CN102061441B - Method for realizing steel surface layer nanocrystallization based on thermal diffusing permeation process - Google Patents
Method for realizing steel surface layer nanocrystallization based on thermal diffusing permeation process Download PDFInfo
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- CN102061441B CN102061441B CN201110031571A CN201110031571A CN102061441B CN 102061441 B CN102061441 B CN 102061441B CN 201110031571 A CN201110031571 A CN 201110031571A CN 201110031571 A CN201110031571 A CN 201110031571A CN 102061441 B CN102061441 B CN 102061441B
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Abstract
The invention discloses a method for realizing steel surface layer nanocrystallization based on a thermal diffusing permeation process, relating to a method for modifying the surface of steel. The method solves the technical problems of poor toughness performance, small thickness and complex process of a modified layer prepared with the traditional thermal diffusing permeation modification method for steel surface layers. The method comprises the following steps of: putting clean solid-solution steel into a pulse plasma multielement carburization furnace; applying voltage of 450-700V after evacuating, and keeping for 10-20min; introducing a dopant, and keeping for 2-100h at the temperature of 340-520DEG C and the pressure of 100-600Pa; and cooling to finish the process of steel surface layer nanocrystallization. The thickness of the nanocrystallization modified layer is 10-500mum, the surface hardness is 1020-1400HV, and a friction coefficient is lowered by 12-38% than that of unprocessed steel. The method can be used for long service life surface modification for a high-speed impact transmission piece.
Description
Technical field
The present invention relates to the method for the surface-treated of steel.
Background technology
Because the inefficacy (for example wearing and tearing, fatigue, corrosion etc.) of steelwork generally occurs in the surface, so surface-treated receives investigation of materials person's attention always.Common surface modifying method is a chemical heat treatment method, and instant heating expands infiltration method, and it comprises nitriding, carburizing and carbonitriding etc.Can improve its surface property (like anti-corrosion, wear-resisting, anti-fatigue performance etc.) after the steel alloy product is handled through nitriding, prolong its service life.But the common problem that nitrided case exists is that intensity is high, toughness is low.For stainless steel; Can increase substantially its surface strength through the nitriding processing; Can expand its Application Areas, but owing in upper layer, can form the nitride or the carbide of chromium behind conventional nitriding/carbonitriding, so the surface reforming layer corrosion resisting property significantly descends; And fragility is high, under impact loading, is prone to burst apart.
Open day be on July 25th, 2000 application number be that patent and the T.Christiansen of Denmark etc. of U.S. of 6093303 have carried out low-temperature plasma carburizing and gas cementation exploration to the austenitic stainless steel surface respectively at the disclosed Low TemperatureGaseous of " Surface Engineering " 2005 the 21st volumes 5-6 phase 445-455 page or leaf Nitriding and Carburising of Stainless Steel.; In its upper layer, obtained toughness modified layer preferably; But, adopt above-mentioned Technology can't realize the infiltration layer nanometer.Therefore, the carburized layer hardness＜1000HV that obtains, hardness is relatively low, and the thickness of surface cementation layer is less than 50 μ m in addition, and cementation zone still approaches and poor toughness, and the contact load that can bear is lower.
Lin Yimin etc. utilize the nitrided case of the method for making Nano surface and low temperature nitriding at the surface of steel acquisition hardness height and good toughness at 22 the 3rd phases of volume of " thermal treatment " 2007 29 pages disclosed " the pulse direct current plasma nitriding research of ferrous materials " and W.P.Tong etc. at " Science " 2003 the 299th volumes the 31st phase 686-688 page or leaf disclosed " Nitriding Iron at Lower Temperatures "; This method adopts the method for surface mechanical attrition to obtain certain thickness making Nano surface layer on the surface of steel earlier; Carrying out nitriding then at low temperatures handles; Modified layer hardness H.T. is better; But technology is comparatively complicated; Especially complicated shape are implemented comparatively difficulty of surperficial mechanical nanometer, so the range of application of this recombining process is restricted.
Summary of the invention
The present invention is that the modified layer toughness and tenacity that will solve the method for existing steel surface heat penetration modification preparation is worked poor, the technical problem of thin thickness and complex process, expands the method that the technology of oozing realizes steel upper layer nanometer and provide a kind of based on heat.
Of the present inventionly a kind ofly expand the technology of oozing based on heat and realize that the method for steel upper layer nanometer carries out according to the following steps: one, with 240#, 800# and 1200# waterproof abrasive paper with solid solution attitude steel surface finish light after; Be successively placed on ultrasonic cleaning in ethanol and the zero(ppm) water, obtain clean solid solution attitude steel; Two, the solid solution attitude steel that step 1 is obtained is put on the specimen mounting of pulsed plasma multiple permeation stove, is 20Pa～0.1Pa with pulsed plasma multiple permeation stove evacuation to vacuum tightness, applies the voltage of 450V～700V then and keeps 10min～20min; Three, feeding penetration enhancer to pulsed plasma multiple permeation stove, is that 340 ℃～520 ℃, pressure are to keep 2h～100h under the condition of 100Pa～600Pa in temperature; Four, after insulation finishes, make steel at N
2Or NH
3Be cooled to room temperature under the atmosphere, accomplish the process of steel upper layer nanometer; Wherein the penetration enhancer in the step 3 is compsn, nitriding medium or the carburizing agent of compsn, nitriding medium and the RE-Carburizing agent of nitriding medium and carburizing agent; Wherein the steel in the step 1 is a steel alloy.
Of the present inventionly expand the technology of oozing based on heat and realize that the method for steel upper layer nanometer is directly handled on solution hardening attitude steel alloy surface through the nitriding of low-temperature ion body, carburizing, carbonitriding or rare earth carbonitriding and form thickness at the regulatable nanometer crystal layer of 10 μ m～500 mu m ranges; The toughness on steel surface is improved; Surface hardness reaches 1020HV～1400HV simultaneously; Have good tough cooperation, wear rate obviously reduces than untreated steel, and coefficient of friction reduces by 12%～38% than untreated steel; The steel that oozes processing through overheated expansion is compared the corrosion potential ratio and is shuffled with untreated steel, corrosion electric current density reduces, and corrosion resistance nature improves; Nanometer crystal layer through the steel surface that the heat expansion is oozed can bear up to the contact load of 1kg does not have the phenomenon of bursting apart, and has high toughness, can be used for high speed impact driving member long lifetime surface-treated.
Method of the present invention does not reduce the erosion resistance of steel improving steel surface hardness and wear resistance and improving flexible simultaneously.And can be directed against solid solution attitude Nitralloy, PH Stainless Steel is directly implemented plasma surface and oozed altogether, follows timeliness to make matrix be able to strengthen when oozing altogether, simplifies heat treatment step, and is simple to operate.
Description of drawings
Fig. 1 is the X-ray diffraction analysis spectrogram of the stainless co-penetration layer of 17-4PH of step 1 obtains in the embodiment 22 solid solution attitude 17-4PH stainless steel and the upper layer nanometer that obtains through step 4; Wherein a is the stainless X ray diffracting spectrum of solid solution attitude 17-4PH that step 1 obtains, and b is the X ray diffracting spectrum at the surperficial 40 μ m places of distance in the stainless co-penetration layer of 17-4PH of the upper layer nanometer that step 4 obtains; Fig. 2 is the stainless metallography microscope photo of solid solution attitude 17-4PH that step 1 obtains in the embodiment 22; Fig. 3 be in the embodiment 22 ree content in the stainless co-penetration layer of 17-4PH of the upper layer nanometer that step 4 obtains with graph of relation apart from surface distance; Fig. 4 is the transmission electron microscope photo at the surperficial 40 μ m places of distance of the stainless co-penetration layer of 17-4PH of the upper layer nanometer that obtains through step 4 in the embodiment 22; Fig. 5 is the electron-diffraction diagram of tissue at the surperficial 40 μ m places of the stainless distance of 17-4PH of the upper layer nanometer that obtains through step 4 in the embodiment 22; Fig. 6 is the microhardness distribution curve of the stainless co-penetration layer of 17-4PH of the upper layer nanometer that obtains through step 4 in the embodiment 22; Fig. 7 is the stainless frictional coefficient of 17-4PH of the solid solution attitude 17-4PH stainless steel that obtains of the step 1 of embodiment 23 and the upper layer nanometer that obtains through the step 4 change of time graph of relation that rubs at any time; Wherein a is the stainless frictional coefficient of solid solution attitude 17-4PH that step 1 the obtains change of time relation curve that rubs at any time, and b is the frictional coefficient of the stainless co-penetration layer of 17-4PH of the upper layer nanometer that obtains through the step 4 change of time relation curve that rubs at any time; Fig. 8 is the stainless electrokinetic potential polarization of electrode of the 17-4PH graphic representation of the solid solution attitude 17-4PH stainless steel that obtains through step 1 in the embodiment 23 and the upper layer nanometer that obtains through step 4; Wherein a is the stainless electrokinetic potential polarization of electrode of the solid solution attitude 17-4PH curve that step 1 obtains, and b is the stainless electrokinetic potential polarization of electrode of the 17-4PH curve of the upper layer nanometer that obtains through step 4; Fig. 9 is the X-ray diffraction analysis spectrogram of co-penetration layer of the 8CrMoAl steel of step 1 obtains in the embodiment 24 solid solution attitude 8CrMoAl steel and the upper layer nanometer that obtains through step 4; Wherein a is the X-ray diffraction spectrum of the solid solution attitude 38CrMoAl steel that obtains of step 1; B be in the co-penetration layer of solid solution attitude 38CrMoAl steel of the upper layer nanometer that obtains of step 4 apart from the X-ray diffraction spectrum at surperficial 30 μ m places, c is the X-ray diffraction spectrum at the surperficial 80 μ m places of distance in the co-penetration layer of solid solution attitude 38CrMoAl steel of the upper layer nanometer that obtains of step 4; Figure 10 be in the embodiment 24 in the co-penetration layer of the 8CrMoAl steel of the upper layer nanometer that step 4 obtains apart from the transmission electron microscope photo at surperficial 30 μ m places; Figure 11 is the microhardness distribution curve of the 8CrMoAl steel co-penetration layer of the upper layer nanometer that obtains through step 4 in the embodiment 24; Figure 12 is the microhardness distribution curve of the 8CrMoAl steel co-penetration layer of the upper layer nanometer that obtains through step 4 in the embodiment 25.Figure 13 is the microhardness distribution curve of the 8CrMoAl steel co-penetration layer of the upper layer nanometer that obtains through step 4 in the embodiment 26.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment a kind of expands the technology of oozing based on heat and realizes that the method for steel upper layer nanometer carries out according to the following steps: one, with 240#, 800# and 1200# waterproof abrasive paper with solid solution attitude steel surface finish light after; Be successively placed on ultrasonic cleaning in ethanol and the zero(ppm) water, obtain clean solid solution attitude steel; Two, the solid solution attitude steel that step 1 is obtained is put on the specimen mounting of pulsed plasma multiple permeation stove, is 20Pa～0.1Pa with pulsed plasma multiple permeation stove evacuation to vacuum tightness, applies the voltage of 450V～700V then and keeps 10min～20min; Three, feeding penetration enhancer to pulsed plasma multiple permeation stove, is that 340 ℃～520 ℃, pressure are to keep 2h～100h under the condition of 100Pa～600Pa in temperature; Four, after insulation finishes, make steel at N
2Or NH
3Be cooled to room temperature under the atmosphere, accomplish the process of steel upper layer nanometer; Wherein the penetration enhancer in the step 3 is compsn, nitriding medium or the carburizing agent of compsn, nitriding medium and the RE-Carburizing agent of nitriding medium and carburizing agent; Wherein the steel in the step 1 is a steel alloy.
The effect of step 2 is pollutant and the oxide layer stripping with stainless steel surfaces in the present embodiment, after stainless steel surfaces does not have obvious arc to show, illustrates that the pollutant of stainless steel surfaces and oxide layer peel off removal fully.
The expanding the technology of oozing based on heat and realize that the method for steel upper layer nanometer is directly handled on solution hardening attitude steel alloy surface through the nitriding of low-temperature ion body, carburizing, carbonitriding or rare earth carbonitriding and form thickness of this embodiment at the regulatable nanometer crystal layer of 10 μ m～500 mu m ranges; The toughness on steel surface is improved; Surface hardness reaches 1020HV～1400HV simultaneously; Has good tough cooperation; Wear rate obviously reduces than untreated steel, and coefficient of friction reduces by 12%～38% than untreated steel; The steel that oozes processing through overheated expansion is compared the corrosion potential ratio and is shuffled with untreated steel, corrosion electric current density reduces, and corrosion resistance nature improves; The nanometer crystal layer that expands the steel surface of oozing through heat can bear the contact load of 1kg and not have the phenomenon of bursting apart, and has high toughness, can be used for high speed impact driving member long lifetime surface-treated.The method of this embodiment does not reduce the erosion resistance of steel improving the steel surface hardness and wear resistance and improving flexible simultaneously.And can be directed against solid solution attitude Nitralloy, PH Stainless Steel is directly implemented plasma surface and oozed altogether, follows timeliness to make matrix be able to strengthen when oozing altogether, simplifies heat treatment step, and is simple to operate.
Embodiment two: what this embodiment and embodiment one were different is: the solution treatment of the steel in the step 1 be with steel be placed on temperature be incubated 0.5h～2h under 900 ℃～1200 ℃ the condition after, oil cooling is accomplished solution treatment.Other is identical with embodiment one.
Embodiment three: what this embodiment and embodiment one were different is: the solution treatment of the steel in the step 1 be with steel be placed on temperature be incubated 0.8h～1.8h under 950 ℃～1150 ℃ the condition after, oil cooling is accomplished solution treatment.Other is identical with embodiment one.
Embodiment four: what this embodiment and embodiment one were different is: the solution treatment of the steel in the step 1 is that steel is placed on temperature is under 1000 ℃ the condition behind the insulation 1.2h, and oil cooling is accomplished solution treatment.Other is identical with embodiment one.
Embodiment five: what this embodiment was different with one of embodiment one to four is: described nitriding medium is H
2With NH
3Be 1～3: 1 mixed gas by volume or be H
2With N
2Be 1～9: 1 mixed gas or NH by volume
3Other is identical with one of embodiment one to four.
Embodiment six: what this embodiment was different with one of embodiment one to four is: described nitriding medium is H
2With NH
3Be 1.2～2.8: 1 mixed gas by volume or be H
2With N
2Be 2～8: 1 mixed gas by volume.Other is identical with one of embodiment one to four.
Embodiment seven: what this embodiment was different with one of embodiment one to four is: described nitriding medium is H
2With NH
3The mixed gas that is 2: 1 by volume perhaps is H
2With N
2Be 5: 1 mixed gas by volume.Other is identical with one of embodiment one to four.
Embodiment eight: what this embodiment was different with one of embodiment one to four is: described carburizing agent is methyl alcohol, ethanol or Virahol.Other is identical with one of embodiment one to four.
Embodiment nine: what this embodiment was different with one of embodiment one to four is: described RE-Carburizing agent is with containing La or/and the salt of Ce dissolves in the saturated alcohol solution that forms in methyl alcohol, ethanol or the Virahol.Other is identical with one of embodiment one to four.
Embodiment ten: what this embodiment was different with one of embodiment one to nine is: when penetration enhancer was nitriding medium, the volumetric flow rate of nitriding medium was 0.025L/min～0.3L/min.Other is identical with one of embodiment one to nine.
Embodiment 11: what this embodiment was different with one of embodiment one to nine is: when penetration enhancer was nitriding medium, the volumetric flow rate of nitriding medium was 0.2L/min.Other is identical with one of embodiment one to nine.
Embodiment 12: what this embodiment was different with one of embodiment one to nine is: when penetration enhancer was carburizing agent, the volumetric flow rate of carburizing agent was 0.025L/min～0.3L/min.Other is identical with one of embodiment one to nine.
Embodiment 13: what this embodiment was different with one of embodiment one to nine is: when penetration enhancer was carburizing agent, the volumetric flow rate of carburizing agent was 0.2L/min.Other is identical with one of embodiment one to nine.
Embodiment 14: what this embodiment was different with one of embodiment one to nine is: when penetration enhancer was nitriding medium and carburizing agent combination, the volumetric flow rate of nitriding medium was 0.025L/min～0.3L/min, alcohol in the carburizing agent and the N in the nitriding medium
2Or NH
3The ratio of volumetric flow rate be 0.25～3: 1.Other is identical with one of embodiment one to nine.
Embodiment 15: what this embodiment was different with one of embodiment one to nine is: when penetration enhancer was nitriding medium and carburizing agent combination, the volumetric flow rate of nitriding medium was 0.2L/min, alcohol in the carburizing agent and the N in the nitriding medium
2Or NH
3The ratio of volumetric flow rate be 1.5: 1.Other is identical with one of embodiment one to nine.
Embodiment 16: what this embodiment was different with one of embodiment one to nine is: when penetration enhancer is the compsn of nitriding medium and RE-Carburizing agent formation; The volumetric flow rate of nitriding medium is 0.025L/min～0.3L/min, alcohol in the carburizing agent and the N in the nitriding medium
2Or NH
3The ratio of volumetric flow rate be 0.25～3: 1.Other is identical with one of embodiment one to nine.
Embodiment 17: what this embodiment was different with one of embodiment one to nine is: when penetration enhancer was the compsn of nitriding medium and RE-Carburizing agent formation, the volumetric flow rate of nitriding medium was 0.15L/min, alcohol in the carburizing agent and the N in the nitriding medium
2Or NH
3The ratio of volumetric flow rate be 2: 1.Other is identical with one of embodiment one to nine.
Embodiment 18: what this embodiment was different with one of embodiment one to 17 is: the vacuum tightness that pulsed plasma multiple permeation stove is taken out in the step 2 is 18Pa～0.5Pa, and voltage is 500V～650V, and the hold-time is 11min～18min.Other is identical with one of embodiment one to 17.
Embodiment 19: what this embodiment was different with one of embodiment one to 17 is: the vacuum tightness that pulsed plasma multiple permeation stove is taken out in the step 2 is 10Pa, and voltage is 550V, and the hold-time is 15min.Other is identical with one of embodiment one to 17.
Embodiment 20: what this embodiment was different with one of embodiment one to 19 is: temperature is 350 ℃～500 ℃ in the step 3, and pressure is 200Pa～550Pa, and the hold-time is 3h～80h.Other is identical with one of embodiment one to 19.
Embodiment 21: what this embodiment was different with one of embodiment one to 19 is: temperature is 400 ℃ in the step 3, and pressure is 300Pa, and the hold-time is 10h.Other is identical with one of embodiment one to 19.
Embodiment 22: this embodiment a kind of expands the technology of oozing based on heat and realize that the method for steel upper layer nanometer carries out according to the following steps: one, the 17-4PH stainless steel being placed on temperature is under 1040 ℃ the condition behind the insulation 1h; Oil cooling; Obtain solid solution attitude 17-4PH stainless steel; With 240#, 800# and 1200# waterproof abrasive paper that the polishing of solid solution attitude 17-4PH stainless steel surface is bright successively then, be successively placed on ultrasonic cleaning in ethanol and the zero(ppm) water again, obtain clean solid solution attitude 17-4PH stainless steel; Two, the solid solution attitude 17-4PH stainless steel that step 1 is obtained is put on the specimen mounting of pulsed plasma multiple permeation stove, is 10Pa with pulsed plasma multiple permeation stove evacuation to vacuum tightness, applies the voltage of 650V then and keeps 15min; Three, with H
2And N
2The mixed gas that is 3: 1 by volume is a nitriding medium, is that 1: 1 the Lanthanum trinitrate and the saturated ethanolic soln of cerous nitrate are the RE-Carburizing agent with mol ratio, and the speed with 0.1L/min feeds H to pulsed plasma multiple permeation stove earlier
2, when temperature rises to 200 ℃, with H
2Flow velocity increase and to be 0.3L/min, and feed N to pulsed plasma multiple permeation stove with the speed of 0.1L/min
2When temperature rises to 440 ℃, again the RE-Carburizing agent is fed in the pulsed plasma multiple permeation stove ethanol in the RE-Carburizing agent and N
2Volume ratio be 1: 1, be that 500 ℃, pressure are to keep 4h under the condition of 300Pa in temperature then; Four, after insulation finishes, stop to import H
2With the RE-Carburizing agent, make steel at N
2Be cooled to room temperature under the atmosphere, accomplish the process of 17-4PH Stainless Steel Watch surface layer nanometer.
It is the nanometer crystal layer of 55 μ m～60 μ m that this embodiment of this embodiment has obtained thickness at solid solution attitude 17-4PH stainless steel surface.
The stainless co-penetration layer of 17-4PH of solid solution attitude 17-4PH stainless steel that step 1 is obtained and the upper layer nanometer that obtains through step 4 carries out X-ray diffraction analysis; Testing tool: D/max-rB type rotating anode X-ray diffractometer; Diffraction conditions: Cu-K α radiation; Voltage 40kV, electric current 80mA.The X ray diffracting spectrum that obtains is as shown in Figure 1, and wherein a is the stainless X ray diffracting spectrum of solid solution attitude 17-4PH that step 1 obtains; B is the X ray diffracting spectrum at the surperficial 40 μ m places of the stainless distance of 17-4PH of the upper layer nanometer that obtains through step 4.As can beappreciated from fig. 1; Solid solution attitude 17-4PH stainless steel is α '-Fe; And be organized as single-phase α '-Fe apart from surperficial 40 μ m places in the co-penetration layer of the 17-4PH stainless steel surface of upper layer nanometer; With standard card contrast, obvious wideization of each diffraction peak also has certain skew to the low angle scope, has nanocrystalline characteristic.
This embodiment is tested the stainless original grain of solid solution attitude 17-4PH, and method is: the K that takes by weighing 1g
2MnO
4, 10mL H
2SO
4With the zero(ppm) water of 100mL and mix, obtain corrosive fluid; Solid solution attitude 17-4PH stainless steel sample is corroded with corrosive fluid with 240#～1500# sand paper grinding and polishing back, dry up then, under the CMM-33E metaloscope, observe and photograph, the stainless metallography microscope photo of solid solution attitude 17-4PH that obtains is as shown in Figure 2.As can beappreciated from fig. 2 solid solution attitude 17-4PH stainless steel original grain size is at 30 μ m～50 mu m ranges.
The ree content of this embodiment in the stainless co-penetration layer of 17-4PH of the upper layer nanometer that step 4 obtains is as shown in Figure 3 with the relation curve apart from surface distance; Wherein the content of
expression lanthanum is with the relation curve apart from surface distance; The content of
expression cerium is with apart from the relation curve of surface distance as can beappreciated from fig. 3; At the thickness that this embodiment obtains is in the nanocrystalline co-penetration layer of 55 μ m～60 μ m, has infiltrated REE more equably.
The stainless co-penetration layer of 17-4PH of the upper layer nanometer that this embodiment is obtained through step 4 cuts down from substrate; Co-penetration layer thickness is 0.3mm; The surface is manual to be milled to apart from surperficial 40 μ m from oozing altogether earlier; Be milled to 50 μ m from base side is manual then, carry out thinning single surface with the ion milling etching apparatus from substrate one side again, obtain the plane transmission electron microscopic sample of co-penetration layer; Utilize Philips CM12 type TEM that the stainless co-penetration layer of 17-4PH of the upper layer nanometer that obtains through step 4 is carried out transmission electron microscope (TEM) apart from the tissue at surperficial 40 μ m places then and observe, test condition: acceleration voltage is 120kV.The transmission electron microscope photo that obtains is as shown in Figure 4, as can beappreciated from fig. 4, is nanocrystal apart from surperficial 40 μ m places.
The electron-diffraction diagram of the tissue at the surperficial 40 μ m places of the stainless distance of the 17-4PH of upper layer nanometer is as shown in Figure 5, can find out from Fig. 4 and Fig. 5, and the single-phase α ' in this zone, grain-size is 40nm～60nm nanometer.
The stainless co-penetration layer of 17-4PH of the upper layer nanometer that this embodiment is obtained through step 4 carries out micro-hardness testing; Test condition: adopt HV-1000 type micro Vickers; Load is 100g, and the loading time is 15s, and the microhardness distribution curve of acquisition is as shown in Figure 6.As can beappreciated from fig. 6, the thickness of the stainless co-penetration layer of 17-4PH of upper layer nanometer is 40 μ m～45 μ m, and the hardness of co-penetration layer is up to HV
0.11286.
The method of this embodiment does not reduce stainless erosion resistance improving the stainless steel surface hardness and wear resistance and improving flexible simultaneously.And directly implement plasma surface and ooze altogether, follow timeliness to make matrix be able to strengthen when oozing altogether, simplify heat treatment step, simple to operate.
Embodiment 23: this embodiment a kind of expands the technology of oozing based on heat and realize that the method for steel upper layer nanometer carries out according to the following steps: one, the 17-4PH stainless steel being placed on temperature is under 1040 ℃ the condition behind the insulation 1h; Oil cooling; Obtain solid solution attitude 17-4PH stainless steel; With 240#, 800# and 1200# waterproof abrasive paper that the polishing of solid solution attitude 17-4PH stainless steel surface is bright successively then, be successively placed on ultrasonic cleaning in ethanol and the zero(ppm) water again, obtain clean solid solution attitude 17-4PH stainless steel; Two, the solid solution attitude 17-4PH stainless steel that step 1 is obtained is put on the specimen mounting of pulsed plasma multiple permeation stove, is 8Pa with pulsed plasma multiple permeation stove evacuation to vacuum tightness, applies the voltage of 650V then and keeps 15min; Three, with H
2And N
2The mixed gas that is 3: 1 by volume is a nitriding medium, is carburizing agent with ethanol, and the speed with 0.1L/min feeds H to pulsed plasma multiple permeation stove earlier
2, when temperature rises to 200 ℃, with H
2Flow velocity increase and to be 0.9L/min, and feed N to pulsed plasma multiple permeation stove with the speed of 0.3L/min
2When temperature rises to 410 ℃, again ethanol is fed in the pulsed plasma multiple permeation stove ethanol and N
2Volume ratio be 2.5: 1, be that 430 ℃, pressure are to keep 8h under the condition of 500Pa in temperature then; Four, after insulation finishes, stop to import H
2And ethanol, make steel at N
2Be cooled to room temperature under the atmosphere, accomplish the process of steel upper layer nanometer.
It is 40 μ m～45 μ m nanometer crystal layers that this embodiment has obtained thickness at solid solution attitude 17-4PH stainless steel surface.
The stainless co-penetration layer of 17-4PH of solid solution attitude 17-4PH stainless steel that this embodiment step 1 is obtained and the upper layer nanometer that obtains through step 4 carries out rub(bing)test; The frictional coefficient that the obtains change of time relation curve that rubs at any time is as shown in Figure 7; Wherein a is the stainless frictional coefficient of the solid solution attitude 17-4PH change of time relation curve that rubs at any time; B is the frictional coefficient of the stainless co-penetration layer of 17-4PH of the upper layer nanometer change of time relation curve that rubs at any time; As can beappreciated from fig. 7, the stainless coefficient of friction of the 17-4PH of the upper layer nanometer coefficient of friction low 14.7%～35% more stainless than solid solution attitude 17-4PH.
The stainless co-penetration layer of 17-4PH of the upper layer nanometer that this embodiment is obtained through step 4 carries out the test of electrochemistry corrosion resistance nature; And with the solid solution attitude 17-4PH stainless steel that obtains in this embodiment step 1 as contrast; Corrosive nature testing tool and condition: the Model 273A type potentiostat of U.S. Perkin Elmer company and corresponding 352SoftCorr III software, adopting traditional three-electrode system (is that working electrode is a 17-4PH stainless steel sample; Reference electrode is the SCE that includes KCl solution; Supporting electrode is a graphite rod); Ionogen is selected the NaCl solution of 3.5wt.% for use, and it is 10mm that electrode test face exposes diameter.Earlier sample is stablized 300s in electrolyte solution before the test, begin scanning with the 0.5mV/s scanning speed with respect to the following 200mV of open circuit potential then, when current density reaches 10
-2A/cm
2In time, finish to scan.The electrokinetic potential polarization of electrode curve that test obtains is as shown in Figure 8; Wherein a is the stainless electrokinetic potential polarization of electrode of the 17-4PH curve of the upper layer nanometer that obtains through step 4; The solid solution attitude 17-4PH stainless electrokinetic potential polarization of electrode curve of b for obtaining through step 1; Can know that by Fig. 8 the stainless corrosion potential of the 17-4PH of upper layer nanometer is-278mV, compare and the stainless corrosion potential of the solid solution attitude 17-4PH (408mV) 130mV that shuffled; And Passivation Curve obviously moves to left, and shows that the stainless corrosion resistance nature of 17-4PH of upper layer nanometer is greatly improved.
The method that technology realization steel upper layer nanometer is oozed in the expansion based on heat of this embodiment directly forms the nanometer crystal layer through low-temperature ion body carbonitriding at solid solution attitude stainless steel surface; Improve surface hardness and wear resistance and improving flexible simultaneously; The erosion resistance of steel is not reduced, and simple to operate.
Embodiment 24: this embodiment a kind of expands the technology of oozing based on heat and realizes that the method for steel upper layer nanometer carries out according to the following steps: one, with 240#, 800# and 1200# waterproof abrasive paper with solid solution attitude 38CrMoAl steel surface finish light after; Be successively placed on ultrasonic cleaning in ethanol and the zero(ppm) water, obtain clean solid solution attitude 38CrMoAl steel; Two, the solid solution attitude 38CrMoAl steel that step 1 is obtained is put on the specimen mounting of pulsed plasma multiple permeation stove, is 8Pa with pulsed plasma multiple permeation stove evacuation to vacuum tightness, applies the voltage of 680V then and keeps 10min; Three, with H
2And N
2The mixed gas that is 1: 1 by volume is a nitriding medium, and the speed with 0.1L/min feeds H to pulsed plasma multiple permeation stove earlier
2, when temperature rises to 200 ℃, with H
2Flow velocity increase and to be 0.3L/min, and feed N to pulsed plasma multiple permeation stove with the speed of 0.3L/min
2, be that 460 ℃, pressure are to keep 4h under the condition of 300Pa in temperature then; Four, after insulation finishes, stop to import H
2, make the 38CrMoAl steel at N
2Be cooled to room temperature under the atmosphere, accomplish the process of 38CrMoAl steel upper layer nanometer.
It is the nanometer crystal layer of 100 μ m～120 μ m that this embodiment has obtained thickness on solid solution attitude 38CrMoAl steel surface.
The co-penetration layer of the solid solution attitude 38CrMoAl steel of the upper layer nanometer that this embodiment is obtained through step 4 carries out Phase Structure Analysis; Test condition: detect the co-penetration layer phase structure with D/max-rB type rotating anode X-ray diffractometer; Diffraction conditions: Cu-K α radiation, voltage 40kV, electric current 80mA.According to the X-ray diffraction result; The X-ray diffraction spectrogram that obtains is as shown in Figure 9; The X-ray diffraction spectrum of the solid solution attitude 38CrMoAl steel that obtains for this embodiment step 1 of a wherein; The X-ray diffraction spectrum at the surperficial 30 μ m places of distance in the co-penetration layer of the solid solution attitude 38CrMoAl steel of the upper layer nanometer that b obtains for this embodiment step 4, the X-ray diffraction spectrum at the surperficial 80 μ m places of distance in the co-penetration layer of the solid solution attitude 38CrMoAl steel of the upper layer nanometer that c obtains for this embodiment step 4.As can beappreciated from fig. 9, in the co-penetration layer apart from surperficial 30 μ m and 80 μ m places be single-phase α ' mutually, but contrast with standard card, obvious wideization of each diffraction peak also has certain skew to the low angle direction, has nanocrystalline characteristic.
The co-penetration layer of the solid solution attitude 38CrMoAl steel of the upper layer nanometer that this embodiment is obtained through step 4 carries out tem observation, test condition apart from surperficial 30 μ m places: utilize FEI TECHNAI type high resolution TEM transmission electron microscope (HRTEM) to carry out delicate tissues and observe.Acceleration voltage is respectively 300kV.The plane transmission preparing electron microscopy specimen of co-penetration layer: co-penetration layer reached the standard grade from substrate to be cut down, and the thickness of co-penetration layer is 0.3mm, is milled to below the 60 μ m from the matrix side is manual.Carry out observing behind the two-sided attenuate from both sides with two spraying equipments, the transmission electron microscope photo that obtains is shown in figure 10.As can beappreciated from fig. 10, the surperficial 30 μ m places of distance are nanocrystalline in the co-penetration layer, and structure is single-phase α ', and grain-size is less than 10nm, and a small amount of amorphous that mixes.
The co-penetration layer of the solid solution attitude 38CrMoAl steel of the upper layer nanometer that this embodiment is obtained through step 4 carries out micro-hardness testing, test condition: adopt HV-1000 type micro Vickers, load is 100g, and the loading time is 15s.The microhardness of the co-penetration layer that test obtains is shown in figure 11.As can beappreciated from fig. 12, the thickness of the co-penetration layer of the solid solution attitude 38CrMoAl steel of upper layer nanometer is 100 μ m～120 μ m, and hardness is up to HV
0.11286.
The expansion based on heat of this embodiment is oozed the technological method of steel upper layer nanometer that realizes and is directly passed through low-temperature ion body carbonitriding at steel alloy surface formation nanometer crystal layer; Improve surface hardness and wear resistance and improving flexible simultaneously; The erosion resistance of steel is not reduced, and simple to operate.
Embodiment 25: this embodiment a kind of expands the technology of oozing based on heat and realizes that the method for steel upper layer nanometer carries out according to the following steps: one, with 240#, 800# and 1200# waterproof abrasive paper with solid solution attitude 38CrMoAl steel surface finish light after; Be successively placed on ultrasonic cleaning in ethanol and the zero(ppm) water, obtain clean solid solution attitude 38CrMoAl steel; Two, the solid solution attitude 38CrMoAl steel that step 1 is obtained is put on the specimen mounting of pulsed plasma multiple permeation stove, is 18Pa with pulsed plasma multiple permeation stove evacuation to vacuum tightness, applies the voltage of 400V then and keeps 13min; Three, with H
2And N
2The mixed gas that is 1: 1 by volume is a nitriding medium, is carburizing agent with ethanol, and the speed with 0.1L/min feeds H to pulsed plasma multiple permeation stove earlier
2, when temperature rises to 200 ℃, with H
2Flow velocity increase and to be 0.3L/min, and feed N to pulsed plasma multiple permeation stove with the speed of 0.1L/min
2, simultaneously ethanol is fed pulsed plasma multiple permeation stove with the speed of 0.05L/min, be that 360 ℃, pressure are to keep 16h under the condition of 400Pa in temperature then; Four, after insulation finishes, stop to import H
2And ethanol, make the 38CrMoAl steel at N
2Be cooled to room temperature under the atmosphere, accomplish the process of 38CrMoAl steel upper layer nanometer.
It is the nanometer crystal layer of 100 μ m that this embodiment has obtained thickness on solid solution attitude 38CrMoAl steel surface.
The co-penetration layer of the solid solution attitude 38CrMoAl steel of the upper layer nanometer that this embodiment is obtained through step 4 carries out micro-hardness testing, test condition: adopt HV-1000 type micro Vickers, load is 100g, and the loading time is 15s.The microhardness of the co-penetration layer that test obtains is shown in figure 12.As can beappreciated from fig. 12, the thickness of the co-penetration layer of the solid solution attitude 38CrMoAl steel of upper layer nanometer is 100 μ m, and hardness is up to HV
0.11085.
The expansion based on heat of this embodiment is oozed the technological method of steel upper layer nanometer that realizes and is directly passed through low-temperature ion body carbonitriding at steel alloy surface formation nanometer crystal layer; Improve surface hardness and wear resistance and improving flexible simultaneously; The erosion resistance of steel is not reduced, and simple to operate.
Embodiment 26: this embodiment a kind of expands the technology of oozing based on heat and realizes that the method for steel upper layer nanometer carries out according to the following steps: one, with 240#, 800# and 1200# waterproof abrasive paper with solid solution attitude 38CrMoAl steel surface finish light after; Be successively placed on ultrasonic cleaning in ethanol and the zero(ppm) water, obtain clean solid solution attitude 38CrMoAl steel; Two, the solid solution attitude 38CrMoAl steel that step 1 is obtained is put on the specimen mounting of pulsed plasma multiple permeation stove, is 18Pa with pulsed plasma multiple permeation stove evacuation to vacuum tightness, applies the voltage of 400V then and keeps 13min; Three, with H
2And N
2The mixed gas that is 1: 1 by volume is a nitriding medium, is that 1: 1 the Lanthanum trinitrate and the saturated ethanolic soln of cerous nitrate are the RE-Carburizing agent with mol ratio, and the speed with 0.1L/min feeds H to pulsed plasma multiple permeation stove earlier
2, when temperature rises to 200 ℃, with H
2Flow velocity increase and to be 0.3L/min, and feed N to pulsed plasma multiple permeation stove with the speed of 0.3L/min
2When temperature rises to 440 ℃, again the RE-Carburizing agent is fed in the pulsed plasma multiple permeation stove ethanol in the RE-Carburizing agent and N
2Volume ratio be 2: 1, be that 460 ℃, pressure are to keep 8h under the condition of 400Pa in temperature then; Four, after insulation finishes, stop to import H
2With the RE-Carburizing agent, make the 38CrMoAl steel at N
2Be cooled to room temperature under the atmosphere, accomplish the process of 38CrMoAl steel upper layer nanometer.
It is the nanometer crystal layer of 100 μ m that this embodiment has obtained thickness on solid solution attitude 38CrMoAl steel surface.
The co-penetration layer of the solid solution attitude 38CrMoAl steel of the upper layer nanometer that this embodiment is obtained through step 4 carries out micro-hardness testing, test condition: adopt HV-1000 type micro Vickers, load is 100g, and the loading time is 15s.The microhardness of the co-penetration layer that test obtains is shown in figure 13.As can beappreciated from fig. 13, the thickness of the co-penetration layer of the solid solution attitude 38CrMoAl steel of upper layer nanometer is 100 μ m, and hardness is up to HV
0.11400.
The expansion based on heat of this embodiment is oozed the technological method of steel upper layer nanometer that realizes and is directly passed through low-temperature ion body carbonitriding at steel alloy surface formation nanometer crystal layer; Improve surface hardness and wear resistance and improving flexible simultaneously; The erosion resistance of steel is not reduced, and simple to operate.
Claims (10)
1. one kind is expanded the method that the technology of oozing realizes steel upper layer nanometer based on heat; It is characterized in that expanding the technology of oozing based on heat realizes that the method for steel upper layer nanometer carries out according to the following steps: one, with 240#, 800# and 1200# waterproof abrasive paper with solid solution attitude steel surface finish light after; Be successively placed on ultrasonic cleaning in ethanol and the zero(ppm) water, obtain clean solid solution attitude steel; Two, the solid solution attitude steel that step 1 is obtained is put on the specimen mounting of pulsed plasma multiple permeation stove, is 20Pa～0.1Pa with pulsed plasma multiple permeation stove evacuation to vacuum tightness, applies the voltage of 450V～700V then and keeps 10min～20min; Three, feeding penetration enhancer to pulsed plasma multiple permeation stove, is that 350 ℃～500 ℃, pressure are to keep 3h～80h under the condition of 200Pa～550Pa in temperature; Four, after insulation finishes, make steel at N
2Or NH
3Be cooled to room temperature under the atmosphere, accomplish the process of steel upper layer nanometer; Wherein the penetration enhancer in the step 3 is compsn, nitriding medium or the carburizing agent of compsn, nitriding medium and the RE-Carburizing agent of nitriding medium and carburizing agent; Wherein the steel in the step 1 is a steel alloy.
2. a kind of method of oozing technology realization steel upper layer nanometer that expands based on heat according to claim 1; The solution treatment that it is characterized in that the steel in the step 1 be with steel be placed on temperature be incubated 0.5h～2h under 900 ℃～1200 ℃ the condition after; Oil cooling is accomplished solution treatment.
3. a kind of the expansion based on heat according to claim 1 and 2 oozed the technological method that realizes steel upper layer nanometer, it is characterized in that described nitriding medium is H
2With NH
3Be 1～3: 1 mixed gas by volume or be H
2With N
2Be 1～9: 1 mixed gas or NH by volume
3
4. a kind of the expansion based on heat according to claim 1 and 2 oozed the technological method that realizes steel upper layer nanometer, it is characterized in that described carburizing agent is methyl alcohol, ethanol or Virahol.
5. a kind of the expansion based on heat according to claim 1 and 2 oozed the technological method that realizes steel upper layer nanometer, it is characterized in that described RE-Carburizing agent is with containing La or/and the salt of Ce dissolves in the saturated alcohol solution that forms in methyl alcohol, ethanol or the Virahol.
6. a kind of the expansion based on heat according to claim 1 and 2 oozed the technological method that realizes steel upper layer nanometer, and when it is characterized in that penetration enhancer is nitriding medium, the volumetric flow rate of nitriding medium is 0.025L/min～0.3L/min.
7. a kind of the expansion based on heat according to claim 1 and 2 oozed the technological method that realizes steel upper layer nanometer, and when it is characterized in that penetration enhancer is carburizing agent, the volumetric flow rate of carburizing agent is 0.025L/min～0.3L/min.
8. a kind of method of oozing technology realization steel upper layer nanometer that expands based on heat according to claim 1 and 2; When it is characterized in that penetration enhancer is nitriding medium and carburizing agent combination; The volumetric flow rate of nitriding medium is 0.025L/min～0.3L/min, alcohol in the carburizing agent and the N in the nitriding medium
2Or NH
3The ratio of volumetric flow rate be 0.25～3: 1.
9. a kind of method of oozing technology realization steel upper layer nanometer that expands based on heat according to claim 1 and 2; When it is characterized in that penetration enhancer is the compsn of nitriding medium and RE-Carburizing agent formation; The volumetric flow rate of nitriding medium is 0.025L/min～0.3L/min, alcohol in the carburizing agent and the N in the nitriding medium
2Or NH
3The ratio of volumetric flow rate be 0.25～3: 1.
10. a kind of method of oozing technology realization steel upper layer nanometer that expands based on heat according to claim 1 and 2; It is characterized in that the vacuum tightness that pulsed plasma multiple permeation stove is taken out in the step 2 is 18Pa～0.5Pa; Voltage is 500V～650V, and the hold-time is 11min～18min.
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| CN101818320A (en) * | 2010-05-12 | 2010-09-01 | 哈尔滨工业大学 | Method for obtaining rigidity continuous distribution modified layer on surface of stainless steel |
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| CN101818320A (en) * | 2010-05-12 | 2010-09-01 | 哈尔滨工业大学 | Method for obtaining rigidity continuous distribution modified layer on surface of stainless steel |
Non-Patent Citations (3)
| Title |
|---|
| 赵丽艳等.稀土对42CrMo钢等离子体氮碳共渗组织及性能的影响.< * |
| 赵丽艳等.稀土对42CrMo钢等离子体氮碳共渗组织及性能的影响.<金属热处理》.2009,第34卷(第11期),69-73. |
| 金属热处理》.2009,第34卷(第11期),69-73. * |
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