CN110983261B - Corrosion-resistant bearing steel and ion implantation surface treatment method thereof - Google Patents
Corrosion-resistant bearing steel and ion implantation surface treatment method thereof Download PDFInfo
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- CN110983261B CN110983261B CN201911305569.8A CN201911305569A CN110983261B CN 110983261 B CN110983261 B CN 110983261B CN 201911305569 A CN201911305569 A CN 201911305569A CN 110983261 B CN110983261 B CN 110983261B
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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
- 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
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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
- 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
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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
- 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
- C23C14/48—Ion implantation
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Abstract
The invention relates to corrosion-resistant bearing steel, wherein a chromium film is deposited on the surface of a bearing steel matrix, and 10-15 at% of Ti and 30-60 at% of C are distributed on the chromium film. The ion implantation surface treatment method for preparing the corrosion-resistant bearing steel comprises the following steps: the method comprises the following steps of (a) depositing a chromium film on a bearing steel matrix, (b) injecting titanium ions and carbon ions into the surface of the matrix by an ion injection method, wherein the chromium film enables the surface of the bearing steel matrix to have good hardness, toughness, wear resistance and corrosion resistance, ion injection is carried out on the basis, reaction is carried out on the surface of the chromium film to form an amorphous layer and a ceramic phase, a plurality of dislocation defects are caused, the enrichment of passive element chromium on the surface can be promoted, the stability of a passive film is improved, and the corrosion resistance of the film is improved, so that the bearing steel prepared by the surface treatment method has good corrosion resistance and mechanical property at the same time.
Description
Technical Field
The invention relates to the field of stainless steel surface treatment, in particular to corrosion-resistant bearing steel and an ion implantation surface treatment method thereof.
Background
The main shaft bearing is one of the most critical parts of an aircraft engine, works under severe conditions of high rotating speed, high load, high temperature, high DN value and the like, the service life and reliability of the main shaft bearing directly influence the service life and reliability of the engine, and once the main shaft bearing fails, catastrophic consequences can be brought to the engine which runs at high speed and the airplane which flies at high altitude. The manufacturing technology of the main shaft bearing of the aero-engine in China is started late, and although great progress is made, compared with the strong countries of the aero-bearings in Europe, America and the like, a great gap still exists. Statistics of outdoor use of the engine also proves that the generation mechanism of most bearing failure modes is related to bearing materials, the working environment of the advanced aero-engine main shaft bearing in the future is worse, and the bearing materials are required to have higher temperature resistance, surface hardness and wear resistance, good impact toughness and fracture toughness of a core part and excellent corrosion resistance.
However, the surface corrosion resistance of the bearing steel is still different from that of the future ideal bearing steel, and further improvement of the surface corrosion resistance of the bearing steel is required. In the surface treatment technology for improving the corrosion resistance of bearing steel, the composite strengthening heat treatment and coating technology still have the problems of difficult process control, large internal stress and the like, so that the popularization and the application of the technology are limited. Ion implantation is widely used for surface strengthening of steel materials, and for example, patent document CN110241394A entitled "a method for strengthening alloy steel surface and alloy steel" discloses a method for improving corrosion resistance of surface by sequentially implanting Ti ions and Cr ions. However, the improvement of the surface corrosion resistance by this method still hardly satisfies the severe requirements of the working conditions of the bearing steel, and further improvement of the surface corrosion resistance of the bearing steel is required.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a corrosion-resistant bearing steel capable of further improving the corrosion resistance of the bearing steel, aiming at the current state of the prior art.
The second technical problem to be solved by the invention is to provide an ion implantation surface treatment method for preparing the corrosion-resistant bearing steel.
The technical scheme adopted by the invention for solving the technical problems is as follows: a corrosion-resistant bearing steel characterized by: the surface of the bearing steel matrix is deposited with a chromium film, and 10-15 at% Ti and 30-60 at% C are distributed on the chromium film.
Preferably, the thickness of the chromium film is 0.5 to 3 μm, and more preferably, the thickness of the chromium film is 0.5 to 1.5 μm.
Preferably, the bearing steel is any one of CSS-42L, M50NiL, Cronidur 30, 316L stainless steel and Cr4Mo4Ni 4V.
The ion implantation surface treatment method of the corrosion-resistant bearing steel comprises the following steps:
(a, depositing a chromium film on a bearing steel substrate;
and (b) implanting titanium ions and carbon ions into the surface of the substrate by an ion implantation method, wherein the implantation sequence can be that titanium ions are implanted firstly and then carbon ions are implanted, or carbon ions are implanted firstly and then titanium ions are implanted.
And c, performing surface cleaning and Cr ion implantation on the bearing steel substrate by using a Cr ion beam before the step a in order to remove the surface oxidation layer and make the chromium film have better bonding force.
Preferably, the conditions of the Cr ion implantation of step a are as follows: 5-10kV, 2-6mA beam, 5000-7000mC of injected charge amount, and 2.1 of average charge amount Qr of chromium ions. More preferably, the voltage is 7-8kV, the beam current is 4mA, and the injected charge quantity is 5900mC-6000 mC.
Preferably, the step a uses a magnetic filtration cathode vacuum arc deposition technique (FCVA) to deposit the chromium film. The Cr film is formed by the FCVA technology, has high film forming density, no air holes, better bonding force with a substrate and lower defect density, and therefore has good hardness, toughness, wear resistance and corrosion resistance.
Preferably, the deposition conditions of the chromium film deposition of step a are as follows: 90-120A arc flow, bias voltage of-70 to-90V, beam current of 450-500mA, duty ratio of 90%, total charge amount of 6100 × 100mC, deposition time of 40-60 min. Further preferably, the arc flow 100 and 110A has a bias voltage of-80V, a beam current of 470mA, a duty ratio of 90%, a total charge amount of 6100 × 100mC, and a deposition time of 50 min.
Preferably, the parameters of the ion implantation in step c are as follows: the implantation energy is 20-100keV, and the implantation dosage is 1 × 1016-1×1018ions/cm2. Further preferably, the implantation energy is 30keV and the implantation dose is 3X 1017ions/cm2
Compared with the prior art, the invention has the advantages that: the chromium film enables the surface of a bearing steel substrate to have good hardness, toughness, wear resistance and corrosion resistance by combining deposition of the chromium film and ion implantation, and the ion implantation is carried out on the basis, so that an amorphous layer and a ceramic phase are formed on the surface of the chromium film through reaction, a plurality of dislocation defects are caused, the enrichment of passive element chromium on the surface can be promoted, the stability of a passivation film is improved, and the corrosion resistance of the film is improved, so that the bearing steel prepared by adopting the surface treatment method has good corrosion resistance and mechanical property, and the current density and the corrosion rate can be reduced by more than 10 times; the brittleness of the Cr coating is also improved, and the Young modulus is reduced to 98.7 GPa; the nano-hardness can reach 7.33 GPa.
Drawings
FIG. 1 is an SEM photograph of a Cr sample according to an embodiment of the present invention;
FIG. 2 is an SEM photograph of a Cr + C sample according to an embodiment of the present invention;
FIG. 3 is an SEM photograph of a Cr + Ti sample of an embodiment of the present invention;
FIG. 4 is an SEM photograph of a Cr + (Ti + C) sample of an example of the present invention
FIG. 5 is a graph showing the results of Young's modulus tests of examples of the present invention;
FIG. 6 is a graph of nano-hardness test results for an embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples.
The sample composition of CSS-42L used in this example was
Preparing materials: 10X 5mm are cut from hardened CSS-42L ingots3Mechanically polishing the sample to 3000# by using SiC carborundum paper, then polishing the sample to a mirror surface by using a diamond polishing agent with the granularity of 1.5 mu m, cleaning and drying.
Cr film preparation and ion implantation: the samples were ultrasonically cleaned with acetone prior to the preparation of the chromium film. Adopting a high-purity chromium target as a cathode, and before deposition, firstly, carrying out surface cleaning and Cr ion implantation by using a Cr ion beam led out from a magnetic filtration cathode arc vacuum system, wherein the implantation conditions are as follows: the voltage of 8kV, the beam current of 4mA, the injected charge amount is 5900mC, and the average charge amount Qr of chromium ions is 2.1. Then carrying out chromium film deposition on the substrate, wherein the deposition conditions are as follows: arc 110A, 80V, beam current 470mA, duty cycle 90%, total charge 6100 × 100 mC. The injection process of titanium and carbon is carried out in MEVVA ion implanter, titanium ion is injected first, then carbon ion is injected, and the numerical parameters used are as follows: implant energy 30keV, implant dose 3X 1017ions/cm2。
In this example, samples coated with only a Cr film, a Cr film and Ti, and a Cr film and C were simultaneously prepared as comparative examples, and the CSS-42L substrate coated with a Cr film was abbreviated as Cr, and samples implanted with Ti, C, and (Ti + C) were respectively labeled as Cr + Ti, Cr + C, and Cr + (Ti + C).
The above samples were subjected to electrochemical corrosion testing at 30 ℃ in a 3.5 wt.% NaCl solution, the results of which are shown in the following table
The self-corrosion potential of the Cr coating was-0.348V and there was no significant passivation. After ion implantation, the corrosion potential of CSS-42L was shifted in the positive direction, and the self-corrosion potentials of the C, Ti and (Ti + C) implanted samples were increased to-0.274V, -0.259V and-0.257V, respectively. The self-etching current is reduced by about 1 order of magnitude after ion implantation, and the current density is from 1.98E-7A/cm especially after (Ti + C) double-element implantation2Reduced to 2.28E-8A/cm2. In addition, the corrosion rates of the C, Ti and (Ti + C) injected samples were 0.38X 10, respectively-3mm/A，0.48×10-3mm/A and 0.26X 10-3mm/A. In the active dissolution zone, ion implantation creates a new passivation film to protect the coating and substrate from further corrosion. The increase in the self-corrosion potential indicates that ion implantation enhances the chemical stability of CSS-42L steel and reduces the corrosion tendency. The Ti + C double-element injection obviously improves the corrosion resistance.
The above samples were observed for their SEM images, and the photographs of Cr, Cr + C, Cr + Ti and Cr + (Ti + C) are shown in FIGS. 1, 2, 3 and 4. Wherein, FIG. 1 shows the surface corrosion morphology of Cr layer without ion implantation, the surface preservation of Cr layer is complete, pitting corrosion pits exist locally, the preservation of coating is complete, and corrosion products and pitting corrosion pits appear on the surface. After Ti or C single element implantation, the pit number decreases but the size increases. After ion implantation, there is a phenomenon of local cracking, and the internal stress generated by the ion implantation process may be one of the causes of coating cracking. After the (Ti + C) double element injection, the surface is relatively complete, and the corrosion cracking degree of the coating is reduced, which is probably caused by the reduction of the internal stress. Ion implantation processThe pitting corrosion sensitivity of the Cr coating is reduced, the corrosion resistance is obviously improved, and the dual-element injection effect is better. At the same time, an amorphous phase and a ceramic phase Cr are formed on the surface2C/TiC is also a factor in the improvement of corrosion resistance
The results of the tests on the samples described above for Young's modulus, mechanical properties in nanometer hardness are shown in FIGS. 5 and 6, where the substrate in both figures is a CSS-42L matrix control without any treatment.
In FIG. 5, the Young's modulus of the Cr coating is 105.2GPa, which is higher than that of the CSS-42L matrix; after the Ti and C single elements are injected into the Cr layer, the Young modulus is reduced to 69GPa and 57.5GPa respectively; however, the Young's modulus after the (Ti + C) double element injection is 98.7 GPa; the (Ti + C) double-element injection can effectively improve the brittleness of the Cr coating.
In FIG. 6, the nano-hardness increased from 3.95GPa to 7.04GPa after Cr deposition; after Ti and C are injected into the single element, the hardness of the Cr coating is reduced, and the hardness values of the Ti and the C after injection are respectively 6.45GPa and 5.20 GPa; however, the nano-hardness of the (Ti + C) double-element injection is greatly improved to 7.33GPa, which is higher than that of the Cr coating. After the (Ti + C) double-element is injected, the interaction between different ions is more frequent, so that more collision cascades are formed underground and the structural strength is improved; in addition, a ceramic phase Cr is formed2C and TiC also contribute to the increase in surface hardness.
In this example, only CSS-42L was tested, but other bearing steels such as M50NiL, Cronidur 30, 316L stainless steel, Cr4Mo4Ni4V and the like also had similar effects.
The technical means disclosed in the invention scheme are not limited to the technical means disclosed in the above embodiments, but also include the technical scheme formed by any combination of the above technical features. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.
Claims (6)
1. An ion implantation surface treatment method for preparing corrosion-resistant bearing steel is characterized by comprising the following steps:
a. carrying out surface cleaning and Cr ion implantation on the bearing steel matrix by using a Cr ion beam, and then depositing a chromium film on the bearing steel matrix;
b. then titanium ions are injected into the surface of the substrate by an ion injection method, and then carbon ions are injected to obtain the corrosion-resistant bearing steel;
a chromium film is deposited on the surface of a substrate of the corrosion-resistant bearing steel, and 10-15 at.% of Ti and 30-60 at.% of C are distributed on the chromium film; the surface of the chromium film also contains Cr2C and TiC;
the step a adopts a magnetic filtration cathode vacuum arc plasma deposition coating process to deposit a chromium film, the thickness of the chromium film is 0.5-3 mu m, and the parameters of the ion implantation in the step b are as follows: the implantation energy is 20-100keV, and the implantation dosage is 1 × 1016-1×1018ions/cm2。
2. The ion implantation surface treatment method of corrosion-resistant bearing steel according to claim 1, characterized in that: the conditions of the Cr ion implantation of the step a are as follows: 5-10kV, 2-6mA beam, and 5000-7000mC of injected charge.
3. The ion implantation surface treatment method of corrosion-resistant bearing steel according to claim 1, characterized in that: the deposition conditions of the chromium film deposition in the step a are as follows: 90-120A arc flow, bias voltage of-70 to-90V, beam current of 450-500mA, duty ratio of 90%, total charge amount of 6100 × 100mC, deposition time of 40-60 min.
4. The ion implantation surface treatment method of corrosion-resistant bearing steel according to claim 1, characterized in that: the parameters of the ion implantation in the step b are as follows: implant energy 30keV, implant dose 3X 1017ions/cm2。
5. A corrosion-resistant bearing steel characterized by: the corrosion-resistant bearing steel is prepared by the ion implantation surface treatment method according to any one of claims 1 to 4.
6. The corrosion resistant bearing steel of claim 5, wherein: the bearing steel is any one of CSS-42L, M50NiL, Cronidur 30, 316L stainless steel and Cr4Mo4Ni 4V.
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