CN115261772B - Method for rapidly preparing ceramic modified layer on surface of zirconium alloy - Google Patents
Method for rapidly preparing ceramic modified layer on surface of zirconium alloy Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 60
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000010791 quenching Methods 0.000 claims abstract description 16
- 230000000171 quenching effect Effects 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims description 13
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 7
- 230000003746 surface roughness Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- 239000008213 purified water Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 239000007769 metal material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000007545 Vickers hardness test Methods 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 239000007943 implant Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 239000004744 fabric Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000010200 validation analysis Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000009417 prefabrication Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/186—High-melting or refractory metals or alloys based thereon of zirconium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/80—After-treatment
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention relates to the technical field of metal material surfaces, and provides a method for rapidly preparing a ceramic modified layer on a zirconium alloy surface, which comprises the following steps: s1, surface pretreatment of a zirconium alloy sample; s2, carrying out quenching treatment on the pretreated zirconium alloy sample after heating treatment at 1000-1200 ℃; s3, wiping and cleaning after quenching treatment. By the technical scheme, the problems of poor wear resistance, poor compatibility, poor corrosion resistance and complex preparation process of the zirconium alloy modified layer of medical zirconium alloy in the related technology are solved.
Description
Technical Field
The invention relates to the technical field of surface treatment of metal materials, in particular to a method for rapidly preparing a ceramic modified layer on the surface of a zirconium alloy.
Background
Zirconium alloys have corrosion resistance and biocompatibility and are therefore useful for implantation into the body. In medicine, zr-2.5Nb alloy can be made into knee or hip implants, which can reduce friction, increase wear resistance while maintaining overall performance (manufacturability, fracture toughness and ductility), providing a good solution for medical implants. As an applied biomedical implant material, zirconia ceramic has extremely high surface hardness, frictional wear performance and corrosion resistance, but also has brittleness of ceramic materials. Aiming at the service standard of partial implant materials, zirconium alloy is difficult to meet the clinical use requirements in the aspects of wear resistance, surface hardness and the like; and zirconia ceramics also present a risk of brittle fracture during implantation. The surface modification of the metal material for organisms by adopting a surface treatment method can better combine the metal characteristics of the matrix with the surface bioactivity of the matrix, thereby laying a good foundation for the application of the metal biological material.
The patent of application number 201810454617.9 is a method for preparing a black ceramic layer on the surface of a zirconium-based alloy, wherein the zirconium alloy is industrial grade zirconium alloy containing hafnium (Hf), the preparation stage of the ceramic layer needs to be kept for 50-60 min, the ceramic layer is cooled to room temperature along with a furnace under the air atmosphere and then subjected to surface polishing treatment, the thickness of the ceramic layer is 1-11 mu m, and the hardness is 386-506 HV.
The patent of 201910173412.8 is a method for preparing oxidized ceramic layer on zirconium and zirconium alloy surface and its application, in which the preparation stage of ceramic layer needs to be heat-preserved for 6h, argon gas is introduced, cooled to below 100 deg.C, and the thickness of oxidized ceramic layer is 1-20 micrometers.
Therefore, the preparation method of the zirconium alloy surface oxide ceramic layer in the prior art has the problems of long heat preservation time and long cooling time, the preparation process needs to be filled with oxidizing atmosphere, the preparation method is complex, and the ceramic layer has low thickness and low hardness.
Disclosure of Invention
The invention provides a method for rapidly preparing a ceramic modified layer on the surface of a zirconium alloy, which solves the problems of poor wear resistance, poor compatibility, poor corrosion resistance and complex preparation process of the zirconium alloy modified layer in medical zirconium alloy in the related technology.
The technical scheme of the invention is as follows:
A method for rapidly preparing a ceramic modified layer on the surface of a zirconium alloy comprises the following steps:
S1, surface pretreatment of a zirconium alloy sample;
S2, carrying out quenching treatment on the pretreated zirconium alloy sample after heating treatment at 1000-1200 ℃;
S3, wiping and cleaning after quenching treatment.
The zirconium alloy of the invention is applicable to all pure zirconium and zirconium alloy systems and has wide application range.
The sample prepared by the method is not required to be cooled along with a furnace, can be prepared without waiting for temperature cooling, can avoid coarsening and degradation of microstructure caused by long-time high-temperature influence, can greatly refine the grain structure of a metal matrix by adopting water quenching treatment, and improves the mechanical property of the matrix material by fine-grain strengthening effect.
In the quenching treatment process, the high-temperature beta phase in the zirconium alloy is rapidly converted into the normal-temperature alpha phase to generate non-diffusion phase change, meanwhile, crystal grains in a matrix structure cannot sufficiently grow, and the microstructure is refined, so that the mechanical property of the matrix alloy is further improved, and the strength is improved.
As a further technique, the surface pretreatment in the step S1 is to perform surface treatment to a surface roughness of 0.001-0.005 μm on the zirconium alloy sample, and then to perform cleaning and air-drying.
The surface treatment comprises polishing treatment and finish turning treatment. (the method is not particularly limited).
As a further technique, the cleaning is performed by immersing a zirconium alloy sample in a solution for ultrasonic cleaning.
As a further technique, the ultrasonic cleaning is performed in acetone, deionized water, and absolute ethanol, respectively.
As a further technique, the ultrasonic cleaning time is 10 to 20 minutes.
As a further technique, in the treatment process of the step S2, the vacuum degree is 1X 10 -1～5×10-1 Pa, and the heat preservation time is 5-15 min.
The process cost of the surface zirconia ceramic layer prepared by the method is low, a sample is instantaneously oxidized at a high temperature, the high-temperature heat preservation time is short, the low vacuum degree state of the furnace chamber is kept in the high-temperature heat preservation process, inert protective gas or oxidizing gas is not required to be introduced, and no consumption is generated.
As a further technique, in the step S2, the temperature raising process is ended until the quenching is performed for not more than 20S.
As a further technique, the step S3 is a step of ultrasonic cleaning in absolute ethanol for 10 to 20 minutes.
The thickness of the ceramic modified layer obtained by the method for rapidly preparing the ceramic modified layer on the surface of the zirconium alloy is 15-22 mu m.
The working principle and the beneficial effects of the invention are as follows:
1. The invention firstly uses the oxidizing atmosphere in high-temperature air to perform the prefabrication film, then the surface of the alloy with the high-temperature Wen Gao in water quenching treatment is further reacted under the oxidizing condition in purified water, and the substrate fine-grain strengthening and the surface zirconia ceramic layer preparation are realized. Zirconium and zirconium alloy have excellent corrosion resistance and good biocompatibility, after the preparation of the surface ceramic layer is finished, the zirconium and zirconium alloy not only has the plasticity and toughness of the matrix alloy, but also greatly increases the surface strength and corrosion resistance, and the zirconium oxide ceramic layer has excellent biocompatibility, and the ceramic barrier layer can further inhibit ion precipitation in a metal matrix.
2. The preparation method is simple, high in production efficiency, capable of being applied in large scale, short in period and low in preparation cost, and can be used for preparing a plurality of batches of samples by heating at one time, wherein the temperature of the furnace chamber is maintained after the heat treatment and the temperature rise are completed for the first time, and the repeated heating and cooling processes are not needed; the sample is directly quenched without cooling along with the furnace, so that the sampling time is greatly shortened; after the ceramic modified layer is prepared, surface post-treatment is not needed, and the surface is directly cleaned.
3. The invention improves the surface performance of the medical zirconium alloy and enhances the toughness of zirconia ceramics, improves the surface performance of the zirconium alloy and prolongs the service life of the zirconium alloy in human body environment. The generated zirconia ceramic layer is prepared in situ by high-temperature instantaneous oxidation, and other substances are not introduced, and the zirconia ceramic layer is not a coating. Therefore, there is a cation-rich diffusion layer between the ceramic layer and the substrate, and there is no problem of poor surface binding force.
On one hand, the zirconia ceramic layer produced by instantaneous high-temperature oxidation and quenching treatment has fine instantaneous cooling structure, and the macroscopic surface is smooth without post-treatment, on the other hand, oxidation reaction further occurs, so that the thickness of the ceramic layer can be increased.
4. The invention prepares a uniform and compact zirconia ceramic layer on the surface of the zirconium alloy, and the matrix is still a metal matrix, so that the toughness of a sample is ensured, the surface performance is ensured, and the thickness of the zirconia ceramic layer on the surface is thicker than that in the prior art, and can reach 15-22 mu m; the microhardness is improved by 335-351%, the nanoindentation hardness is improved by 218-234%, and the surface performance is improved remarkably.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a photograph of a cross section of a sample prepared in example 1 under a microscope;
FIG. 2 is a photograph of a cross section of a sample prepared in example 2 under a microscope;
FIG. 3 is a photograph of a cross section of a sample prepared in example 3 under a microscope;
FIG. 4 is a photograph of a cross section of a sample prepared in comparative example 2 under a microscope;
FIG. 5 is a photograph of a cross section of a sample prepared in comparative example 3 under a microscope.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The method for rapidly preparing the ceramic modified layer on the surface of the zirconium alloy comprises the following steps:
S1, polishing the surface of the zirconium alloy sample, wherein the surface roughness is controlled to be 0.001 mu m. After the treatment, the zirconium alloy samples are respectively immersed in acetone, deionized water and absolute ethyl alcohol for respectively ultrasonic cleaning for 10min, and the surfaces are air-dried.
S2, heating the furnace temperature to 1100 ℃ in the air atmosphere by utilizing a vacuum tube type heat treatment furnace, keeping the furnace temperature constant, then placing the air-dried zirconium alloy sample into a furnace chamber by utilizing crucible tongs, closing a tube type furnace chamber, pumping the vacuum degree in the chamber to 1X 10 -1 Pa, preserving heat for 5min in a low vacuum environment, then opening a vent valve, recovering the atmospheric pressure in the chamber, simultaneously opening a furnace door, clamping the zirconium alloy sample out by utilizing the crucible tongs, and rapidly placing the zirconium alloy sample into purified water for quenching treatment within 20S.
S3, taking out the sample in purified water, wiping the sample by dust-free wiping cloth, and then carrying out ultrasonic cleaning in absolute ethyl alcohol for 10min to obtain the zirconia ceramic layer sample.
Example 2
Example 2 produced a surface zirconia modified layer with different process parameters (see table 1) than example 1, otherwise identical to example 1.
Example 3
Example 3 produced a surface zirconia modified layer with different process parameters (see table 1) than example 1, otherwise identical to example 1.
Comparative example 1
Comparative example 1 is a zirconium alloy substrate.
Comparative example 2
The method for rapidly preparing the ceramic modified layer on the surface of the zirconium alloy comprises the following steps:
S1, polishing the surface of the zirconium alloy sample, wherein the surface roughness is controlled to be 0.001 mu m. After the treatment, the zirconium alloy samples are respectively immersed in acetone, deionized water and absolute ethyl alcohol for respectively ultrasonic cleaning for 10min, and the surfaces are air-dried.
S2, heating the furnace temperature to 1100 ℃ in the air atmosphere by utilizing a vacuum tube type heat treatment furnace, keeping the furnace temperature constant, then placing the air-dried zirconium alloy sample into a furnace chamber by utilizing crucible tongs, sealing a tube type furnace chamber, pumping the vacuum degree in the chamber to 1X 10 -1 Pa, preserving heat in a low vacuum environment for 5min, and cooling along with the furnace (keeping the vacuum environment).
S3, taking out the sample, wiping the sample by dust-free wiping cloth, and then carrying out ultrasonic cleaning in absolute ethyl alcohol for 10min to obtain the zirconia ceramic layer sample.
Comparative example 3
S1, polishing the surface of the zirconium alloy sample, wherein the surface roughness is controlled to be 0.001 mu m. After the treatment, the zirconium alloy samples are respectively immersed in acetone, deionized water and absolute ethyl alcohol for respectively ultrasonic cleaning for 10min, and the surfaces are air-dried.
S2, heating the furnace temperature to 1100 ℃ by using a vacuum tube type heat treatment furnace under the air atmosphere, keeping the furnace temperature constant, then placing the air-dried zirconium alloy sample into a furnace chamber by using crucible tongs, sealing the tube type furnace chamber, preserving heat for 5min, introducing air in the heating and heat preserving process, and cooling along with the furnace under the air atmosphere without the vacuum degree.
S3, taking out the sample, wiping the sample by dust-free wiping cloth, and then carrying out ultrasonic cleaning in absolute ethyl alcohol for 10min to obtain the zirconia ceramic layer sample.
TABLE 1 examples 1-3 preparation of surface zirconia modification layer Process parameters
| Parameters (parameters) | Example 1 | Example 2 | Example 3 |
| Thickness of ceramic layer (mum) | 15 | 18 | 22 |
| Alloy surface roughness (μm) | 0.001 | 0.002 | 0.005 |
| Ultrasonic wave pre-cleaning time (min) | 10 | 15 | 20 |
| Heating temperature (. Degree. C.) | 1100 | 1000 | 1200 |
| Vacuum degree of insulation (Pa) | 1×10-1 | 2×10-1 | 5×10-1 |
| Low vacuum holding time (min) | 5 | 10 | 15 |
| Sample final cleaning time (min) | 10 | 15 | 20 |
The zirconia ceramic layer samples prepared in examples 1 to 3 and the zirconium alloy substrate of comparative example 1 were subjected to vickers hardness test and nanoindentation test.
Vickers hardness test: GB/T4340.1-2009 section 1 of Vickers hardness test of Metal Material: test methods were tested according to the validation criteria of table 2.
Nano indentation test: based on JB/T12721-2016 technical specifications of "solid Material in situ nanoindentation scratch tester", the adopted pressing needle is a commonly used diamond Boshi pressing needle (Berkovich diamond tip), and the test is carried out according to the verification standard of Table 3.
Thickness of ceramic layer: the cross section of the sample ceramic layer was observed using a scanning electron microscope, and the ceramic layer thickness was measured.
TABLE 2 Vickers hardness test validation criteria
| Item times | Test parameters | Setting standard |
| 1 | Load of | 100gf |
| 2 | Loading and dwell time | 10s |
| 3 | Number of tests | 30 |
TABLE 3 nanoindentation test validation criteria
| Item times | Test parameters | Setting standard |
| 1 | Maximum loading load of 5000. Mu.N | 5000μN |
| 2 | Load rate | 500-1000μN/s |
| 3 | Time of load retention | 2s |
| 4 | Number of tests | 10 |
TABLE 4 test criteria and Vickers hardness test results for examples 1-3
Table 5 test criteria and nanoindentation test results for examples 1-3
As is clear from tables 4 and 5, the surface hardness of the prepared zirconia ceramic layer samples of examples 1 to 3 of the present invention is significantly enhanced, the hardness is 1074 to 1113HV, and the hardness is improved by 335 to 351% compared with the sample of comparative example 1; the nano indentation hardness of the zirconia ceramic layer sample surface is also obviously enhanced, the hardness is 10.37-10.89 GPa, and the hardness is improved by 218-234%. As can be seen from FIGS. 1 to 3, the zirconia ceramic modified layers of examples 1 to 3 were uniform and dense, and had a thickness of 15 to 22. Mu.m.
Compared with example 1, comparative example 2 did not undergo quenching treatment, and after heat preservation, it was cooled with the furnace (kept in a vacuum atmosphere), and since the sample was subjected to heat treatment in a vacuum atmosphere in strict accordance with the experimental conditions, the surface was not changed at all, and only the microstructure was recovered and grown to be coarse. Therefore, the ceramic modified layer was not formed on the surface of comparative example 2, and the surface hardness was similar to that of the substrate (comparative example 1).
Compared with the embodiment 1, the comparative example 3 is heated and insulated by introducing air, and cooled in an air atmosphere along with a furnace, the surface is seriously oxidized, and the surface oxide layer is cracked due to large difference of thermal expansion coefficients between the ceramic layer and the matrix and large internal stress. Due to uneven surface cracking, reasonable hardness results cannot be measured.
Therefore, it is clear from comparative examples 2 and 3 that the ceramic modified layer is not formed on the surface of the ceramic substrate by cooling (maintaining vacuum environment) with the furnace after heat preservation without quenching treatment in the preparation process; air is introduced in the heating and heat preserving process, and the ceramic modified layer is formed on the surface of the ceramic modified layer after being cooled along with a furnace in the air atmosphere, but the ceramic modified layer is cracked, so that the zirconia ceramic modified layer with uniform compactness and higher thickness can be formed only by the scheme of the invention.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. The method for rapidly preparing the ceramic modified layer on the surface of the zirconium alloy is characterized by comprising the following steps of:
S1, surface pretreatment of a zirconium alloy sample;
s2, carrying out quenching treatment on the pretreated zirconium alloy sample after heating treatment at the temperature of 1000-1200 ℃;
S3, wiping and cleaning after quenching treatment;
In the treatment process of the step S2, the vacuum degree is 1 multiplied by 10 -1～5×10-1 Pa, and the heat preservation time is 5-15 min;
in the step S2, the process from the end of the heating treatment to the quenching is not more than 20S;
The medium for quenching treatment in the step S2 is purified water;
And the surface pretreatment in the step S1 is to clean and air-dry the zirconium alloy sample after the surface treatment until the surface roughness is 0.001-0.005 mu m.
2. The method for rapidly preparing a ceramic modified layer on a zirconium alloy surface according to claim 1, wherein the cleaning in step S1 is performed by immersing a zirconium alloy sample in a solution for ultrasonic cleaning.
3. The method for rapidly preparing a ceramic modified layer on a zirconium alloy surface according to claim 2, wherein the ultrasonic cleaning is performed in acetone, deionized water and absolute ethyl alcohol, respectively.
4. The method for rapidly preparing a ceramic modified layer on a zirconium alloy surface according to claim 2, wherein the ultrasonic cleaning time is 10 to 20 minutes.
5. The method for rapidly preparing the ceramic modified layer on the surface of the zirconium alloy according to claim 1, wherein the step S3 is to wash the ceramic modified layer in absolute ethyl alcohol for 10-20 min.
6. The ceramic modified layer obtained by the method for rapidly producing a ceramic modified layer on a zirconium alloy surface as claimed in any one of claims 1 to 5, wherein the thickness is 15 to 22 μm.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294631A (en) * | 1978-12-22 | 1981-10-13 | General Electric Company | Surface corrosion inhibition of zirconium alloys by laser surface β-quenching |
| US4690716A (en) * | 1985-02-13 | 1987-09-01 | Westinghouse Electric Corp. | Process for forming seamless tubing of zirconium or titanium alloys from welded precursors |
| FR2683828A1 (en) * | 1991-11-18 | 1993-05-21 | Cezus Co Europ Zirconium | Process for the manufacture of metal sheets of homogeneous structure made of Zircaloy 2 or of Zircaloy 4 |
| CN107142444A (en) * | 2017-03-28 | 2017-09-08 | 广西大学 | A kind of preparation method of the medical zircaloy of β types of surface oxidation |
| CN109706421A (en) * | 2019-03-07 | 2019-05-03 | 苏州微创关节医疗科技有限公司 | Prepare the method and application of zirconium and Zr alloy surface oxidation ceramic layer |
| CN111101089A (en) * | 2020-02-18 | 2020-05-05 | 苏州微创关节医疗科技有限公司 | Method for forming oxide layer on surface of zirconium or zirconium alloy and application |
| WO2022017240A1 (en) * | 2020-07-21 | 2022-01-27 | 苏州微创关节医疗科技有限公司 | Preparation method for oxide ceramic layer on surface of metal base and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101604103B1 (en) * | 2015-04-14 | 2016-03-25 | 한전원자력연료 주식회사 | The composition and fabrication method of corrosion resistance zirconium alloys for nuclear fuel rod and components |
-
2022
- 2022-07-09 CN CN202210807663.9A patent/CN115261772B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294631A (en) * | 1978-12-22 | 1981-10-13 | General Electric Company | Surface corrosion inhibition of zirconium alloys by laser surface β-quenching |
| US4690716A (en) * | 1985-02-13 | 1987-09-01 | Westinghouse Electric Corp. | Process for forming seamless tubing of zirconium or titanium alloys from welded precursors |
| FR2683828A1 (en) * | 1991-11-18 | 1993-05-21 | Cezus Co Europ Zirconium | Process for the manufacture of metal sheets of homogeneous structure made of Zircaloy 2 or of Zircaloy 4 |
| CN107142444A (en) * | 2017-03-28 | 2017-09-08 | 广西大学 | A kind of preparation method of the medical zircaloy of β types of surface oxidation |
| CN109706421A (en) * | 2019-03-07 | 2019-05-03 | 苏州微创关节医疗科技有限公司 | Prepare the method and application of zirconium and Zr alloy surface oxidation ceramic layer |
| CN111101089A (en) * | 2020-02-18 | 2020-05-05 | 苏州微创关节医疗科技有限公司 | Method for forming oxide layer on surface of zirconium or zirconium alloy and application |
| WO2022017240A1 (en) * | 2020-07-21 | 2022-01-27 | 苏州微创关节医疗科技有限公司 | Preparation method for oxide ceramic layer on surface of metal base and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| M5锆合金氧化行为研究;张娴;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第2017年第02期期);第14-16、55-56页 * |
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