by using acetone and absolute ethyl alcohol, and drying the sample for later use;
(2) During the sputtering process of the coating, the back vacuum is 8 multiplied by 10 -4 Pa, the deposition temperature is 300 ℃, the bias voltage of a Zr-4 alloy matrix is-10V, the deposition air pressure is 0.4Pa, the deposition time period is 10h, a Direct Current (DC) power supply is used for driving a Cr target, the sputtering power of the Cr target is fixed to 300W, and the high-purity N is obtained 2 The inlet amount is as follows: 10sccm, the coating N content was controlled at 12.72at.%.
Example 4
The preparation method of the single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy for the nuclear comprises the following steps:
(1) Sequentially polishing the surface of the Zr-4 alloy by using 100# sand paper, 400# sand paper, 1000# sand paper and 2000# sand paper, sequentially polishing the polished Zr-4 alloy substrate by using diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, determining that a polished sample has no scratches, burrs and the like, sequentially ultrasonically cleaning the polished sample by using acetone and absolute ethyl alcohol for 10 minutes, and drying for later use;
(2) During the sputtering process of the coating, the back vacuum is 8 multiplied by 10 -4 Pa, the deposition temperature is 350 ℃, the bias voltage of a Zr-4 alloy matrix is-20V, the deposition air pressure is 0.6Pa, the deposition time period is 9h, a Direct Current (DC) power supply is used for driving a Cr target, the sputtering power of the Cr target is fixed to 300W, and the high-purity N is obtained 2 The amount of the coating was 5sccm, and the N content in the coating was 14.26 at%.
Example 5
The preparation method of the single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy for the nuclear comprises the following steps:
(1) Sequentially polishing the surface of the Zr-4 alloy by using 100# sand paper, 400# sand paper, 1000# sand paper and 2000# sand paper, sequentially polishing the polished Zr-4 alloy substrate by using diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, determining that a polished sample has no scratches, burrs and the like, sequentially ultrasonically cleaning the polished sample by using acetone and absolute ethyl alcohol for 10 minutes, and drying for later use;
(2) During the sputtering process of the coating, the back vacuum is 8 multiplied by 10 -4 Pa, the deposition temperature is 250 ℃, the bias voltage of a Zr-4 alloy matrix is-5V, the deposition air pressure is 0.3Pa, the deposition time period is 12h, a Direct Current (DC) power supply is used for driving a Cr target, the sputtering power of the Cr target is fixed to 300W, and the high-purity N is obtained 2 The amount of the coating was 5sccm, and the N content in the coating was 8.94 at%.
Performance test:
(1) Mechanical property test
Generally, the higher the hardness of the material, the better its antifriction and wear-resistant properties, which is beneficial for improving the tribological properties of the zirconium cladding in normal operating conditions. The hardness and the elastic modulus of the coating can be improved by doping N atoms in the Cr coating. The hardness test results of the coatings prepared in examples 1-5 and each comparative example of the present invention are shown in Table 1, wherein a pure Cr coating was prepared by magnetron sputtering according to the parameters of example 1 (N.noon during deposition) 2 And (5) opening).
Table 1: microhardness of as-deposited coating
| Coating layer | N doping amount (at.%) | Coating thickness (μm) | Coating hardness (GPa) |
| Pure Cr coating | - | 14.94 | 3.11 |
| Example 1 | 9.89 | 15.13 | 18.06 |
| Example 2 | 8.61 | 15.22 | 16.51 |
| Example 3 | 12.72 | 14.96 | 21.58 |
| Example 4 | 14.26 | 14.24 | 25.16 |
| Example 5 | 8.94 | 16.62 | 17.28 |
| Comparative example 1 | - | 14.92 | 5.66 |
| Comparative example 2 | 12.57 | 15.18 | 6.29 |
The microhardness of the Cr coating without N doping is found to be 3.11GPa, and the hardness of the Cr-rich N-doped coating prepared by each embodiment of the invention is in an ascending trend along with the increase of the doping amount of N. While the Cr-enriched N-doped coating prepared by increasing the substrate bias and then depositing has a remarkable improvement in N doping amount compared with the coating prepared in the example 1, the hardness of the Cr-enriched N-doped coating is not improved, but rather, the hardness of the Cr-enriched N-doped coating is remarkably reduced. The hardness of the coating is improved, the wear resistance and antifriction performance of the coating can be enhanced, and the service life of the coating is prolonged.
(2) High temperature antioxidant performance test
The Cr-enriched N-doped zirconium alloy prepared in example 1 was tested by high temperature steam oxidation weight gain tests at different temperatures. As shown in FIG. 6, it can be seen that the Cr-Rich N-doped Zr-4 coating significantly reduced the oxidation weight gain of the zirconium alloy at different temperatures compared to the bare Zr-4 alloy. To investigate the effect of N doping on the high temperature oxidation resistance of the coating, N was added on the basis of example 3 2 The amount of the introduced material was increased to prepare Cr-rich N-doped coatings having a thickness of about 15. Mu.m, and N-doped amounts of 17.44at.% and 20.15at.%, which were respectively designated as comparative example 2 and comparative example 3, and the coatings prepared in each example and each comparative example were subjected to oxidation treatment in a steam atmosphere at 1200℃for 30 minutes, and the oxidation weight gain was counted, as shown in Table 2.
Table 2: high temperature oxidation resistance of coatings with different N doping levels
| Coating of zirconium alloy surfaces | N doping amount (at.%) | Oxidative weight gain (mg/cm) 2 ) |
| - | - | 31.33 |
| Pure Cr coating | - | 27.67 |
| Example 1 | 9.89 | 19.89 |
| Example 2 | 8.61 | 20.58 |
| Example 3 | 12.72 | 17.94 |
| Example 4 | 14.26 | 15.63 |
| Example 5 | 8.94 | 20.09 |
| Comparative example 1 | 12.57 | 25.16 |
| Comparative example 2 | 17.44 | 25.25 |
| Comparative example 3 | 20.15 | 26.68 |
As is clear from the above table, the oxidation weight can be increased from 31.33mg/cm under the water vapor environment of 1200 DEG C 2 Reducing the temperature to 16.63mg/cm 2 . Under the same conditions, the oxidized weight gain of example 3 was 17.94mg/cm 2 While the oxidation weight gain of comparative example 1, which is similar to the N-doping amount thereof, was 25.16mg/cm 2 . It can be seen that as the doping amount of N in the coating increases, the more compact and uniform the nanocrystalline structure of the coating is, the more the nanocrystalline structure isThe better the inhibiting effect on the oxidation weight gain, but when the N doping amount in the coating is higher than 15at%, N is generated when the coating is in a high-temperature steam environment for a long time 2 Resulting in an oxidation resistance of the coating that is exacerbated as the amount of N doping increases.
(3) Element interdiffusion performance detection
The Cr-enriched N-doped coating prepared in the embodiment 1 is oxidized in a high-temperature vapor environment at 1200 ℃, and in the single-layer Cr-enriched N-doped coating, N can be effectively diffused from a columnar nanocrystalline structure to the inside due to the fact that columnar crystals are converted into the columnar nanocrystalline structure, and a continuous twin crystal ZrN layer is formed with Zr in situ at the interface of the zirconium alloy and the coating, so that mutual diffusion of Zr and Cr in the coating is effectively prevented. After oxidation for 30min in a 1200 ℃ water vapor environment, the cross-sectional morphology and element distribution of the coating are shown in fig. 7, and it can be seen that the oxidized Cr-rich N-doped coating forms a continuous twin crystal layer at the interface with the zirconium alloy, meanwhile, the Cr-rich N-doped coating has no Zr, and the zirconium alloy matrix has no Cr, which shows that the continuous twin crystal layer has a remarkable effect of preventing Zr-Cr interdiffusion. The Cr-rich N-doped coating prepared in comparative example 1 was also subjected to a corresponding test, and found that a discontinuous twin structure was formed at the interface between the coating and the Zr alloy, and that the interdiffusion barrier effect was weak for Cr and Zr, and that a small amount of Zr was present in the final coating and a small amount of Cr was also diffused in the Zr alloy.
Claims (7)
1. A single-layer Cr-enriched N-doped coating on the surface of a zirconium alloy for a core is characterized in that: in the single-layer Cr-enriched N-doped coating, the doping amount of N is 8-15 at%, specifically, by magnetron sputtering, a Cr target is used as a sputtering target, and N is introduced during sputtering 2 Is prepared.
2. A single layer Cr-rich N-doped surface coating of a zirconium alloy for nuclear use as claimed in claim 1, wherein: the base bias voltage of the magnetron sputtering is-5 to-20V, the deposition air pressure is 0.3 to 0.6Pa, and the deposition time is 8 to 12 hours.
3. A core as claimed in claim 1 or 2The single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy is characterized in that: the driving power of the Cr target is a direct current power supply, and the sputtering power is 300W and N 2 The amount of the mixture to be introduced is 3-10 sccm.
4. A method for preparing the single-layer Cr-rich N-doped coating on the surface of the zirconium alloy for nuclear use according to claim 1, which is characterized in that: specifically, a Cr target is used as a sputtering target, and N is introduced at the same time 2 And (3) performing magnetron sputtering, wherein the base bias voltage of the magnetron sputtering is-5 to-20V.
5. The method for preparing the single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy for the nuclear, as claimed in claim 4, wherein the method comprises the following steps: in the magnetron sputtering process, the deposition air pressure is 0.3-0.6 Pa, and the deposition time is 8-12 h.
6. The method for preparing the single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy for the nuclear use according to claim 4 or 5, which is characterized in that: the driving power of the Cr target is a direct current power supply, and the sputtering power is 300W and N 2 The amount of the mixture to be introduced is 3-10 sccm.
7. The preparation method of the single-layer Cr-enriched N-doped coating on the surface of the zirconium alloy for the nuclear is characterized by comprising the following steps:
(1) Sequentially polishing the surface of the zirconium alloy by using 100# sand paper, 400# sand paper, 1000# sand paper and 2000# sand paper, sequentially polishing the polished zirconium alloy substrate by using diamond polishing solution with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the zirconium alloy substrate by using acetone and absolute ethyl alcohol for 10min, and drying for later use;
(2) During the sputtering process of the coating, the back vacuum is 8 multiplied by 10 -4 Pa, the deposition temperature is 250-350 ℃, the bias voltage of a Zr-4 alloy matrix is-5 to-20V, the deposition air pressure is 0.3-0.6 Pa, the deposition time is 8-12 h, a Direct Current (DC) power supply is used for driving a Cr target, the sputtering power of the Cr target is fixed to 300W, and the high-purity N is obtained 2 The introducing amount is 3-10 sccm, and the N content of the coating is controlled between 8 and 15at percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310520440.9A CN116516309B (en) | 2023-05-10 | 2023-05-10 | Single-layer Cr-enriched N-doped coating on surface of zirconium alloy for nuclear and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310520440.9A CN116516309B (en) | 2023-05-10 | 2023-05-10 | Single-layer Cr-enriched N-doped coating on surface of zirconium alloy for nuclear and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116516309A true CN116516309A (en) | 2023-08-01 |
| CN116516309B CN116516309B (en) | 2024-07-19 |
Family
ID=87391903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310520440.9A Active CN116516309B (en) | 2023-05-10 | 2023-05-10 | Single-layer Cr-enriched N-doped coating on surface of zirconium alloy for nuclear and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116516309B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118086848A (en) * | 2024-03-07 | 2024-05-28 | 重庆文理学院 | High-temperature oxidation resistant composite coating for surface of zirconium alloy for core and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0000638D0 (en) * | 2000-01-13 | 2000-03-01 | Hauzer Techno Coating Europ Bv | Method of applying a coating of physical vapour deposition |
| US20020106048A1 (en) * | 2001-02-02 | 2002-08-08 | General Electric Company | Creep resistant zirconium alloy and nuclear fuel cladding incorporating said alloy |
| CN103741108A (en) * | 2013-12-27 | 2014-04-23 | 晨光真空技术（深圳）有限公司 | Preparation method of decorating protective coating for CrNx-based component gradient transition |
| CN109852943A (en) * | 2019-03-15 | 2019-06-07 | 成都理工大学 | The preparation method and product of nuclear-used zirconium alloy surface C rN coating |
| CN109972098A (en) * | 2019-05-05 | 2019-07-05 | 大连理工大学 | A kind of preparation method of cladding materials surface C rN thick coating |
| CN110055496A (en) * | 2019-04-04 | 2019-07-26 | 中国核动力研究设计院 | A kind of preparation process preparing Cr coating in nuclear-used zirconium alloy substrate surface |
| CN110129752A (en) * | 2019-05-24 | 2019-08-16 | 山东省科学院激光研究所 | Zirconium alloy tube surface treatment method and device |
| CN113684460A (en) * | 2021-07-30 | 2021-11-23 | 哈尔滨工业大学 | Preparation method of accident-resistant cladding Cr/CrN composite coating |
-
2023
- 2023-05-10 CN CN202310520440.9A patent/CN116516309B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0000638D0 (en) * | 2000-01-13 | 2000-03-01 | Hauzer Techno Coating Europ Bv | Method of applying a coating of physical vapour deposition |
| US20020106048A1 (en) * | 2001-02-02 | 2002-08-08 | General Electric Company | Creep resistant zirconium alloy and nuclear fuel cladding incorporating said alloy |
| CN103741108A (en) * | 2013-12-27 | 2014-04-23 | 晨光真空技术（深圳）有限公司 | Preparation method of decorating protective coating for CrNx-based component gradient transition |
| CN109852943A (en) * | 2019-03-15 | 2019-06-07 | 成都理工大学 | The preparation method and product of nuclear-used zirconium alloy surface C rN coating |
| CN110055496A (en) * | 2019-04-04 | 2019-07-26 | 中国核动力研究设计院 | A kind of preparation process preparing Cr coating in nuclear-used zirconium alloy substrate surface |
| CN109972098A (en) * | 2019-05-05 | 2019-07-05 | 大连理工大学 | A kind of preparation method of cladding materials surface C rN thick coating |
| CN110129752A (en) * | 2019-05-24 | 2019-08-16 | 山东省科学院激光研究所 | Zirconium alloy tube surface treatment method and device |
| CN113684460A (en) * | 2021-07-30 | 2021-11-23 | 哈尔滨工业大学 | Preparation method of accident-resistant cladding Cr/CrN composite coating |
Non-Patent Citations (6)
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118086848A (en) * | 2024-03-07 | 2024-05-28 | 重庆文理学院 | High-temperature oxidation resistant composite coating for surface of zirconium alloy for core and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116516309B (en) | 2024-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN116516309B (en) | Single-layer Cr-enriched N-doped coating on surface of zirconium alloy for nuclear and preparation method thereof | |
| CN112760610B (en) | High-entropy nitride coating for surface protection of aviation bearing and preparation method thereof | |
| CN108690956B (en) | Arc ion plating-magnetron sputtering composite deposition high-temperature wear-resistant antifriction AlTiN nano multilayer coating and preparation method and application thereof | |
| US11545273B2 (en) | Nuclear reactor component having a coating of amorphous chromium carbide | |
| US20220002865A1 (en) | Nuclear component with metastable cr coating, dli-mocvd method for producing same, and uses for controlling oxidation/hydridation | |
| US11118260B2 (en) | Zirconium alloy cladding with improved oxidation resistance at high temperature and method for manufacturing same | |
| US20230227967A1 (en) | Process of Manufacture a Nuclear Component with Metal Substrate by Dlimocvd and Method against Oxidation/Hydriding of Nuclear Component | |
| CN118086848B (en) | High-temperature oxidation resistant composite coating for surface of zirconium alloy for core and preparation method thereof | |
| CN109207953A (en) | Resistance to high temperature oxidation ZrNx/ (ZrAlFe) N/ (ZrAlFeM) N complex gradient coating preparation process | |
| CN109943811B (en) | Preparation method of coating for zirconium alloy cladding | |
| CN109811316B (en) | Zirconium alloy coating with high burnup and long service life and preparation method thereof | |
| KR102362999B1 (en) | Sliding elements, especially piston rings | |
| CN114574827B (en) | Carbon-containing high-entropy alloy film and preparation method and application thereof | |
| CN117721417A (en) | Super wear-resistant zirconium alloy cladding surface composite coating and preparation method thereof | |
| CN115142018A (en) | High-entropy alloy coating resistant to high-temperature liquid lead/lead bismuth alloy corrosion and preparation method thereof | |
| CN114182213A (en) | Titanium alloy wear-resistant antioxidant composite coating and preparation method thereof | |
| CN113430488B (en) | Nano composite coating for nuclear reactor fuel cladding and preparation method thereof | |
| CN110629176A (en) | Cr-Al alloy film with Zr as substrate and preparation method thereof | |
| CN111979543B (en) | Coating material for forming self-lubricating amorphous carbon film based on friction-induced catalysis and preparation method thereof | |
| CN114959569A (en) | Cr (chromium) 2 Preparation method of AlC diffusion impervious layer | |
| CN110527970B (en) | Full ceramic-based high-temperature solar energy absorbing coating and preparation method thereof | |
| CN114438493A (en) | High-temperature steam corrosion resistant coating for surface of zirconium alloy cladding tube of nuclear power plant and preparation method thereof | |
| CN117604473A (en) | CrSiC composite coating with high-temperature oxidation resistance and structural thermal stability, preparation method and application | |
| CN109943822B (en) | Post-treatment method for improving wear resistance and friction reduction performance of CrN coating | |
| CN114921756B (en) | Tungsten-containing diamond-like coating and preparation method thereof |
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 |