CN109504996B - Cathode micro-arc oxidation solution and method for preparing DLC composite oxide film on steel surface - Google Patents

Cathode micro-arc oxidation solution and method for preparing DLC composite oxide film on steel surface Download PDF

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CN109504996B
CN109504996B CN201710826521.6A CN201710826521A CN109504996B CN 109504996 B CN109504996 B CN 109504996B CN 201710826521 A CN201710826521 A CN 201710826521A CN 109504996 B CN109504996 B CN 109504996B
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oxide film
composite oxide
steel
dlc
arc oxidation
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CN109504996A (en
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薛文斌
张亦凡
余佳浩
魏克俭
金小越
杜建成
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Beijing Normal University
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Beijing Normal University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires

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Abstract

The invention discloses a solution and a method for preparing a diamond-like carbon (DLC) composite oxide film on the surface of steel by using a cathode micro-arc oxidation method, belonging to the field of material surface treatment. The solution is an aqueous solution, and the contents of the components are as follows: 10-15% of methanol, 15-30% of ethanolamine, 10-25% of urea, 1-5% of nickel sulfate, 1-4% of nano carbon powder, 5-10% of sodium chloride and 25-55% of deionized water. The specific method is that the steel workpiece to be treated is used as a cathode, graphite is used as an anode, and the steel workpiece and the graphite are immersed in an electrolytic tank filled with the prepared solution together, the voltage is rapidly increased to 250V-550V at room temperature and is kept for 2min-15min, and a DLC composite oxide film can be generated on the surface of the steel, the thickness of the DLC composite oxide film is 20 mu m-100 mu m, the highest hardness can reach 1200HV, and the DLC composite oxide film exceeds four times of a matrix. The method has simple process, wide applicable materials and high treatment efficiency, and obviously improves the hardness and the friction resistance of the steel material.

Description

Cathode micro-arc oxidation solution and method for preparing DLC composite oxide film on steel surface
Technical Field
The invention belongs to the field of material surface treatment, and relates to a solution and a method for preparing a DLC composite oxide film on the surface of steel by using a cathode micro-arc oxidation method.
Background
Steel is widely used as the most common metal material, but most types of steel materials, particularly low-carbon steel, have low hardness and poor wear resistance. Steel parts with high requirement for wear resistance usually need surface strengthening treatment to improve its wear resistance and corrosion resistance, and the common surface treatment methods include quenching heat treatment, laser hardening, gas carburizing, vacuum carburizing, ion nitriding, boriding and the like. Patents 200710050131.0 and 200880005440.9 are conventional techniques for obtaining a carburized layer on a steel surface.
Micro-arc oxidation is a metal material surface treatment technology developed in recent years, and a ceramic film layer mainly comprising matrix metal oxide grows on the surfaces of valve metals such as aluminum, magnesium, titanium and the like through the action of instantaneous high temperature and high pressure generated by arc discharge on the electrode surface in electrolyte. Patent 201310108560.4 discloses obtaining a dense micro-arc oxide film on the surface of a zirconium alloy anode. In the micro-arc oxidation process, the aluminum, magnesium, titanium and zirconium sample piece is usually used as an anode, but the steel material does not belong to valve metal, and a high-quality anode micro-arc oxidation film is not easy to form. The micro-arc oxidation of the anode is difficult to grow a compact oxide film, and the film layer is not compact and has poor binding force, which limits the improvement of the friction performance of the film layer.
The cathode micro-arc oxidation is a novel steel surface treatment technology developed on the basis of anode gas film discharge in recent years. The technology generally takes inert materials as an anode and a workpiece to be processed as a cathode, and the inert materials and the workpiece are jointly immersed in a specific electrolyte solution. Applying a certain voltage between the electrodes, the heat effect of current and electrolytic reaction to form a gas film on the surface of the cathode. When the voltage reaches a certain degree, the gas film is broken down to generate micro-arc discharge. The instantaneous high temperature of the plasma micro-arc discharge area enables the electrolyte to be decomposed to generate oxygen atoms, and the oxygen atoms and the surface of the steel quickly react to form a layer of compact oxide film. According to patent 201310062490.3, the hardness of the steel surface can be greatly improved by cathode micro-arc oxidation treatment, and the friction coefficient and the wear rate are reduced.
Diamond-like carbon (DLC), which is an amorphous metastable carbon material composed of amorphous carbon and a diamond phase, is a new material of intense research due to its excellent mechanical, electrical, acoustical, optical, thermal, chemical properties and good biocompatibility. In recent years, people have paid attention to a method for preparing a carbon material by utilizing a discharge phenomenon in an aqueous solution, and patent 201310097289.9 discloses a method for preparing a nano diamond-like carbon powder material by utilizing a cathode micro-arc discharge technology. This indicates that the arc discharge is in a local high-temperature and high-pressure environmentUnder proper process conditions, partial activated carbon atoms or ions decomposed by discharge can be directly bonded into sp under the action of instantaneous high temperature and high pressure in a plasma region and the induction action of hydrogen elements3C, forming a diamond-like carbon component.
On the basis of the cathode micro-arc oxidation technology, the invention forms a diamond-like synthetic environment in a discharge area by selecting proper electrolyte and process parameters and adding a nickel-based catalyst and nano carbon powder, thereby quickly preparing the DLC-component-containing composite oxide film on the surface of steel. The method has simple process, wide applicable materials and high treatment efficiency, and obviously improves the hardness and the friction resistance of the steel material.
Disclosure of Invention
The invention provides a preparation method of a novel cathode micro-arc oxidation DLC composite oxide film. The method improves the cathode micro-arc oxidation technology to prepare the composite oxide film containing DLC components. Steel is used as a cathode, the steel is subjected to cathode micro-arc oxidation treatment in the electrolyte disclosed by the patent, and a certain diamond-like carbon (DLC) component is synthesized to enter a film layer while an oxidation film grows, so that a DLC composite oxidation film is formed. The maximum hardness of the composite film prepared based on the method can reach 1200HV, and the wear resistance of steel is improved. Meanwhile, the solution and the process are suitable for all steel materials. The specific process flow is as follows:
step one, preparing a cathode micro-arc oxidation electrolyte. Calculating the content of each component by mass percent: 10-15% of methanol, 15-30% of ethanolamine, 10-25% of urea, 1-5% of nickel sulfate, 1-4% of nano carbon powder, 5-10% of sodium chloride and 25-55% of deionized water.
Step two, the surface of the steel sample is pretreated by 200-#And (3) polishing the surface of the steel by using abrasive paper, rinsing the steel by using acetone, rinsing the steel by using deionized water, and drying the steel.
Step three, connecting the pretreated sample to a cathode of a self-made cathode micro-arc oxidation power supply, using graphite as an anode, immersing the sample in an electrolytic bath filled with the prepared solution together, and continuously stirring; rapidly raising the voltage to 250-550V at room temperature, and keeping for 2-15 min.
The steel surface treated by the method and the solution can obtain a DLC composite oxide film, the thickness of the DLC composite oxide film is 20-100 mu m, and the highest hardness can reach 1200 HV.
Compared with the prior steel surface hardening method, the invention has the following remarkable characteristics: (1) on the basis of the traditional cathode micro-arc oxidation, the composite oxide film contains the DLC component with high hardness, so that the hardness of the composite oxide film is greatly improved; (2) the electrolyte used in the invention has wide sources, the nickel-based catalyst is added, and the nano carbon powder is added to increase the carbon source, thereby improving the DLC content and the growth speed of the composite oxide film; (3) the invention is suitable for various grades of steel materials, has high treatment efficiency, small environmental pollution in the preparation process, and repeated utilization of the electrolyte, and is suitable for large-scale production.
Drawings
The attached figure 1 in the specification is a scanning electron microscope picture of the cross section of the DLC composite oxide film prepared by the invention.
Description attached figure 2 is a Raman spectrum of the DLC composite oxide film, the excitation wavelength is 633nm, the use power is 5mW, and the scanning range is as follows: 200-2000cm-1. As can be seen from FIG. 2, at 1331cm-1Appear to originate from sp3Diamond characteristic peak of bond, which shows sp contained in the cathode micro-arc oxidation film layer3A hybrid diamond-like carbon (DLC) component.
Detailed Description
According to the working method and the electrolyte system, a plurality of electrolytes are prepared, the cathode micro-arc oxidation process condition provided by the invention is adopted to carry out cathode micro-arc oxidation treatment on the Q235 low-carbon steel, and the thickness and the microhardness of the DLC composite oxide film obtained under different conditions are measured. The following examples are provided in conjunction with the technical solutions of the present invention:
example 1
In this example, the ferrous material being processed is a Q235 mild steel coupon.
Firstly, preprocessing steel materials to be processed, polishing the surface of steel step by using sand paper (200# -1200#), rinsing with acetone, rinsing with deionized water and drying.
Then preparing a cathode micro-arc oxidation solution. The cathode micro-arc oxidation solution is as follows: 200mL of methanol, 200mL of ethanolamine, 210g of urea, 15g of nickel sulfate, 20g of nano carbon powder, 100g of sodium chloride and 450mL of deionized water.
After the electrolyte is prepared, immersing the two electrodes in an electrolytic tank filled with the prepared electrolyte, and ventilating and stirring; the voltage was rapidly raised to 420V at room temperature for 12 min.
Through the steps, the Q235 low-carbon steel with the surface covered with the uniform DLC composite oxide film is finally obtained.
The workpiece was cut and mounted with bakelite powder, and after buffing and polishing, the thickness of the composite oxide film was measured by Hitachi S-4800 scanning electron microscope to be 50 μm. The microhardness of the film layer is 950HV as determined by HX-1000TM Vickers microhardness tester.
Example 2
The Q235 low-carbon steel sample was pretreated, the electrolyte was prepared, and the low-carbon steel was subjected to cathodic micro-arc oxidation in the same manner as in example 1. Different from the embodiment 1, in the embodiment, the electrolyte comprises 240mL of methanol, 300mL of ethanolamine, 200g of urea, 15g of nickel sulfate, 15g of nano carbon powder, 80g of sodium chloride and 560mL of deionized water. The voltage is applied at 350V for 4 min.
Through the steps, the Q235 low-carbon steel with the surface covered with the uniform DLC composite oxide film is finally obtained. The thickness of the composite oxide film was measured to be 25 μm and the microhardness of the film layer was measured to be 610HV in the same manner as in example 1.
Example 3
The Q235 low-carbon steel sample was pretreated, the electrolyte was prepared, and the low-carbon steel was subjected to cathodic micro-arc oxidation in the same manner as in example 1. In the embodiment, the electrolyte contains 280mL of methanol, 200mL of ethanolamine, 300g of urea, 15g of nickel sulfate, 30g of nano carbon powder, 100g of sodium chloride and 450mL of deionized water. The voltage 520V was applied and the treatment was carried out for 12 min.
Through the steps, the Q235 low-carbon steel with the surface covered with the uniform DLC composite oxide film is finally obtained. The thickness of the composite oxide film was measured to be 100 μm and the microhardness of the film layer was measured to be 1150HV in the same manner as in example 1.
And detecting the Raman spectrum of the DLC composite oxide film by using a Horiba LabRAM Aramis Raman spectrometer to determine that the film layer contains diamond-like carbon (DLC) components.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (2)

1. The cathode micro-arc oxidation electrolyte for preparing the DLC composite oxide film is characterized by comprising the following components in percentage by mass: 10-15% of methanol, 15-30% of ethanolamine, 10-25% of urea, 1-5% of nickel sulfate, 1-4% of nano carbon powder, 5-10% of sodium chloride and 25-55% of deionized water.
2. A cathode micro-arc oxidation method for preparing a DLC composite oxide film is characterized by comprising the following steps:
step one, preparing the electrolyte of claim 1;
step two, pretreating the surface of the steel sample, polishing the surface of the steel with 200-grade 1200# abrasive paper, rinsing with acetone, cleaning with deionized water and drying;
thirdly, connecting the pretreated sample to a power supply cathode, using graphite as an anode, immersing the pretreated sample in an electrolytic bath filled with prepared electrolyte together, and continuously stirring; rapidly raising the voltage to 250-550V at room temperature, and maintaining for 2-15 min to obtain DLC composite oxide film with thickness of 20-100 μm.
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CN104018201A (en) * 2013-02-28 2014-09-03 北京师范大学 Solution and method for rapid cathode micro-arc oxidation treatment on steel surface
CN104073834A (en) * 2013-03-26 2014-10-01 北京师范大学 Preparation method of nanometer diamond-like powder
CN104131249A (en) * 2013-05-03 2014-11-05 北京师范大学 Solution used for steel surface quick plasma electrolysis boro-carbonization and boro-carbonization method
CN104141104A (en) * 2013-05-08 2014-11-12 北京师范大学 Solution for rapid plasma electrolytic carbonitriding on steel surface and carbonitriding method
CN104294343A (en) * 2013-07-18 2015-01-21 北京师范大学 Preparation method of diamond-like composite carburizing layer of steel surface

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CN104018201A (en) * 2013-02-28 2014-09-03 北京师范大学 Solution and method for rapid cathode micro-arc oxidation treatment on steel surface
CN104073834A (en) * 2013-03-26 2014-10-01 北京师范大学 Preparation method of nanometer diamond-like powder
CN104131249A (en) * 2013-05-03 2014-11-05 北京师范大学 Solution used for steel surface quick plasma electrolysis boro-carbonization and boro-carbonization method
CN104141104A (en) * 2013-05-08 2014-11-12 北京师范大学 Solution for rapid plasma electrolytic carbonitriding on steel surface and carbonitriding method
CN104294343A (en) * 2013-07-18 2015-01-21 北京师范大学 Preparation method of diamond-like composite carburizing layer of steel surface

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