CN105755427A - Austenitic stainless steel and composite plasma strengthening method thereof - Google Patents

Austenitic stainless steel and composite plasma strengthening method thereof Download PDF

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CN105755427A
CN105755427A CN201610245921.3A CN201610245921A CN105755427A CN 105755427 A CN105755427 A CN 105755427A CN 201610245921 A CN201610245921 A CN 201610245921A CN 105755427 A CN105755427 A CN 105755427A
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plasma
stainless steel
austenitic stainless
workpiece
nitriding
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CN105755427B (en
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孙耀明
周祎
陈寿
李明雨
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Shenzhen 863 New Material Technology Co ltd
Shenzhen Tongchan Lixing Technology Group Co ltd
Shenzhen Graduate School Harbin Institute of Technology
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SHENZHEN 863 PROGRAM RESEARCH AND DEVELOPMENT CENTER
Shenzhen Graduate School Harbin Institute of Technology
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C8/00Solid 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
    • C23C8/06Solid 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
    • C23C8/36Solid 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 using ionised gases, e.g. ionitriding
    • C23C8/38Treatment of ferrous surfaces
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C8/00Solid 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
    • C23C8/02Pretreatment of the material to be coated

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Abstract

The invention discloses austenitic stainless steel and composite plasma strengthening method thereof.The strengthening method includes: cleaning a workpiece, performing plasma electrochemical nano pretreatment, cleaning and drying, performing plasma bombardment cleaning and performing low-temperature plasma nitriding.By the strengthening method, a composite strengthened layer can be formed on the surface of the austenitic stainless steel.The strengthening method has the advantages that the plasma electrochemical nano pretreatment is fast in treatment, free of workpiece deformation and capable of evenly treating special-shaped workpieces; the plasma bombardment cleaning can remove the porous layer generated by the plasma electrochemical method, and the hardness and corrosion resistance of the workpiece can be increased favorably; the low-temperature plasma nitriding does not generate chromium nitride, and the corrosion resistance of the workpiece is increased evidently as compared with other methods; the plasma nitride layer generated by the low-temperature plasma nitriding is high in hardness, and the plasma nitride layer coordinated with a nano structural layer of a certain thickness is good in toughness and can bear large load.

Description

A kind of austenitic stainless steel and compound plasma intensifying method thereof
Technical field
The present invention relates to technical field of metal surface modification, particularly relate to a kind of austenitic stainless steel and compound plasma intensifying method thereof.
Background technology
Austenitic stainless steel corrosion resistance (i.e. corrosion resistance) is excellent, is widely used in various fields, but its hardness and wearability are not good, limit the application of austenitic stainless steel.Glow discharge nitriding is, under the effect of plasma, nitrogen element is penetrated into steel, forms Intensive intervention body, can be obviously enhanced case hardness and wearability, be conventional process for modifying surface.Conventional ion nitriding temperature higher (about 550 DEG C), when being used for processing austenitic stainless steel, although can improving workpiece hardness, but chromium nitride can be caused to precipitate out, corrosion resistance significantly reduces.Temperature is reduced to less than 450 DEG C by low temperature nitriding, it is possible to generate high rigidity, corrosion resistant S-phase.But if the time of process is short, hardness is relatively low;The process time is long, and the S-phase of generation decomposites chromium nitride in the later stage processes, and causes that corrosion resistance declines.
By pretreating process such as ultrasonic shot peening, high-energy shot, surface mechanical attritions, strong plastic deformation is produced at surface of the work, make its surface microstructure nanorize, carry out nitriding afterwards, the high diffusivity coefficient utilizing nanometer layer realizes less treatment temperature, reduce the precipitation of chromium compound, maintenance corrosion resistance of austenitic stainless steels basis obtains more high surface hardness, but pretreatment time is longer, workpiece is easily deformed, to workpiece shapes requirement harshness so that this technology is subject to a lot of restriction in industrialized production.
Plasma electrochemical pre-treatment can form one layer of nanostructured layers at material surface, and processing speed is fast, corrosion resistance excellent, is suitable for processing abnormal workpieces, has splendid development prospect, but after processing, rustless steel hardness is relatively low, limits its application.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of austenitic stainless steel and compound plasma intensifying method thereof, it is intended to solve that existing austenitic stainless steel process for treating surface efficiency is low, workpiece shapes requirement is harsh, easily affect the problems such as workpiece quality.
Technical scheme is as follows:
A kind of austenitic stainless steel compound plasma intensifying method, wherein, including step:
A, austenite stainless steel workpiece is carried out, removes surface and oil contaminant and impurity;
B, in the electrolytic solution austenite stainless steel workpiece is carried out plasma electrochemical pre-treatment, generate nanostructured layers at austenite stainless steel workpiece surface;
C, pretreated austenite stainless steel workpiece is carried out and dries;
D, the austenite stainless steel workpiece after drying is loaded in ion-nitriding furnace, by glow discharge nitriding stove evacuation, then pass into argon and hydrogen, be then electrified to carry out plasma bombardment cleaning and plasma bombardment hyperthermic treatment;
E, reach design temperature after, close argon, pass into nitrogen, be incubated a period of time, complete low temperature plasma nitriding and process.
Described austenitic stainless steel compound plasma intensifying method, wherein, the electrolyte of plasma electrochemical pre-treatment, by mass percentage, including: glycerol 65-88%, ethylene glycol 10-20%, sodium carbonate 1-5%, deionized water 1-10%.
Described austenitic stainless steel compound plasma intensifying method, wherein, in plasma electrochemical pre-treatment, adopting direct current pulse power source, austenite stainless steel workpiece is negative electrode, graphite is anode, voltage is 200-600 volt, and frequency is 350-650 hertz, dutycycle 15-50%, electrolyte temperature is less than 50 DEG C, and the process time is 0.5-10 minute.
Described austenitic stainless steel compound plasma intensifying method, wherein, in plasma bombardment temperature-rise period, the volume ratio of argon and hydrogen is 1:3-3:1, and air pressure is 80-150Pa.
Described austenitic stainless steel compound plasma intensifying method, wherein, in low temperature plasma nitriding process, the volume ratio of nitrogen and hydrogen is 1:6-1:1, and air pressure is 80-150Pa, and low temperature plasma nitriding temperature is 350-420 DEG C, and the low temperature plasma nitriding time is 2-10h.
Described austenitic stainless steel compound plasma intensifying method, wherein, the thickness of described nanostructured layers is 20-100 micron.
Described austenitic stainless steel compound plasma intensifying method, wherein, the average grain size of described nanostructured layers is 10-100 nanometer.
Described austenitic stainless steel compound plasma intensifying method, wherein, in described step D, is evacuated down to 0.5Pa.
A kind of austenitic stainless steel, wherein, adopts method as above strengthening to obtain.
Beneficial effect: (1) nanorize pretreatment using plasma electrochemical method, processing speed is fast, and workpiece is indeformable, and abnormal workpieces also can uniform treatment;(2) plasma bombardment cleans and can remove the weaker zone that plasma electrochemical method generates, and contributes to workpiece hardness and corrosion proof raising;(3) low temperature plasma nitriding will not generate chromium nitride, relative additive method, and workpiece corrosion resistance is significantly improved;(4) plasma nitrided layer that low temperature plasma nitriding generates has higher hardness, coordinates certain thickness nanostructured layers, and toughness is better, it is possible to carry bigger load.
Accompanying drawing explanation
Fig. 1 is the flow chart of a kind of austenitic stainless steel compound plasma intensifying method preferred embodiment provided by the invention.
Fig. 2 is the austenitic stainless steel Making programme figure of the present invention.
Detailed description of the invention
The present invention provides a kind of austenitic stainless steel and compound plasma intensifying method thereof, and for making the purpose of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
Referring to the flow chart that Fig. 1, Fig. 1 are a kind of austenitic stainless steel compound plasma intensifying method preferred embodiment provided by the invention, it includes step:
S1, austenite stainless steel workpiece is carried out, removes surface and oil contaminant and impurity;
S2, in the electrolytic solution austenite stainless steel workpiece is carried out plasma electrochemical pre-treatment, generate nanostructured layers at austenite stainless steel workpiece surface;
S3, pretreated austenite stainless steel workpiece is carried out and dries;
S4, the austenite stainless steel workpiece after drying is loaded in ion-nitriding furnace, by glow discharge nitriding stove evacuation, then pass into argon and hydrogen, be then electrified to carry out plasma bombardment cleaning and plasma bombardment hyperthermic treatment;
S5, reach design temperature after, close argon, pass into nitrogen, be incubated a period of time, complete low temperature plasma nitriding and process.
Austenitic stainless steel surface is carried out nanorize process by plasma electrochemical method by the present invention, significantly increase nitrogen Elements Diffusion coefficient, Rapid Ion Nitriding at a lower temperature, realize the perfect adaptation of high rigidity and high corrosion-resistant, processing speed is fast, workpiece is without deformation, it is adaptable to various difform surfaces.
As shown in Figure 2, the master operation of the present invention, it is in the electrolytic solution austenite stainless steel workpiece 10 is carried out plasma electrochemical pre-treatment, thus at austenite stainless steel workpiece 10 Surface Creation nanostructured layers 20, then carry out low temperature plasma nitriding process, thus at nanostructured layers 20 Surface Creation plasma nitrided layer 30, so form final complex intensifying layer, its good toughness, hardness is high, and can improve decay resistance.The combination that the present invention is processed with low temperature plasma nitriding by plasma electrochemical pre-treatment, it is achieved that the perfect adaptation of austenitic stainless steel high rigidity and high-wearing feature, is more suitable in industrialized production and applies.Additionally the present invention has also combined plasma bombardment cleaning and plasma bombardment hyperthermic treatment, namely while cleaning, hyperthermic treatment is carried out, this processing method can effectively remove the weaker zone that plasma electrochemical method generates, thus improving workpiece hardness and corrosion resistance.
Further, the electrolyte of plasma electrochemical pre-treatment, by mass percentage, and including: glycerol 65-88%, ethylene glycol 10-20%, sodium carbonate 1-5%, deionized water 1-10%.When this electrolyte, austenite stainless steel workpiece will not deform, and can process various abnormal workpieces, reduces the requirement to workpiece shapes, the nanostructured layers (also can claim nano modification layer) being simultaneously generated has higher corrosion resistance, and processing speed is also faster.
Further, in plasma electrochemical pre-treatment, adopting direct current pulse power source, austenite stainless steel workpiece is negative electrode, graphite is anode, and voltage is 200-600 volt, and frequency is 350-650 hertz, dutycycle 15-50%, electrolyte temperature, less than 50 DEG C, processes 0.5-10 minute time.Above-mentioned treatment conditions, can improve treatment effeciency and processing speed, and its thickness of nanostructured layers generated is moderate.In the present invention, the thickness of nanostructured layers is preferably 20-100 micron, and its thickness is too small, then corrosion resistance reduces, and its thickness is excessive, then can increase the process time, improves cost, it is also possible to affecting rustless steel hardness, what more have choosing is 30 ~ 60 microns.The average grain size of nanostructured layers is 10-100 nanometer, and this crystallite dimension can improve nanostructured layers corrosion resistance, and guarantees that rustless steel has preferably hardness.
Further, in plasma bombardment temperature-rise period, the volume ratio of argon and hydrogen is 1:3-3:1, and air pressure is 80-150Pa.Under this condition, the weaker zone that more effective removal workpiece generates in plasma electrochemical pre-treatment process, the low temperature plasma nitriding that can be also simultaneously follow-up processes and prepares certain temperature conditions.
Further, in low temperature plasma nitriding process, the volume ratio of nitrogen and hydrogen is 1:6-1:1, and air pressure is 80-150Pa, and low temperature plasma nitriding temperature is 350-420 DEG C, and nitriding time is 2-10h.Carry out low temperature plasma nitriding under this condition, the chromium compounds such as chromium nitride can be prevented effectively from and precipitate out, thus ensureing that the austenite stainless steel workpiece after final process has enough corrosion resistances.
Further, in described step S4, being evacuated down to 0.5Pa, it is pass into argon and hydrogen in order to follow-up that evacuation processes, in order to carry out plasma bombardment cleaning and hyperthermic treatment.
The present invention also provides for a kind of austenitic stainless steel, and it adopts method as above strengthening to obtain.
Embodiment 1:
A kind of austenitic stainless steel compound plasma intensifying method, comprises the steps of:
(1) to austenitic stainless steel workpiece cleaning, surface and oil contaminant and impurity are removed;
(2) in the electrolytic solution austenite stainless steel workpiece being carried out plasma electrochemical pre-treatment, each component of electrolyte and mass percent be: glycerol 65%, ethylene glycol 20%, sodium carbonate 5%, deionized water 10%.Adopting direct current pulse power source, workpiece is negative electrode, and graphite is anode, and voltage is 200 volts, and frequency is 650 hertz, and dutycycle is 15%, and electrolyte temperature is less than 50 DEG C, and the process time is 10 minutes.The nanostructured layer thickness generated is 20 microns, and average grain size is 10 nanometers;
(3) pretreated austenite stainless steel workpiece is carried out and dries;
(4) being loaded in ion-nitriding furnace by austenite stainless steel workpiece, be evacuated down to 0.5Pa, pass into argon and hydrogen, energising carries out plasma bombardment cleaning and plasma bombardment hyperthermic treatment;The volume ratio of argon and hydrogen is 1:3, and air pressure is 80Pa;
(5) closing argon, pass into nitrogen, the volume ratio regulating nitrogen and hydrogen is 1:6, and air pressure is 80Pa, and nitriding temperature is 350 DEG C, and nitriding time is 10h, completes whole process technique.
Austenite stainless steel workpiece after process, case hardness is more than 1200HV, and the neutral salt spray time, abnormal workpieces uniformity was good more than 200h.
Embodiment 2:
A kind of austenitic stainless steel compound plasma intensifying method, comprises the steps of:
(1) to austenitic stainless steel workpiece cleaning, surface and oil contaminant and impurity are removed;
(2) in the electrolytic solution austenite stainless steel workpiece being carried out plasma electrochemical pre-treatment, each component of electrolyte and mass percent be: glycerol 75%, ethylene glycol 15%, sodium carbonate 3%, deionized water 7%.Adopting direct current pulse power source, workpiece is negative electrode, and graphite is anode, and voltage is 400 volts, and frequency is 550 hertz, and dutycycle is 35%, and electrolyte temperature is less than 50 DEG C, and the process time is 5 minutes.The nanostructured layer thickness generated is 60 microns, and average grain size is 40 nanometers;
(3) it is carried out pretreated austenite stainless steel workpiece drying;
(4) loading in ion-nitriding furnace by workpiece, be evacuated down to 0.5Pa, pass into argon and hydrogen, energising carries out plasma bombardment cleaning and plasma bombardment hyperthermic treatment;The volume ratio of argon and hydrogen is 1:1, and air pressure is 100Pa;
(5) closing argon, pass into nitrogen, the volume ratio regulating nitrogen and hydrogen is 1:4, and air pressure is 100Pa, and nitriding temperature is 370 DEG C, and nitriding time is 5h, completes whole process technique.
Austenite stainless steel workpiece after process, case hardness is more than 1300HV, and the neutral salt spray time, abnormal workpieces uniformity was good more than 200h.
Embodiment 3
A kind of austenitic stainless steel compound plasma intensifying method, comprises the steps of:
(1) to austenitic stainless steel workpiece cleaning, surface and oil contaminant and impurity are removed;
(2) in the electrolytic solution austenite stainless steel workpiece being carried out plasma electrochemical pre-treatment, each component of electrolyte and mass percent be: glycerol 80%, ethylene glycol 15%, sodium carbonate 2%, deionized water 3%.Adopting direct current pulse power source, workpiece is negative electrode, and graphite is anode, and voltage is 600 volts, and frequency is 450 hertz, and dutycycle is 40%, and electrolyte temperature is less than 50 DEG C, and the process time is 0.5 minute.The nanostructured layer thickness generated is 30 microns, and average grain size is 80 nanometers;
(3) it is carried out pretreated austenite stainless steel workpiece drying;
(4) loading in ion-nitriding furnace by workpiece, be evacuated down to 0.5Pa, pass into argon and hydrogen, energising carries out plasma bombardment cleaning and plasma bombardment hyperthermic treatment;The volume ratio of argon and hydrogen is 2:1, and air pressure is 140Pa;
(5) closing argon, pass into nitrogen, the volume ratio regulating nitrogen and hydrogen is 1:2, and air pressure is 140Pa, and nitriding temperature is 420 DEG C, and nitriding time is 2h, completes whole process technique.
Austenite stainless steel workpiece after process, case hardness is more than 1300HV, and the neutral salt spray time, abnormal workpieces uniformity was good more than 200h.
Embodiment 4:
A kind of austenitic stainless steel compound plasma intensifying method, comprises the steps of:
(1) to austenitic stainless steel workpiece cleaning, surface and oil contaminant and impurity are removed;
(2) in the electrolytic solution austenite stainless steel workpiece being carried out plasma electrochemical pre-treatment, each component of electrolyte and mass percent be: glycerol 88%, ethylene glycol 10%, sodium carbonate 1%, deionized water 1%.Adopting direct current pulse power source, workpiece is negative electrode, and graphite is anode, and voltage is 600 volts, and frequency is 350 hertz, and dutycycle is 50%, and electrolyte temperature is less than 50 DEG C, and the process time is 10 minutes.The nanostructured layer thickness generated is 100 microns, and average grain size is 100 nanometers;
(3) it is carried out pretreated austenite stainless steel workpiece drying;
(4) loading in ion-nitriding furnace by workpiece, be evacuated down to 0.5Pa, pass into argon and hydrogen, energising carries out plasma bombardment cleaning and plasma bombardment hyperthermic treatment;The volume ratio of argon and hydrogen is 3:1, and air pressure is 150Pa;
(5) closing argon, pass into nitrogen, the volume ratio regulating nitrogen and hydrogen is 1:1, and air pressure is 150Pa, and nitriding temperature is 400 DEG C, and nitriding time is 10h, completes whole process technique.
Austenite stainless steel workpiece after process, case hardness is more than 1400HV, and the neutral salt spray time, abnormal workpieces uniformity was good more than 200h.
In sum, the compound plasma intensifying method of the present invention, cleans and the operation such as intensification and low temperature plasma nitriding including workpiece cleaning, plasma electrochemical pre-treatment, cleaning, drying, plasma bombardment;The complex intensifying layer ultimately generated comprise 20-100 micron nanostructured layers and above nanostructured layers glow discharge nitriding formed plasma nitrided layer;Surface of the work after process has higher hardness, corrosion resistance and toughness, processing speed is fast, workpiece is indeformable, abnormal workpieces also can uniform treatment, be suitable for industrialized production needs, can be applicable to large-scale production.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, it is possible to improved according to the above description or convert, all these improve and convert the protection domain that all should belong to claims of the present invention.

Claims (9)

1. an austenitic stainless steel compound plasma intensifying method, it is characterised in that include step:
A, austenite stainless steel workpiece is carried out, removes surface and oil contaminant and impurity;
B, in the electrolytic solution austenite stainless steel workpiece is carried out plasma electrochemical pre-treatment, generate nanostructured layers at austenite stainless steel workpiece surface;
C, pretreated austenite stainless steel workpiece is carried out and dries;
D, the austenite stainless steel workpiece after drying is loaded in ion-nitriding furnace, by glow discharge nitriding stove evacuation, then pass into argon and hydrogen, be then electrified to carry out plasma bombardment cleaning and plasma bombardment hyperthermic treatment;
E, reach design temperature after, close argon, pass into nitrogen, be incubated a period of time, complete low temperature plasma nitriding and process.
2. austenitic stainless steel compound plasma intensifying method according to claim 1, it is characterised in that the electrolyte of plasma electrochemical pre-treatment, by mass percentage, including glycerol 65-88%, ethylene glycol 10-20%, sodium carbonate 1-5%, deionized water 1-10%.
3. austenitic stainless steel compound plasma intensifying method according to claim 1, it is characterized in that, in plasma electrochemical pre-treatment, adopting direct current pulse power source, austenite stainless steel workpiece is negative electrode, graphite is anode, voltage is 200-600 volt, and frequency is 350-650 hertz, dutycycle 15-50%, electrolyte temperature is less than 50 DEG C, and the process time is 0.5-10 minute.
4. austenitic stainless steel compound plasma intensifying method according to claim 1, it is characterised in that in plasma bombardment temperature-rise period, the volume ratio of argon and hydrogen is 1:3-3:1, and air pressure is 80-150Pa.
5. austenitic stainless steel compound plasma intensifying method according to claim 1, it is characterized in that, in low temperature plasma nitriding process, the volume ratio of nitrogen and hydrogen is 1:6-1:1, air pressure is 80-150Pa, low temperature plasma nitriding temperature is 350-420 DEG C, and the low temperature plasma nitriding time is 2-10h.
6. austenitic stainless steel compound plasma intensifying method according to claim 1, it is characterised in that the thickness of described nanostructured layers is 20-100 micron.
7. austenitic stainless steel compound plasma intensifying method according to claim 1, it is characterised in that the average grain size of described nanostructured layers is 10-100 nanometer.
8. austenitic stainless steel compound plasma intensifying method according to claim 1, it is characterised in that in described step D, be evacuated down to 0.5Pa.
9. an austenitic stainless steel, it is characterised in that adopt the strengthening of the method as described in any one of claim 1 ~ 8 to obtain.
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CN108642437A (en) * 2018-05-10 2018-10-12 苏州国立塑料制品有限公司 A kind of metal die surface intensified technique
CN109316042A (en) * 2018-09-14 2019-02-12 深圳市华宇发真空离子技术有限公司 It is a kind of not glue iron pan and preparation method thereof
CN111304581A (en) * 2020-03-21 2020-06-19 哈尔滨工程大学 Circulating carburization treatment method for carburization layer on surface of heavy-duty gear
CN111805022A (en) * 2020-06-04 2020-10-23 南方科技大学 Plasma-assisted electrolytic machining method and device for implementing same

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