CN110172647A - A kind of preprocess method, vacuum carburization method and the steel alloy of steel alloy vacuum carburization - Google Patents
A kind of preprocess method, vacuum carburization method and the steel alloy of steel alloy vacuum carburization Download PDFInfo
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- CN110172647A CN110172647A CN201910636719.7A CN201910636719A CN110172647A CN 110172647 A CN110172647 A CN 110172647A CN 201910636719 A CN201910636719 A CN 201910636719A CN 110172647 A CN110172647 A CN 110172647A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- 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
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- 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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- 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
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- 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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- 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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- 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
- C23C8/20—Carburising
- C23C8/22—Carburising of ferrous surfaces
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Abstract
The present invention provides a kind of pretreated methods of steel alloy vacuum carburization, comprising: carries out supersonic microparticle bombardment to alloy steel matrix, obtains making Nano surface matrix；Rare earth ion injection processing is carried out to the making Nano surface matrix.Rare earth element is injected into alloy steel surface using ion implanting before vacuum carburization to have the function that urge infiltration by the present invention, but it is most only several microns thick to be limited to ion implanted layer, it carries out supersonic microparticle bombardment again before ion implanting rare earth and obtains the metal nano layer with high density of defects, high residual compressive stress, to increase the thickness of ion implanted layer, obtains and preferably urge infiltration effect.The present invention also provides the methods and steel alloy of a kind of steel alloy vacuum carburization.
Description
Technical field
The present invention relates to alloy Carburization Treatment technical field more particularly to a kind of pretreatment sides of steel alloy vacuum carburization
Method, vacuum carburization method and steel alloy.
Background technique
Vacuum carburization is the carburizing heat treatment technics carried out in vacuum environment, compared with atmosphere carburizing, can effectively be solved
Certainly intergranular oxidation and the problem of carbon black, makes material surface obtain high-intensitive, high rigidity martensitic structure, center portion keeps toughness.
Vacuum carburization shortens carburizing time at relatively high temperature, environmental protection and economy, but its that there are still carburizing temperatures is higher, carburizing is all
The problems such as phase is long, energy consumption is big.Therefore, it optimized in terms of vacuum carburization treatment process and improves carburizing efficiency, improved and seep
Layer quality extends alloy service life to meet the industrial requirement increasingly updated and have very big necessity.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preprocess methods of steel alloy vacuum carburization, vacuum carburization
Method and steel alloy, preprocess method provided by the invention are able to solve that diffusion layer organization existing for vacuum carburization is uneven, carburizing
The problems such as period is long, energy consumption is high.
The present invention provides a kind of pretreated methods of steel alloy vacuum carburization, comprising:
Supersonic microparticle bombardment is carried out to alloy steel matrix, obtains making Nano surface matrix；
Rare earth ion injection processing is carried out to the making Nano surface matrix.
The present invention provides it is a kind of for improve vacuum carburization rate and improve diffusion layer organization supersonic microparticle bombardment it is pre-
First carry out the vacuum carburization preprocess method of ion implanting rare earth again after matrix surface forms nano modification layer.
The present invention does not have special limitation, those skilled in the art to the type of the alloy steel matrix, ingredient and source
The steel alloy that can select heterogeneity according to actual needs, using the steel alloy of ingredient known to those skilled in the art.
In the present invention, the alloy steel matrix is preferably the steel alloy of 20Cr2Ni4A ingredient.In the present invention, described
The ingredient of alloy steel matrix is preferred are as follows:
The C of 0.17~0.23wt%；
The Si of 0.17~0.37wt%；
The Mn of 0.3~0.6wt%；
The S of≤0.03wt%；
The P of≤0.03wt%；
The Cr of 1.25~1.65wt%；
The Ni of 3.25~3.65wt%；
Surplus is Fe.
In the present invention, the mass content of the carbon is preferably 0.19~0.21%, and more preferably 0.2%；The Si's
Mass content is preferably 0.2~0.3%, and more preferably 0.23~0.27%, most preferably 0.25%；The mass content of the Mn
Preferably 0.4~0.5%, more preferably 0.45%；The mass content of the S preferably≤0.02%, more preferably≤0.01%；Institute
State P mass content preferably≤0.02%, more preferably≤0.01%；The mass content of the Cr is preferably 1.3~1.6%, more
Preferably 1.4~1.5%；The mass content of the Ni is preferably 3.3~3.6%, and more preferably 3.4~3.5%.
Preferably the alloy steel matrix is cut before carrying out the supersonic microparticle bombardment, is polished, is cleaned and
Drying.
The present invention does not have special limitation to the method for the cutting, is cut using steel alloy well known to those skilled in the art
The method cut is by the alloy steel matrix excision forming.
In the present invention, the polishing is preferably polished using sand paper, more preferably successively using 60#, 240#,
The sand paper of 400#, 600#, 800#, 1000#, 1500#, 2000# are polished.
In the present invention, the method for the cleaning is preferably cleaned by ultrasonic；The reagent of the cleaning is preferably ethyl alcohol, more excellent
It is selected as dehydrated alcohol.
In the present invention, supersonic microparticle bombardment is a kind of machining process of new acquisition making Nano surface, is benefit
It is carried hard solid particle using supersonic airstream as carrier with the basic principle of gas-solid two-phase flow and is bombarded with high kinetic energy
Metal surface, granule amount is very huge, and repeats to bombard, and makes metal surface that intense plastic strain occur, crystal grain refinement is straight
To nanometer scale.
The present invention has the fixture of alloy steel matrix to be placed on Supersonic preferably by alloy steel matrix clamping into fixture, by clamping
Supersonic microparticle bombardment Surface Nanocrystalline is carried out in the device of fast microparticle bombardment.
In the present invention, the hard particles material used during the supersonic microparticle bombardment is preferably aluminium oxide pottery
Porcelain；The granularity of the hard particles is preferably 100~200 microns, more preferably 120~180 microns, most preferably 140~160
Micron；Hard particles spray distance vertical with alloy steel matrix is preferably 10~20cm, more preferably 12~18cm, most preferably
For 14~16cm；The jet velocity of hard particles is preferably 300~1200m/s, more preferably 500~1000m/s, most preferably
600~800m/s.
Present invention preferably employs aluminium oxide ceramics as hard particles, with excellent mechanical strength, bombardment steel alloy
After matrix surface, breaking deformation will not occur for hard particles, generate the nanosizing surface layer of even compact in matrix surface.
In the present invention, preferred mobile spray gun makes alloy steel matrix surface difference position during the supersonic microparticle bombardment
Set the bombardment processing homogenized within the unit time.
In the present invention, nano modification layer, the nano modification layer are contained in the surface of the making Nano surface matrix
Refer to the nanometer deformation layer generated after Supersonic particles bombarding on alloy steel matrix surface, the crystalline substance in the nanometer deformation layer
Particle size reaches Nano grade, and minimum size of microcrystal reaches 5nm, and maximum size of microcrystal reaches 80nm, and average crystal grain partial size is
30nm, particle size distribution meet Gaussian Profile；The thickness of the nano modification layer is preferably 80~100 microns, more preferably
It is 85~95 microns, most preferably 90 microns.
The performance for the nanostructure layer surface pairing gold steel matrix that the present invention is obtained by supersonic microparticle bombardment has significantly
It influences, improves its mechanical property and chemical property, wherein nanometer layer hardness significantly increases, and from outward appearance to inner essence becomes in gradient
Change, gradually decrease, bond strength is high, will not occur to peel off easily and dissociate.
In the present invention, ion implanting is to be injected into required element in material with ionic state using high energy ion beam,
Under conditions of not changing the original size of material and roughness, Uniform Doped is realized；Nothing between ion implantation modification layer and matrix
Sharp interface ensure that the continuous transition of ion implantation modification layer Yu matrix room machine performance, avoid ion implantation modification layer
In conjunction with matrix loosely and caused by surface damage layer.
In the present invention, the rare earth ion that the rare earth ion injection processing uses is preferably ruthenium ion, and yttrium electronegativity is strong
And atomic radius is larger, and the distortion of lattice caused by alloy steel matrix surface is bigger, urges infiltration effect more preferable.
In the present invention, the equipment that the rare earth ion injection processing uses is preferably the linear ion implanting of MEVVA direct current
Machine.
In the present invention, the rare earth ion injection processing preferably carries out under conditions of vacuum, preferably by rare earth ion
The flood chamber of injection device is evacuated to vacuum.In the present invention, the vacuum degree of rare earth ion injection processing be preferably 0.5~
1.5×10-4Pa, more preferably 0.8~1.2 × 10-4Pa, most preferably 1 × 10-4Pa。
In the present invention, argon purge rare earth target (yttrium target) 3 is preferably used before the rare earth ion injection processing
~10min, more preferably 4~8min, most preferably 5~6min；In the cleaning process, preferably baffle is moved at target and is kept away
Exempt from impurity and is splashed to alloy steel matrix surface.
In the present invention, the injecting voltage of the rare earth ion injection processing is preferably 45~60KV, more preferably 50~
55KV；Rare earth ion implantation dosage is preferably 1 × 1017ion/cm2~2 × 1017ion/cm2, more preferably 1.2 × 1017ion/
cm2~1.8 × 1017ion/cm2, most preferably 1.4 × 1017ion/cm2~1.6 × 1017ion/cm2；Injecting temperature is preferably
25~100 DEG C, more preferably 30~80 DEG C, most preferably 40~60 DEG C.
The present invention, which combines supersonic microparticle bombardment with ion implanting, is used for urging infiltration, improving and seep for vacuum carburization heat treatment
Carbon-coating quality.The present invention is that diffusion layer organization is unevenly distributed, carbide is coarse, carburizing in the vacuum carburization heat treatment for solve steel alloy
The problems such as period is long, temperature is high, low efficiency proposes that a kind of supersonic speed making Nano surface technology is mutually tied with rare earth ion injection processing
The composite pretreating method of conjunction.
The present invention provides a kind of methods of steel alloy vacuum carburization, comprising:
Vacuum carburization processing is carried out after pre-processing to steel alloy again, the pretreated method is above-mentioned technical proposal
The pretreated method of steel alloy vacuum carburization.
In the present invention, the pretreated method of steel alloy vacuum carburization and steel alloy vacuum described in above-mentioned technical proposal
The pretreated method of carburizing is consistent, and details are not described herein.
In the present invention, the vacuum carburization processing preferably carries out in ECM vacuum carburization trial furnace；The vacuum carburization
The carburizing mode of processing is preferably gas pulses formula；The carburizing order of the vacuum carburization processing preferably successively carries out carburizing
Gas, cooling air, carburetted gas and cooling air；Carburizing medium, that is, carburetted gas of the vacuum carburization processing is preferably acetylene, cooling air
Preferably nitrogen；The temperature of the vacuum carburization processing is preferably 900~910 DEG C, and more preferably 902~908 DEG C, most preferably
904~906 DEG C；The carburizing time of the vacuum carburization processing is preferably 5~7 hours, and more preferably 6 hours；The carburizing is situated between
Matter, that is, carburetted gas flow is preferably 1000~2000m3/ h, more preferably 1200~1800m3/ h, most preferably 1400~
1600m3/h；The gas purity of the carburetted gas is preferably >=99%；The gas purity of the cooling air is preferably >=99%；It is described true
The vacuum degree of empty Carburization Treatment preferably 1 × 10-3Pa is hereinafter, more preferably 0.2~0.7 × 10-3Pa, most preferably 0.3~0.5
×10-3Pa。
The present invention can reduce carburizing temperature in vacuum carburization processing and contract after carrying out above-mentioned vacuum carburization pretreatment
Short carburizing time.
In the present invention, after the completion of the vacuum carburization processing, it is also preferable to include heat treatments；The heat-treating methods are excellent
It is selected as:
By vacuum carburization, treated that alloy steel matrix successively carries out high tempering processing, oil quenching, cold treatment, lonneal
With it is air-cooled.
The present invention carries out the intensity that high tempering can be improved the product of acquisition during heat treatment, and carrying out oil quenching can
The hardness and toughness of the product obtained are improved, the surface remained austenite content obtained after oil quenching is more and cold treatment ring is added
Section reduces residual austenite content, further increases the intensity of the product of acquisition, finally carry out lonneal, eliminate acquisition
The residual stress of product.The present invention is specifically added cold treatment link during heat treatment can further decrease retained austenite
Content with achieve the purpose that improve intensity.
In the present invention, the temperature of the high tempering processing is preferably 600~700 DEG C, and more preferably 620~680 DEG C,
Most preferably 640~660 DEG C；The time of the high tempering processing is preferably 2~4 hours, and more preferably 3 hours.
In the present invention, the temperature of the oil quenching is preferably 750~850 DEG C, and more preferably 780~820 DEG C, most preferably
800℃；The time of the oil quenching is preferably 1~2 hour, and more preferably 1.5 hours.In the present invention, the oil quenching uses
Oil is preferably vacuum quenching oil.
In the present invention, the temperature of the cold treatment is preferably -60~-130 DEG C, more preferably -70~-110 DEG C, optimal
It is selected as -80~-100 DEG C；The time of the cold treatment is preferably 1.5~2.5 hours, and more preferably 2 hours.
In the present invention, the time of the lonneal is preferably 150~200 DEG C, more preferably 160~190 DEG C, optimal
It is selected as 170~180 DEG C；The time of the lonneal is preferably 2~2.5 hours.
In the present invention, described air-cooled to be preferably air-cooled to room temperature.
In the present invention, heat-treating methods technique preferably as shown in Figure 1.
Rare earth element has very low electronegativity, and chemical property is very active, can make to be seeped matrix and lacks with carbon permeation
Fall into density proliferation, rare-earth energizer can be used to carry out carburizing, but inorganic rare earth energizer that there are rare earth utilization rates in answering is lower,
The problems such as level of residue is larger, energizer is easy failure.Organic rare-earth energizer can preferably solve inorganic rare earth energizer
Blocking pipeline problem, but the comparison of ingredients of organic rare-earth energizer is complicated, to techniques such as carbon potential, temperature in carburization process link
State modulator is more demanding, and the method for this addition rare-earth energizer is not particularly suited for vacuum carburization.
Rare earth element is injected into alloy steel surface using ion implanting before vacuum carburization and urges infiltration to reach by the present invention
Effect, but be limited to ion implanted layer most it is thick only several microns, before ion implanting rare earth again carry out supersonic microparticle bombardment obtain
Metal nano layer with high density of defects, high residual compressive stress, to increase the thickness of ion implanted layer, to improve rare earth member
Element urges infiltration effect.
It can only achieve micron level since the implanted layer of ion implanting is most deep, inject depth to increase, the present invention is right in advance
Metallic matrix carries out Surface Nanocrystalline, and the metal nano layer haveing excellent performance is prepared in matrix surface；Rare earth ion injection
The Microalloying Effect of distortion of lattice and rare earth is generated in matrix surface, forms one layer of rare earth implanted layer.
The present invention carries out vacuum carburization heat treatment after the completion of pre-processing, to pretreated steel alloy, and to infiltration
Hardness, carburized (case) depth of carbon treated alloy steel surface etc. carry out test analysis.
The present invention also provides a kind of steel alloy, the steel alloy is according to steel alloy vacuum described in above-mentioned technical proposal
The steel alloy that the method for carburizing is prepared.
The carburized layer of vacuum carburization method acquisition is carried out after the compound pretreatment of vacuum carburization provided by the invention with excellent
Mechanical property；Compared with existing vacuum carburization treatment process, the present invention is injected by supersonic microparticle bombardment and rare earth ion
The carburized layer obtained after combined processing through vacuum carburization, not only improves the structure property of carburized layer, also substantially reduces true
The cycle period of empty carburizing reduces heat treatment temperature, saves energy consumption.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is process of thermal treatment figure in the present invention；
Fig. 2 is the tissue topography of the steel alloy carburized layer of comparative example 1 of the present invention preparation；
Fig. 3 is the tissue topography of steel alloy carburized layer prepared by the embodiment of the present invention 1；
Fig. 4 is the tissue topography of steel alloy carburized layer prepared by the embodiment of the present invention 2；
Fig. 5 is the hardness distribution of steel alloy prepared by the embodiment of the present invention 1, embodiment 2 and comparative example 1；
Fig. 6 is the hardness distribution of steel alloy prepared by the embodiment of the present invention 3；
Fig. 7 is the hardness distribution of steel alloy prepared by the embodiment of the present invention 4；
Fig. 8 is the hardness distribution of the steel alloy of comparative example 2 of the present invention preparation.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Alloy steel matrix used by following embodiment of the present invention is the 20Cr2Ni4A steel that Iron and Steel Research Geueral Institute provides；
Used supersonic microparticle bombardment device is the supersonic microparticle bombardment equipment that ground force's armored force engineering institute provides；It is used
Rare earth ion injection device be 50 types that provide of Beijing Normal University's Nuclear Science and Technology institute the injection of MEVVA source ion
Machine；Used vacuum carburization device is that the ECM low-voltage vacuum that Inner Mongolia First Machinery Group Co., Ltd. (617 factory) provides seeps
Carbon trial furnace.
Embodiment 1
Alloy steel matrix is cut and formed, using acetone clean substrate material surface, according to this using 60#, 240#, 400#,
600#, 800#, 1000#, 1500#, 2000# sand paper polish smooth the basis material after cutting, then using dehydrated alcohol into
Row ultrasonic cleaning, the basis material after being cleaned after drying；
By the basis material clamping after cleaning into fixture, the fixture that clamping has basis material is obtained；
The fixture that clamping has basis material is placed in supersonic microparticle bombardment device and carries out Surface Nanocrystalline, in table
In the nanosizing treatment process of face, for the hard particles used for alumina ceramic grain, diameter is 100~200 μm, controls vertical spray
Penetrating distance is 15cm, jet velocity 800m/s, and mobile spray gun obtains substrate material surface different location within the unit time
Homogenization Treatments obtain the nano modification layer that depth is 80~100 μm.
The processing of rare earth yttrium ion implantation is carried out to basis material after supersonic microparticle bombardment processing, in MEVVA AC line
Property ion implantation apparatus in carry out rare earth element injection.Before ion implanting, it is 1 × 10 that flood chamber, which is first evacuated to vacuum,-4Pa then makes
With argon purge yttrium 3~10min of target, when cleaning, pays attention to moving to baffle at target, impurity is avoided to be splashed to alloy steel matrix
Surface.It is 50KV, implantation dosage 1.5 × 10 that injecting voltage is controlled in rare earth ion injection process17ion/cm2, inject temperature 60
℃。
The alloy steel matrix obtained after rare earth ion is injected is put into ECM vacuum carburization trial furnace, closes fire door, setting
Carburizing mode is gas pulses formula, and it is 0.5 × 10 that vacuum will be evacuated in furnace-4Pa, according to carburetted gas-cooling air-carburetted gas-cooling
The order of gas carries out Carburization Treatment to alloy steel matrix, and carburetted gas is acetylene (C2H2), cooling air is nitrogen (N2), carburizing temperature
It is 905 DEG C, carburizing time 6h, acetylene flow is 1500m3/ h, acetylene gas purity are 99% or more；Nitrogen gas purity is
99% or more.
After vacuum carburization, furnace is down to 650 DEG C of progress high tempering processing 3h, then takes out alloy base steel
Body carries out 1.5 hours oil quenchings (industrial media Co., Ltd, Shandong Cisco provides senc0-o90 vacuum quenching oil) at 800 DEG C,
Then cold treatment in 2 hours is carried out at -100 DEG C, 2.3 hours lonneals are finally carried out at 170 DEG C, takes out steel alloy
Matrix obtains steel alloy after being air-cooled to room temperature.
Using the infiltration of steel alloy prepared by the Nova NanoSEM450 type scanning electron microscope observation embodiment of the present invention 1
The tissue topography on carbon-coating (part that alloy steel surface contains C element is carburized layer) surface and section, testing result such as Fig. 4 institute
Show, it (b) is carburized layer center portion that (a), which is carburizing layer surface, in Fig. 4, (c) is carburizing layer cross section, uses TH702 type aobvious in the present invention
Microhardness instrument (vickers hardness tester) measures the hardness of carburized layer, and measurement load is 1Kg, hard from carburizing layer surface to Vickers
Degree is that the vertical range at 550HV is effective carburized (case) depth (being denoted as carburized (case) depth), and region of the hardness lower than 550HV is to seep
Carbon-coating center portion is carbonized from fig. 4, it can be seen that bulk carbide tissue does not occur in carburizing layer cross section after the injection of rare earth yttrium
Object is comparatively fine and is evenly distributed, and mating surface hardness and urges infiltration effect, it is known that yttrium injection urges infiltration and tissue to imitate carburizing
The raising of fruit becomes apparent.
Steel alloy carburized layer (the steel alloy table being prepared using the TH702 type microhardness tester test embodiment of the present invention 1
The part that C element is contained in face is carburized layer) section hardness, test load be 1000g, testing result is as shown in figure 5, by scheming
5 it is found that carburized layer section hardness is gradually decreased from surface to center portion after carburizing, and highest hardness is apart from carburizing layer surface 0.2mm
Place, hardness is up to 795HV, carburized (case) depth 1.18mm after pre-processing carburizing.
Embodiment 2
Steel alloy is prepared according to method described in embodiment 1, the difference from embodiment 1 is that the temperature of Carburization Treatment
It is 925 DEG C.
According to the tissue topography for the steel alloy carburized layer that the embodiment of the present invention 2 is prepared in method described in embodiment 1
Detected, testing result as shown in figure 3, in Fig. 3 (a) be carburizing layer surface, (b) be carburized layer center portion, (c) be carburized layer cut
Face, as seen from Figure 3, carburized layer superficial white residual austenite content is reduced after rare earth injection, and section distribution of carbides is more
To be uniform, the distribution of center portion ferrite and size do not occur significant change, Fig. 3 and Fig. 4 central part tissue no significant difference, but Fig. 4
The residual austenite content of middle carburized layer is significantly lower than Fig. 3, and the size of carbide is also more more tiny than Fig. 3, therefore, Fig. 4
In tissue topography it is more preferable.
The section hardness for the steel alloy permeable formation that the embodiment of the present invention 2 is prepared according to the method for embodiment 1 carries out
Detection, for testing result as shown in figure 5, carburized (case) depth is 1.16mm, hardness may be due to carburizing temperature lower than embodiment 1
It is higher to cause retained austenite and carbide more caused.
Embodiment 3
Alloy steel matrix is cut and formed, using acetone clean substrate material surface, according to this using 60#, 240#, 400#,
600#, 800#, 1000#, 1500#, 2000# sand paper polish smooth the basis material after cutting, then using dehydrated alcohol into
Row ultrasonic cleaning, the basis material after being cleaned after drying；
By the basis material clamping after cleaning into fixture, the fixture that clamping has basis material is obtained；
The fixture that clamping has basis material is placed in supersonic microparticle bombardment device and carries out Surface Nanocrystalline, in table
In the nanosizing treatment process of face, for the hard particles used for alumina ceramic grain, diameter is 100~200 μm, controls vertical spray
Penetrating distance is 10cm, jet velocity 300m/s, and mobile spray gun obtains substrate material surface different location within the unit time
Homogenization Treatments obtain the nano modification layer that depth is 80~100 μm.
The processing of rare earth yttrium ion implantation is carried out to basis material after supersonic microparticle bombardment processing, in MEVVA AC line
Property ion implantation apparatus in carry out rare earth element injection.Before ion implanting, flood chamber is first evacuated to vacuum to 1 × 10-4Pa then makes
With argon purge yttrium 3~10min of target, when cleaning, pays attention to moving to baffle at target, impurity is avoided to be splashed to alloy steel matrix
Surface.It is 45KV, implantation dosage 1 × 10 that injecting voltage is controlled in rare earth ion injection process17ion/cm2, inject 25 DEG C of temperature.
The alloy steel matrix obtained after rare earth ion is injected is put into ECM vacuum carburization trial furnace, closes fire door, setting
Carburizing mode is gas pulses formula, and vacuum will be evacuated in furnace to 0.5 × 10-4Pa, according to carburetted gas-cooling air-carburetted gas-cooling
The order of gas carries out Carburization Treatment to alloy steel matrix, and carburetted gas is acetylene (C2H2), cooling gas is nitrogen (N2), carburizing temperature
Degree is 900 DEG C, carburizing time 5h, and acetylene flow is 1000m3/ h, acetylene gas purity are 99% or more；Nitrogen gas purity
It is 99% or more.
After vacuum carburization, furnace is down to 600 DEG C of progress high tempering processing 2h, then takes out alloy base steel
Body carries out 1 hour oil quenching (the oily source used is with embodiment 1) at 750 DEG C, then carries out 2 hours cold places at -60 DEG C
Reason finally carries out 2 hours lonneals at 150 DEG C, takes out alloy steel matrix, obtains steel alloy after being air-cooled to room temperature.
The section hardness for the steel alloy permeable formation that the embodiment of the present invention 3 is prepared according to the method for embodiment 1 carries out
Detection, testing result is as shown in fig. 6, highest hardness appears in the depth of carburizing layer surface to 0.2mm, about 770HV, carburizing
Layer depth is 1.128mm.
Embodiment 4
Alloy steel matrix is cut and formed, using acetone clean substrate material surface, according to this using 60#, 240#, 400#,
600#, 800#, 1000#, 1500#, 2000# sand paper polish smooth the basis material after cutting, then using dehydrated alcohol into
Row ultrasonic cleaning, the basis material after being cleaned after drying；
By the basis material clamping after cleaning into fixture, the fixture that clamping has basis material is obtained；
The fixture that clamping has basis material is placed in supersonic microparticle bombardment device and carries out Surface Nanocrystalline, in table
In the nanosizing treatment process of face, for the hard particles used for alumina ceramic grain, diameter is 100~200 μm, controls vertical spray
Penetrating distance is 20cm, jet velocity 1200m/s, and mobile spray gun obtains substrate material surface different location within the unit time
Homogenization Treatments obtain the nano modification layer that depth is 80~100 μm.
The processing of rare earth yttrium ion implantation is carried out to basis material after supersonic microparticle bombardment processing, in MEVVA AC line
Property ion implantation apparatus in carry out rare earth element injection.Before ion implanting, flood chamber is first evacuated to vacuum to 1 × 10-4Pa then makes
With argon purge yttrium 3~10min of target, when cleaning, pays attention to moving to baffle at target, impurity is avoided to be splashed to alloy steel matrix
Surface.It is 60KV, implantation dosage 2 × 10 that injecting voltage is controlled in rare earth ion injection process17ion/cm2, inject temperature 100
℃。
The alloy steel matrix obtained after rare earth ion is injected is put into ECM vacuum carburization trial furnace, closes fire door, setting
Carburizing mode is gas pulses formula, and vacuum will be evacuated in furnace to 0.5 × 10-4Pa, according to carburetted gas-cooling air-carburetted gas-cooling
The order of gas carries out Carburization Treatment to alloy steel matrix, and carburetted gas is acetylene (C2H2), cooling gas is nitrogen (N2), carburizing temperature
Degree is 910 DEG C, carburizing time 7h, and acetylene flow is 2000m3/ h, acetylene gas purity are 99% or more；Nitrogen gas purity
It is 99% or more.
After vacuum carburization, furnace is down to 700 DEG C of progress high tempering processing 4h, then takes out alloy base steel
Body carries out 2 hours oil quenchings (used oil source is with embodiment 1) at 850 DEG C, then carries out at -130 DEG C 2 hours
Cold treatment finally carries out 2.5 hours lonneals at 200 DEG C, takes out alloy steel matrix, obtains alloy after being air-cooled to room temperature
Steel.
The section hardness for the steel alloy permeable formation that the embodiment of the present invention 4 is prepared according to the method for embodiment 1 carries out
Detection, testing result is as shown in fig. 7, highest hardness appears in carburizing layer surface to 0.2mm depth, for 783HV, carburized layer depth
Degree is 1.15mm.
Comparative example 1
Steel alloy is prepared according to the method for embodiment 2, the difference from example 2 is that, without supersonic microparticle
Bombardment and rare earth ion injection, directly carry out Carburization Treatment for alloy steel matrix.
According to the tissue topography for the steel alloy carburized layer that comparative example 1 of the present invention is prepared in method described in embodiment 1
Detected, testing result as shown in Fig. 2, in Fig. 2 (a) be carburizing layer surface, (b) be carburized layer center portion, (c) be carburized layer cut
Face, as seen from Figure 2, carburizing layer surface are tiny high carbon martensite and a small amount of white residual austenite, core structure
For lath martensite and a small amount of ferrite, section is made of martensite and a small amount of carbide；Carbide in Fig. 3 and Fig. 4 is big
It is small be significantly less than Fig. 2 and also distribution it is more uniform, white retained austenite quantity is considerably less than Fig. 2, the tissue in Fig. 2 compared with
Difference.
The section hardness for the steel alloy permeable formation that comparative example 1 of the present invention is prepared according to the method for embodiment 1 carries out
Detection, testing result is as shown in figure 5, carburized (case) depth is 1.05mm.
Comparative example 2
Steel alloy is prepared according to the method for embodiment 2, the difference from example 2 is that, carry out Carburization Treatment it
It is preceding that rare earth ion injection processing is only carried out without supersonic microparticle bombardment.
The section hardness for the steel alloy permeable formation that comparative example 2 of the present invention is prepared according to the method for embodiment 1 carries out
Detection, testing result is as shown in figure 8, highest hardness appears in carburizing layer surface to 0.2mm depth, for 769HV, carburized layer depth
Degree is 1.08mm.
As seen from the above embodiment, the present invention provides a kind of pretreated methods of steel alloy vacuum carburization, comprising: pairing
Golden steel matrix carries out supersonic microparticle bombardment, obtains making Nano surface matrix；To the making Nano surface matrix carry out rare earth from
Sub- injection processing.Rare earth element is injected into alloy steel surface using ion implanting before vacuum carburization and urges infiltration to reach by the present invention
Effect, but be limited to ion implanted layer most it is thick only several microns, before ion implanting rare earth again carry out supersonic microparticle bombardment obtain
To the metal nano layer with high density of defects, high residual compressive stress, to increase the thickness of ion implanted layer, acquisition is preferably urged
Seep effect.
Claims (10)
1. a kind of pretreated method of steel alloy vacuum carburization, comprising:
Supersonic microparticle bombardment is carried out to alloy steel matrix, obtains making Nano surface matrix；
Rare earth ion injection processing is carried out to the making Nano surface matrix.
2. the method according to claim 1, wherein the ingredient of the alloy steel matrix are as follows:
The C of 0.17~0.23wt%；
The Si of 0.17~0.37wt%；
The Mn of 0.3~0.6wt%；
The S of≤0.03wt%；
The P of≤0.03wt%；
The Cr of 1.25~1.65wt%；
The Ni of 3.25~3.65wt%；
Surplus is Fe.
3. the method according to claim 1, wherein the hard used during the supersonic microparticle bombardment
Grain material is aluminium oxide ceramics；The granularity of the hard particles is 100~200 microns.
4. the method according to claim 1, wherein hard particles and conjunction during the supersonic microparticle bombardment
The vertical spray distance of golden steel matrix is 10~20cm；The jet velocity of hard particles is 300~1200m/s.
5. the method according to claim 1, wherein the rare earth ion injection rare earth ion that uses of processing for
Ruthenium ion.
6. the method according to claim 1, wherein the rare earth ion injection processing injecting voltage be 45~
60KV；Rare earth ion implantation dosage is 1 × 1017ion/cm2~2 × 1017ion/cm2；Injecting temperature is 25~100 DEG C.
7. a kind of method of steel alloy vacuum carburization, comprising:
Vacuum carburization processing is carried out after pre-processing to steel alloy again；
The pretreated method is the pretreated method of steel alloy vacuum carburization described in claim 1.
8. the method according to the description of claim 7 is characterized in that the temperature of vacuum carburization processing is 900~910 DEG C；
The time of the vacuum carburization processing is 5~7 hours.
9. the method according to the description of claim 7 is characterized in that after the completion of vacuum carburization processing further include: heat treatment；
The heat-treating methods are as follows:
By vacuum carburization, treated that alloy steel matrix successively carries out high tempering processing, oil quenching, cold treatment, lonneal and sky
It is cold.
10. a kind of steel alloy that method of claim 7 is prepared.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07138755A (en) * | 1993-11-16 | 1995-05-30 | Nippon Steel Corp | Surface reforming method for iron and steel material |
| JPH07278783A (en) * | 1994-04-11 | 1995-10-24 | Nippon Steel Corp | Surface hardening method |
| JPH1147142A (en) * | 1997-08-07 | 1999-02-23 | Kaijirushi Hamono Kaihatsu Center:Kk | Skin cutting instrument |
| CN103252461A (en) * | 2013-05-13 | 2013-08-21 | 山西太钢不锈钢股份有限公司 | Method for pouring electrode billet |
| CN104928586A (en) * | 2015-06-30 | 2015-09-23 | 宝山钢铁股份有限公司 | Hot stamping die steel and production method thereof |
| CN106868466A (en) * | 2017-01-23 | 2017-06-20 | 哈尔滨工程大学 | A kind of rare earth injection processing method for lifting vacuum carburization efficiency |
| CN108179374A (en) * | 2018-01-30 | 2018-06-19 | 哈尔滨工程大学 | A kind of method for making Nano surface for accelerating vacuum carburization rate |
| CN108179375A (en) * | 2018-01-30 | 2018-06-19 | 哈尔滨工程大学 | The carburizing of alloy steel products surface vacuum and ion implanting compound hardening treatment method |
-
2019
- 2019-07-15 CN CN201910636719.7A patent/CN110172647B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07138755A (en) * | 1993-11-16 | 1995-05-30 | Nippon Steel Corp | Surface reforming method for iron and steel material |
| JPH07278783A (en) * | 1994-04-11 | 1995-10-24 | Nippon Steel Corp | Surface hardening method |
| JPH1147142A (en) * | 1997-08-07 | 1999-02-23 | Kaijirushi Hamono Kaihatsu Center:Kk | Skin cutting instrument |
| CN103252461A (en) * | 2013-05-13 | 2013-08-21 | 山西太钢不锈钢股份有限公司 | Method for pouring electrode billet |
| CN104928586A (en) * | 2015-06-30 | 2015-09-23 | 宝山钢铁股份有限公司 | Hot stamping die steel and production method thereof |
| CN106868466A (en) * | 2017-01-23 | 2017-06-20 | 哈尔滨工程大学 | A kind of rare earth injection processing method for lifting vacuum carburization efficiency |
| CN108179374A (en) * | 2018-01-30 | 2018-06-19 | 哈尔滨工程大学 | A kind of method for making Nano surface for accelerating vacuum carburization rate |
| CN108179375A (en) * | 2018-01-30 | 2018-06-19 | 哈尔滨工程大学 | The carburizing of alloy steel products surface vacuum and ion implanting compound hardening treatment method |
Non-Patent Citations (2)
| Title |
|---|
| 吕晓仁，李曙，刘阳: ""不同含碳量Fe-C合金表面纳米化行为的分析"", 《中国表面工程》 * |
| 张亨金 等: ""Q235钢表面纳米化处理对离子注入的影响"", 《太原理工大学学报》 * |
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