CN110218968B - Method for improving corrosion resistance of steel surface by low-temperature liquid-phase diffusion - Google Patents

Method for improving corrosion resistance of steel surface by low-temperature liquid-phase diffusion Download PDF

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CN110218968B
CN110218968B CN201910541258.5A CN201910541258A CN110218968B CN 110218968 B CN110218968 B CN 110218968B CN 201910541258 A CN201910541258 A CN 201910541258A CN 110218968 B CN110218968 B CN 110218968B
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steel
corrosion resistance
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steel surface
corrosion
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CN110218968A (en
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郝国栋
李聪
郝春丽
尹龙承
邵长斌
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Mudanjiang Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
    • C23C12/02—Diffusion in one step

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

low-temperature liquid-phase diffusion for improving corrosion resistance of steel surfaceThe invention relates to a method for strengthening the surface of steel, which aims to solve the technical problem of high temperature of the existing metal surface diffusion and infiltration method, wherein steel surface is nanocrystallized, and secondly, anhydrous borax and V are used for preparing the metal surface diffusion and infiltration alloy2O5And thirdly, placing the activated steel obtained in the step into a borax salt bath and keeping the activated steel for 2-4 hours, and obtaining a corrosion-resistant film layer on the surface of the steel, wherein the corrosion-resistant film layer is formed by nano sheets growing in situ at a low temperature, the film has strong bonding force with a substrate, the surface has hydrophobicity, and the contact angle is 100-115 degrees, so that the corrosion resistance of the metal is improved.

Description

Method for improving corrosion resistance of steel surface by low-temperature liquid-phase diffusion
Technical Field
The invention relates to a method for strengthening the surface of steel.
Background
The carbon content of steel is equal to or more than 0.3 wt.%, and the steel is easy to oxidize in the air to generate corrosion, so that the metal surface strengthening and protection such as steel is concerned by various circles, wherein the diffusion method is to make the metal or nonmetal element to be diffused penetrate into the surface of the metal material or workpiece by heating diffusion to form a surface alloy layer, and the corrosion resistance, hardness and other properties of the metal surface are improved by the alloy layer.
The existing metal surface diffusion method uses borax as base salt, carbon tool steel and alloy tool steel in ferrovanadium or V2O5And reducing agents such as A1, Si, Ca and the like in borax salt bath with the temperature of more than 1000 ℃, so that a vanadium carbide coating with the diameter of several microns can be formed on the surface, and the hardness of the metal surface is improved. However, the method has the defects of high borax salt bath temperature, high viscosity, poor fluidity, more salt adhesion of workpieces, difficult cleaning, serious corrosion of clamps and the like.
Disclosure of Invention
The invention provides methods for improving the corrosion resistance of the steel surface by low-temperature liquid-phase diffusion, aiming at solving the technical problem of high temperature of the existing metal surface diffusion method.
The method for improving the corrosion resistance of the steel surface by low-temperature liquid phase diffusion comprises the following steps:
, carrying out nanocrystallization treatment on the steel surface;
secondly, weighing 50 to 65 mass percent of anhydrous borax (Na)2B4O7)、15％～20％V2O5Adding 20-30% of aluminum powder into a diffusion furnace, and heating to 780-900 ℃ to obtain a borax salt bath;
and thirdly, placing the steel subjected to the nanocrystallization treatment obtained in the step into a borax salt bath at the temperature of 780-900 ℃ for holding for 2-4 hours, cleaning and drying to obtain a corrosion-resistant film layer on the surface of the steel.
The surface of the steel is nanocrystallized by mechanical grinding or shot blasting treatment, so that the surface layer of a steel matrix has a nanocrystalline structure and the main body of the matrix still keeps the original coarse-grained state, thereby improving the surface reaction activity of the material and preparing for forming an anticorrosion structure; the aluminum powder is added into the borax salt bath, so that the permeability of the salt bath is improved, the steel surface of the invention has the capability of carrying out diffusion reaction at low temperature, and a film with a nano-sheet structure grows in situ on the steel surface, so that the surface has hydrophobicity, and the corrosion resistance of metal is greatly improved. Meanwhile, the film and the substrate have stronger binding force.
The water contact angle of the steel surface corrosion-resistant film layer is 100-115 degrees, and meanwhile, the borax salt bath temperature is low, the energy consumption is low, and the steel surface corrosion-resistant film layer can be used in the field of surface treatment.
Drawings
FIG. 1 is an XRD pattern of a corrosion-resistant film layer obtained on the surface of steel No. 35 in example 1;
FIG. 2 is a scanning electron micrograph of a corrosion-resistant film obtained on the surface of steel No. 35 in example 1 after nanocrystallization;
FIG. 3 is a SEM image of a film layer obtained on the surface of the non-nano-sized No. 35 steel in example 1;
FIG. 4 is a cross-sectional profile and line scan of the corrosion-resistant film obtained on the surface of steel No. 35 after nanocrystallization in example 1;
FIG. 5 is a cross-sectional profile and line scan of the film layer obtained on the surface of the non-nano-grade No. 35 steel of example 1;
FIG. 6 is a photograph showing the contact angle of the corrosion-resistant film layer obtained on the surface of steel No. 35 after nanocrystallization in example 1;
FIG. 7 is a photograph of the contact angle of a comparative film layer obtained on the surface of non-nano-sized No. 35 steel of comparative experiment 1;
FIG. 8 is a photograph of the hydrophobic angle of the comparative film layer obtained on the surface of No. 35 steel after nanocrystallization for comparative experiment 2;
FIG. 9 is a scanning electron micrograph of a corrosion-resistant film layer obtained on the surface of steel No. 35 in example 2 after nanocrystallization.
Detailed Description
Specifically, the method for improving corrosion resistance of steel surface by low temperature liquid phase diffusion according to the present embodiment comprises the following steps:
, carrying out nanocrystallization treatment on the steel surface;
secondly, weighing 50 to 65 mass percent of anhydrous borax (Na)2B4O7)、15％～20％V2O5Adding 20-30% of aluminum powder into a diffusion furnace, and heating to 780-900 ℃ to obtain a borax salt bath;
and thirdly, placing the steel subjected to the nanocrystallization treatment obtained in the step into a borax salt bath at the temperature of 780-900 ℃ for holding for 2-4 hours, cleaning and drying to obtain a corrosion-resistant film layer on the surface of the steel.
Second embodiment the present embodiment is different from embodiment in that the nanocrystallization process in step is a shot peening process, and the other steps are the same as embodiment .
Third embodiment the present embodiment is different from embodiment in that the shot blasting is performed by a mechanical vibration type shot blasting in a vacuum in a shot blasting machine, the shot diameter is 0.5 to 3mm, the frequency of mechanical vibration is 50Hz, the distance between the shot and the steel surface is 10 to 15mm, and the treatment time is 30 to 40min, and the method is otherwise the same as embodiment .
Fourth embodiment this embodiment differs from of embodiments -three in that the steel in step is steel No. 35, and other embodiments are the same as of embodiments -three.
Fifth embodiment mode, this embodiment mode differs from of embodiment modes to third embodiment mode in that the steel in step is H13 steel, and the others are the same as of embodiment modes to third embodiment mode.
Sixthly, the difference between the second embodiment and of the third embodiment -fifth is that 55-60% of anhydrous borax and 16-18% of V are weighed according to mass percentage in the second step2O5And 22% to 29% aluminum powder, other than as in embodiments to fifths.
Seventh embodiment mode differs from embodiments to sixth embodiment mode in that the heating is performed to 790 to 830 ℃ in step two, and other embodiments are the same as of embodiments to sixth embodiment mode.
Eighth embodiment differs from embodiments to seventh embodiment in that the holding time in step three is 2.5 to 3.5 hours, and is otherwise the same as embodiments to seventh embodiment.
The following examples are used to demonstrate the beneficial effects of the present invention:
example 1: the method for improving the corrosion resistance of the steel surface by low-temperature liquid phase diffusion comprises the following steps:
, performing nanocrystallization treatment on the surface of No. 35 steel plate, namely putting No. 35 steel plate into a shot blasting machine, and performing mechanical vibration type shot blasting under the vacuum of 0.7MPa, wherein the diameter of a shot is 2mm, the frequency of mechanical vibration is 50Hz, the distance between the shot and the steel surface is 10mm, and the treatment time is 30min, thus completing the surface nanocrystallization treatment;
secondly, weighing 55 percent of anhydrous borax and 17 percent of V according to mass percentage2O5Mixing with 28% aluminum powder uniformly, adding into a diffusion furnace, heating to 780 ℃, and obtaining a borax salt bath;
and thirdly, placing the nano-treated No. 35 steel plate obtained in the step into a borax salt bath at 780 ℃ for holding for 2.5 hours to obtain a corrosion-resistant film layer on the surface of the nano-treated No. 35 steel plate.
Comparative experiment 1: the test was conducted in the same manner as in example 1 except that no 35 # steel sheet was not subjected to the nanocrystallization treatment, and a comparative film layer was obtained.
In this example, the XRD pattern of the corrosion-resistant film obtained on the surface of steel No. 35 is shown in fig. 1, where a is the XRD spectrum of the surface film of steel No. 35 after nano-treatment and b is the XRD spectrum of the surface film of steel No. 35 without nano-treatment, and as can be seen from fig. 1, compared with the XRD spectrum of the surface film of steel No. 35 without nano-treatment, the diffusion is performed after nano-treatment of steel No. 35, and VC in the film is diffusedXThe diffraction peak intensity of (A) is enhanced while the peak of iron is reduced, which indicates that the film formation is facilitated after the matrix is nanocrystallized.
In the present example, a scanning electron micrograph of the corrosion-resistant film layer obtained on the surface of the nanocrystallized steel No. 35 is shown in fig. 2, and it can be seen from fig. 2 that the film is assembled from nanosheets. While the scanning electron microscope photo of the comparative film layer obtained on the surface of the steel 35 without nanocrystallization is shown in fig. 3, it can be seen from fig. 3 that the film layer on the surface of the steel 35 without nanocrystallization is completely different from the film layer obtained after nanocrystallization, and the film layer without nanocrystallization does not form a nanosheet assembly structure.
In this example, the cross-sectional profile of the corrosion-resistant film layer obtained on the surface of the nano-treated steel 35 is shown in fig. 4, the cross-sectional profile of the comparative film layer on the surface of the non-nano treated steel 35 is shown in fig. 5, it can be seen from fig. 4 that a film layer with a thickness of is obviously formed on the surface of the base steel, and it can be seen from the line scan on the graph that the content of Fe is increased from inside to outside C, V and the content of Fe is decreased, which shows that C, V element diffuses into the steel from outside to inside, and it can be seen from fig. 4 that a diffusion point can be seen at a position deeper from the surface, which shows that the activity of the diffusion reaction is high.
The corrosion-resistant film layer obtained on the surface of the steel 35 subjected to nanocrystallization in the embodiment is subjected to a hydrophobicity test, and a contact angle photograph of the corrosion-resistant film layer obtained on the surface of the steel 35 subjected to nanocrystallization is shown in fig. 6, wherein the contact angle is 114 degrees, and the steel has good hydrophobicity, so that the corrosion resistance of the material can be greatly improved. The contact angle photograph of the comparative film layer obtained on the surface of the non-nano 35 # steel is shown in fig. 7, the contact angle is 36 degrees, and the surface is hydrophilic and is not favorable for corrosion resistance and corrosion resistance of the material.
Comparative experiment 2: the experiment differs from example 1 in that the temperature of the borax salt bath in step two was 1000 ℃, and a comparative film was obtained in the same manner as in example 1.
The photo of the hydrophobic angle of the comparative film obtained in comparative test 2 is 61 ° as shown in fig. 8, and is a hydrophilic surface, which is not good for corrosion protection and corrosion resistance of the material. Although the surface of steel 35 is treated to be nano-sized, it diffuses at a high temperature and is difficult to form a nano-sheet-like hydrophobic structure.
Example 2: the method for improving the corrosion resistance of the steel surface by low-temperature liquid phase diffusion comprises the following steps:
, performing nanocrystallization treatment on the surface of No. 35 steel plate, namely putting No. 35 steel plate into a shot blasting machine, and performing mechanical vibration type shot blasting under the vacuum of 0.5MPa, wherein the diameter of a shot is 1mm, the frequency of mechanical vibration is 50Hz, the distance between the shot and the steel surface is 15mm, and the treatment time is 30min, so as to finish the surface nanocrystallization treatment;
secondly, weighing 65 percent of anhydrous borax and 15 percent of V according to mass percentage2O5Adding 20% of aluminum powder into a diffusion furnace, and heating to 830 ℃ to obtain a borax salt bath;
and thirdly, placing the nano-sized No. 35 steel plate obtained in the step into a borax salt bath at the temperature of 830 ℃ for holding for 3 hours to obtain a corrosion-resistant film layer on the surface of the No. 35 steel plate.
In example 2, a scanning electron micrograph of a corrosion-resistant film layer obtained on the surface of steel No. 35 is shown in fig. 9, and it can be seen from fig. 9 that the film layer on the surface of steel No. 35 is assembled from nanosheets. EDS energy spectrum scanning is carried out at the same time, the obtained element composition is shown in a table 1,
TABLE 1 surface element composition
Figure BDA0002102621400000041
The hydrophobicity test of the corrosion-resistant film layer on the surface of the activated steel 35 in the embodiment shows that the hydrophobic angle of the corrosion-resistant film layer on the surface of the activated steel 35 is 102 degrees, and the corrosion-resistant film layer has good hydrophobicity and can greatly improve the corrosion resistance of the material.

Claims (5)

1, kinds of low temperature liquid phase diffusion method for improving steel surface corrosion resistance, characterized in that the method is carried out according to the following steps:
, performing nanocrystallization treatment on the steel surface, wherein the nanocrystallization treatment is shot blasting treatment, the shot blasting treatment is mechanical vibration type shot blasting in a shot blasting machine under vacuum, the diameter of the shot is 0.5-3 mm, the frequency of mechanical vibration is 50Hz, the distance between the shot and the steel surface is 10-15 mm, and the treatment time is 30-40 min;
secondly, weighing 50 to 65 percent of anhydrous borax and 15 to 20 percent of V according to the mass percentage2O5Adding 20-30% of aluminum powder into a diffusion furnace, and heating to 780-900 ℃ to obtain a borax salt bath;
and thirdly, placing the steel subjected to the nanocrystallization treatment obtained in the step into a borax salt bath at the temperature of 780-900 ℃ for holding for 2-4 hours, cleaning and drying to obtain a corrosion-resistant film layer on the surface of the steel.
2. The method of improving corrosion resistance of steel surface by liquid phase diffusion at kinds of low temperature according to claim 1, wherein the steel in step is steel No. 35 or H13.
3. The method for improving corrosion resistance of steel surface by kinds of low-temperature liquid phase diffusion according to claim 1, wherein in the second step, 55-60% of anhydrous borax and 16-18% of V are weighed according to mass percentage2O5And 22 to 29 percent of aluminum powder.
4. The method for improving the corrosion resistance of the steel surface by kinds of low-temperature liquid phase diffusion according to claim 1, wherein the heating is carried out to 790-830 ℃ in the second step.
5. The method for improving the corrosion resistance of the steel surface by kinds of low-temperature liquid phase diffusion according to claim 1, wherein the holding time in the third step is 2.5-3.5 hours.
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CN1005116B (en) * 1987-05-15 1989-09-06 厦门大学 Corrosion resistance treatment method for stainless steel surface
CN1031950C (en) * 1993-03-19 1996-06-05 福建省冶金工业研究所 Salt bath process for rare-earth-vanadium-boron co-diffusion
CN100582287C (en) * 2008-05-06 2010-01-20 山东建筑大学 Boron-chromium-rare-earth co-seeping agent and its low-temperature co-seeping process below eutectoid line
CN105331926B (en) * 2015-11-05 2018-03-20 广西大学 N C Cr V RE multicomponent thermochemical treatment materials for 45 steel surface reinforcements
CN106222582B (en) * 2016-09-14 2018-04-13 北京航空航天大学 A kind of method for improving bearing steel surface corrosion resistance
CN108359932A (en) * 2017-08-25 2018-08-03 瑞安市中恒金属有限公司 A kind of die surface TD processing methods
CN109321875A (en) * 2018-11-08 2019-02-12 长沙特耐金属材料科技有限公司 The surface metal carbide coating processing method of high-alloy steel materials in a kind of middle low-carbon
CN109136830A (en) * 2018-11-08 2019-01-04 长沙特耐金属材料科技有限公司 A kind of metal material and its preparation method and application containing vanadium coating

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