CN103014621B - Preparation method of Cr-Si-C-N nanoscale composite coating - Google Patents
Preparation method of Cr-Si-C-N nanoscale composite coating Download PDFInfo
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Abstract
The invention belongs to a preparation method of a coating and especially relates to a preparation method of a Cr-Si-C-N nanoscale composite coating on the surface of a super-critical water-cooled reactor casing. The preparation method comprises the following steps of 1, carrying out a matrix plating pretreatment and backwash washing process by grinding and polishing a matrix by a metallographic abrasive paper of 300 to 1200 meshes to obtain a matrix with a mirror surface, putting the matrix with the mirror surface into an ultrasonic container, carrying out degreaser cleaning, carrying out pickling and deionized water rinsing, drying in a vacuum drying oven, putting the dried matrix into a deposition vacuum chamber and carrying out plasma backwash washing, 2, carrying out Cr(C,N) gradient transition layer deposition, 3, carrying out Cr-Si-C-N nanoscale composite coating deposition, and 4, carrying out coating heat treatment. The preparation method has the advantages of high hardness, high antioxidation degree and good coating adhesion.
Description
Technical field
The invention belongs to the preparation method of coating, be specifically related to a kind of preparation method of Supercritical-Pressure Light Water Cooled Reactor fuel sheath surface C r-Si-C-N nano-composite coating.
Background technology
Compare with all multiple-energy-sources such as coal, oil, sun power, water energy, nuclear power is as a kind of efficient, economic and lasting energy, and the comprehensive advantage of the aspects such as the energy dilemma facing in the solution whole world, protection of the environment quality is remarkable.The advantages such as Supercritical-Pressure Light Water Cooled Reactor has that thermo-efficiency is high, designs simplification, security are good, good economy performance.The research of Supercritical-Pressure Light Water Cooled Reactor fuel canning material is one of key of Supercritical-Pressure Light Water Cooled Reactor technical research.At present, low swelling austenitic stainless steel as D9,1.4970,316Ti etc. be main Supercritical-Pressure Light Water Cooled Reactor fuel canning material, these materials have the advantages such as intensity is high, void swelling is low, weldability is good, neutron economy is better.Yet, the high temperature oxidation corrosion resistance poor-performing of above-mentioned materials in supercritical water, in long service process, excessive oxidation corrosion speed certainly will affect the structural integrity of fuel sheath.
Nano-composite coating in Supercritical-Pressure Light Water Cooled Reactor fuel sheath surface deposition high temperature oxidation resistance excellence, can solve an above-mentioned difficult problem effectively, and this also becomes the study hotspot of academia and engineering circles in recent years.At the research initial stage, people trend towards the alloy coat at involucrum surface deposition Cr, because itself and steel substrate can form Fe-Cr compound at interface, realize chemical metallurgy combination, thereby have good coating/base material bonding force.Meanwhile, in coating, Cr element can form protection by oxide films layer with the O in corrosive environment on surface, hinders soaking into of corrosive medium, thereby has good high temperature oxidation resistance.But, the alloy coat that Cr and other metals form is in aspect shortcoming advantages such as intensity, hardness, wear resistancies, strong high-temperature water thermal shocking may cause the distortion of coating ductility, premature failure, as document [Wang Jianping, Xu Lianyong, permitted Yongtai, the resistance to high temperature corrosion performance research of Li Jia .FeCrAl and nickelic chromium alloy coating. China Power, 2007,40 (4): 54-57].Afterwards, more research trends towards paying close attention to the metal nitride coatings such as CrN, TiN and CrAlN.With respect to Cr alloy coat, nitride coatings has more advantage at aspects such as corrosion resistance, hardness and wear resistancies.For example, TiN coating has higher hardness, about 20GPa, its oxidation resistance temperature is 400 ℃～500 ℃, as document [Song Guihong, Du Hao, He Chunlin. hard and superhard coating-properity, preparation with sign, Beijing: Chemical Industry Press, 2007]; CrN coating also has higher hardness, about 18GPa, also there is good toughness and high temperature oxidation resistance, as document [M.A.Djouadi, C.Nouveau, P.Beer, M.Lambertin.CrxNy hard coatings deposited with PVD method on tools for wood machining.Surface and Coatings Technology, 2000,133,478-483].In recent years, along with developing rapidly of nanotechnology, nano-composite coating is owing to all having very significant advantage with respect to conventional washcoat material at aspect of performances such as resistance to high temperature oxidation, hardness, frictional wear, anti-thermal shocks, thereby caused investigator's extensive concern.For example, the hardness of Ti-Al-Si-N nano-composite coating can be up to 45GPa, wear rate can be lower than 1.0 * 10
-14m
2n
-1as document [E.Ribeiro, A.Malczyk, S.Carvalho, et al.Effects of ion bombardment on properties of d.c.sputtered superhard (Ti, Si, Al) N nanocomposite coatings.Surface and Coatings Technology, 2002,151-152,515-520]; The resistance to high temperature oxidation temperature of Ti-Si-C-N nano-composite coating can reach more than 900 ℃, and at high temperature it still has excellent mechanical property, as coating hardness value can reach about 40GPa 900 ℃ time, as document [D.Ma, S.Ma, K.Xu.Superhard nanocomposite Ti-Si-C-N coatings prepared by pulsed-d.c plasma enhanced CVD.Surface and Coatings Technology, 2005,200,382-386].Suchlike research shows, nano-composite coating has more excellent high temperature oxidation corrosion resistance performance and mechanical property.At present, the research of nano-composite coating is mainly comprised in the following areas: the first, develop the nano-composite coating novel material of various element constituent elements, as Cr-Al-Si-N, Ti-Si-C-N, W-Si-C-N etc.; The second, Reasonable Regulation And Control design coating forms structure, makes it have the pattern structure of (amorphous phase+nanometer crystalline phase) form; The 3rd, optimize buffer layer material, to improve bonding strength between nano-composite coating and matrix etc., as document [P.Holubar, M.Jilek, M.Sima.Present and possible future applications of superhard nanocomposite coatings.Surface and Coatings Technology, 2000,133-134,145-151].
To sum up, at present also not at satisfactory alloy all in nature such as hardness, intensity, wear resistance, erosion resistance.
Summary of the invention
The present invention is directed to the defect of prior art, provide a kind of hardness high, the preparation method of the Cr-Si-C-N nano-composite coating of oxidation-resistance number.
Technical scheme of the present invention is: a kind of preparation method of Cr-Si-C-N nano-composite coating, comprises the steps
Step 1: matrix plating pre-treatment and backwash clean
With 300 order～1200 object abrasive paper for metallograph, base material is carried out to grinding and polishing, reach mirror status, then base material is placed in to ultrasonic container and carries out degreaser cleaning, after having cleaned, degreaser carries out in vacuum drying oven, drying after pickling and rinsed with deionized water, finally oven dry base material is placed in to deposition vacuum chamber and carries out the cleaning of plasma body backwash
Step 2: Cr (C, N) gradient transitional lay deposition
Adopt JW-500 type arc ion intensified response magnetron sputtering equipment to deposit Cr (C, N) gradient transitional lay at substrate surface, first the vacuum tightness of environment is extracted into 5 * 10
-4pa, is then filled with Ar gas, and Ar airshed is 50sccm, and air pressure is 0.5Pa, ventilates 10 minutes, then by N
2with CH
4the flow of gas is adjusted to 50sccm and 40sccm gradually from 0sccm and 0sccm respectively, and air pressure is also 0.5Pa, and 3 kinds of source of the gas purity are 99.99%; The sputtering power of 1 magnetic control Cr target is transferred to the arc current of 2.0kW, 2 post arc Cr targets and is transferred to 70A, Cr target purity is 99.99%, and be transferred to-50V of deposition bias voltage, depositing temperature are transferred to 200 ℃, open subsequently chip bench baffle plate, deposition 30min, deposit thickness is about 1 μ m
Step 3: Cr-Si-C-N nano-composite coating deposition
Adopt JW-500 type arc ion intensified response magnetron sputtering equipment, after deposition transition layer, under the condition of uninterrupted vacuum environment, continue deposition Cr-Si-C-N nano-composite coating, in deposition process, environment vacuum tightness, Ar, N
2with CH
4the parameters such as gas flow and air pressure, magnetic control Cr target sputtering power, post arc Cr target arc current, depositing temperature all remain unchanged, magnetic control Si target sputtering power is transferred to 0.5kW, and matrix is deposited to bias voltage by-be transferred to-200V of 50V, depositing time is 1.5～2.0h, deposit thickness is about 2～3 μ m
Step 4: coating thermal treatment
After deposition Cr-Si-C-N nano-composite coating, uninterrupted vacuum environment, carries out in-situ annealing to sample, and its processing parameter is: vacuum tightness 5 * 10
-4pa, 500 ℃ of annealing temperatures, 10 ℃/min of temperature rise rate, soaking time 60 minutes, be chilled to room temperature with stove after insulation finishes, and takes out subsequently.
The preparation method of a kind of Cr-Si-C-N nano-composite coating as above, wherein, the base material described in step 1 comprises D9,1.4970,316Ti austenitic stainless steel.
The preparation method of a kind of Cr-Si-C-N nano-composite coating as above, wherein, ultrasonic container that base material is placed in described in step 1 carries out degreaser cleaning, the composition of degreaser comprises sodium carbonate 180g/L, Trisodium Citrate 50g/L, fatty alcohol-polyoxyethylene ether 5g/L, sodium phosphate 40g/L, and scavenging period is 10～15min.
The preparation method of a kind of Cr-Si-C-N nano-composite coating as above, wherein, after pickling described in step 1 and rinsed with deionized water, in vacuum drying oven, dry and comprise, pickling adopts the hydrochloric acid soln that concentration is 10% at room temperature to clean about 5min, rinses for several times subsequently with deionized water; The vacuum tightness of vacuum drying oven is 300Pa, and bake out temperature is 150 ℃, and baking time is longer than 1 hour.
The preparation method of a kind of Cr-Si-C-N nano-composite coating as above, wherein, the backwash cleaning parameters described in step 1 is: base vacuum degree 5 * 10
-4pa, backwash bias voltage-200V, sputter Ar air pressure 0.3Pa, backwash time 15min.
Effect of the present invention is: the dense oxidation film protective layer that (1) forms due to Cr and O can effectively stop the transmission of corrosive medium; and adopt Cr-Si-C-N coating process of the present invention can form the composite structure of amorphous phase+nanometer crystalline phase; thereby this nano-composite coating possesses excellent resistance to high temperature corrosion performance and mechanical property; its oxidation resistance temperature can reach 900 ℃, and hardness value can reach 35GPa.(2) Cr (C, N) gradient transitional lay structure makes Cr-Si-C-N nano-composite coating and stainless steel substrate have good interface bond strength, and coating adhesion can reach 35N.Adopt coating on the Supercritical-Pressure Light Water Cooled Reactor fuel sheath of Cr-Si-C-N nano-composite coating technique of the present invention can realize the coordinating and unifying that is coated with sheet building and function, use properties and the work-ing life of having improved Supercritical-Pressure Light Water Cooled Reactor fuel sheath.
Embodiment
A preparation method for Cr-Si-C-N nano-composite coating, comprises the steps
Step 1: matrix plating pre-treatment and backwash clean
With 300 order～1200 object abrasive paper for metallograph, base material is carried out to grinding and polishing, reach mirror status, described base material comprises D9,1.4970,316Ti austenitic stainless steel, and above-mentioned three kinds of base materials are commercially available material.Then base material is placed in to ultrasonic container and carries out degreaser cleaning, the composition of degreaser comprises sodium carbonate 180g/L, Trisodium Citrate 50g/L, fatty alcohol-polyoxyethylene ether 5g/L, sodium phosphate 40g/L.Scavenging period is 10～15min.After having cleaned, degreaser carries out in vacuum drying oven, drying after pickling and rinsed with deionized water.Pickling adopts the hydrochloric acid soln that concentration is 10% at room temperature to clean about 5min, rinses for several times subsequently with deionized water; The vacuum tightness of vacuum drying oven is 300Pa, and bake out temperature is 150 ℃, and baking time is longer than 1 hour.Finally oven dry base material is placed in to deposition vacuum chamber and carries out the cleaning of plasma body backwash, backwash cleaning parameters is: base vacuum degree 5 * 10
-4pa, backwash bias voltage-200V, sputter Ar air pressure 0.3Pa, backwash time 15min.
Step 2: Cr (C, N) gradient transitional lay deposition
Adopt JW-500 type arc ion intensified response magnetron sputtering equipment to deposit Cr (C, N) gradient transitional lay at substrate surface.First the vacuum tightness of environment is extracted into 5 * 10
-4pa, is then filled with Ar gas, and Ar airshed is 50sccm (standard cubic centimeters per minute), and air pressure is 0.5Pa, ventilates 10 minutes, then by N
2with CH
4the flow of gas is adjusted to 50sccm and 40sccm gradually from 0sccm and 0sccm respectively, and air pressure is also 0.5Pa, and 3 kinds of source of the gas purity are 99.99%; The sputtering power of 1 magnetic control Cr target is transferred to the arc current of 2.0kW, 2 post arc Cr targets and is transferred to 70A, Cr target purity is 99.99%, and be transferred to-50V of deposition bias voltage, depositing temperature are transferred to 200 ℃, opens subsequently chip bench baffle plate, deposition 30min, deposit thickness is about 1 μ m.
Step 3: Cr-Si-C-N nano-composite coating deposition
Adopt JW-500 type arc ion intensified response magnetron sputtering equipment, after deposition transition layer, under the condition of uninterrupted vacuum environment, continue deposition Cr-Si-C-N nano-composite coating.Target used, except 1 magnetic control Cr target and 2 post arc Cr targets, also has 2 magnetic control Si targets, and the purity of Si target is also 99.99%.In deposition process, environment vacuum tightness, Ar, N
2with CH
4the parameters such as gas flow and air pressure, magnetic control Cr target sputtering power, post arc Cr target arc current, depositing temperature all remain unchanged, magnetic control Si target sputtering power is transferred to 0.5kW, and matrix is deposited to bias voltage by-be transferred to-200V of 50V, and depositing time is 1.5～2.0h, deposit thickness is about 2～3 μ m.
Step 4: coating thermal treatment
After deposition Cr-Si-C-N nano-composite coating, uninterrupted vacuum environment, carries out in-situ annealing to sample, and its processing parameter is: vacuum tightness 5 * 10
-4pa, 500 ℃ of annealing temperatures, 10 ℃/min of temperature rise rate, soaking time 60 minutes, be chilled to room temperature with stove after insulation finishes, and takes out subsequently.
Claims (1)
1. a preparation method for Cr-Si-C-N nano-composite coating, is characterized in that: comprise the steps
Step 1: matrix plating pre-treatment and backwash clean
With 300 order～1200 object abrasive paper for metallograph, base material is carried out to grinding and polishing, reach mirror status, then base material is placed in to ultrasonic container and carries out degreaser cleaning, after having cleaned, degreaser carries out in vacuum drying oven, drying after pickling and rinsed with deionized water, finally oven dry base material is placed in to deposition vacuum chamber and carries out the cleaning of plasma body backwash
Step 2: Cr (C, N) gradient transitional lay deposition
Adopt JW-500 type arc ion intensified response magnetron sputtering equipment to deposit Cr (C, N) gradient transitional lay at substrate surface, first the vacuum tightness of environment is extracted into 5 * 10
-4pa, is then filled with Ar gas, and Ar airshed is 50sccm, and air pressure is 0.5Pa, ventilates 10 minutes, then by N
2with CH
4the flow of gas is adjusted to 50sccm and 40sccm gradually from 0sccm and 0sccm respectively, and air pressure is also 0.5Pa, and 3 kinds of source of the gas purity are 99.99%; The sputtering power of 1 magnetic control Cr target is transferred to the arc current of 2.0kW, 2 post arc Cr targets and is transferred to 70A, Cr target purity is 99.99%, and be transferred to-50V of deposition bias voltage, depositing temperature are transferred to 200 ℃, open subsequently chip bench baffle plate, deposition 30min, deposit thickness is about 1 μ m
Step 3: Cr-Si-C-N nano-composite coating deposition
Adopt JW-500 type arc ion intensified response magnetron sputtering equipment, after deposition transition layer, under the condition of uninterrupted vacuum environment, continue deposition Cr-Si-C-N nano-composite coating, in deposition process, environment vacuum tightness, Ar, N
2with CH
4the parameters such as gas flow and air pressure, magnetic control Cr target sputtering power, post arc Cr target arc current, depositing temperature all remain unchanged, magnetic control Si target sputtering power is transferred to 0.5kW, and matrix is deposited to bias voltage by-be transferred to-200V of 50V, depositing time is 1.5～2.0h, deposit thickness is 2～3 μ m
Step 4: coating thermal treatment
After deposition Cr-Si-C-N nano-composite coating, uninterrupted vacuum environment, carries out in-situ annealing to sample, and its processing parameter is: vacuum tightness 5 * 10
-4pa, 500 ℃ of annealing temperatures, 10 ℃/min of temperature rise rate, soaking time 60 minutes, be chilled to room temperature with stove after insulation finishes, and takes out subsequently.
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| CN106381471B (en) * | 2016-09-19 | 2018-11-23 | 中国科学院宁波材料技术与工程研究所 | A kind of wear-resistant coating and preparation method and application of the wide change of hardness |
| CN110484867B (en) * | 2018-05-15 | 2021-09-21 | 蓝思科技（长沙）有限公司 | Dark black coating Logo for non-metal cover plate and preparation method thereof |
| CN109957757B (en) * | 2019-04-04 | 2021-06-08 | 中国核动力研究设计院 | Method for preparing ultra-thick Ti-Al-C ternary coating by two-step PVD (physical vapor deposition) technology |
| CN111826616B (en) * | 2020-07-23 | 2022-05-13 | 北京市辐射中心 | Nuclear fuel cladding coating and preparation method thereof |
| CN112281125B (en) * | 2020-09-29 | 2022-07-12 | 维达力实业(深圳)有限公司 | Composite metal film and preparation method and application thereof |
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| CN101608299A (en) * | 2009-07-13 | 2009-12-23 | 四川大学 | High hard, the low friction Cr/CrCN gradient coating technology in abnormity reed surface |
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| CN101608299A (en) * | 2009-07-13 | 2009-12-23 | 四川大学 | High hard, the low friction Cr/CrCN gradient coating technology in abnormity reed surface |
Non-Patent Citations (2)
| Title |
|---|
| Chul Sik Jang, Young Rae Cho, Myung Chang Kang, Won Sub Chung, K.Microstructure and Mechanical Properties of Cr-C-N, Cr-Si-N and Cr-Si-C-N Coatings by a Hybrid Coating System.《Key Engineering Materials》.2007,第336-338卷全文. * |
| Microstructure and Mechanical Properties of Cr-C-N, Cr-Si-N and Cr-Si-C-N Coatings by a Hybrid Coating System;Chul Sik Jang, Young Rae Cho, Myung Chang Kang, Won Sub Chung, K;《Key Engineering Materials》;20070430;第336-338卷;全文 * |
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