CN109234712B - Treatment process of stainless steel fluoropolymer synergistic coating - Google Patents

Treatment process of stainless steel fluoropolymer synergistic coating Download PDF

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CN109234712B
CN109234712B CN201710564647.0A CN201710564647A CN109234712B CN 109234712 B CN109234712 B CN 109234712B CN 201710564647 A CN201710564647 A CN 201710564647A CN 109234712 B CN109234712 B CN 109234712B
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fluoropolymer
stainless steel
content
etching
plating layer
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CN109234712A (en
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邹洪庆
钱建才
吕基成
许斌
张强宏
吴厚昌
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Southwest Institute of Technology and Engineering of China South Industries Group
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No 59 Research Institute of China Ordnance Industry
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1646Characteristics of the product obtained
    • C23C18/165Multilayered product
    • C23C18/1653Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/02Processes for applying liquids or other fluent materials performed by spraying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254After-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1689After-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1689After-treatment
    • C23C18/1692Heat-treatment
    • C23C18/1696Control of atmosphere
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00Electrolytic etching or polishing
    • C25F3/02Etching
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2506/00Halogenated polymers
    • B05D2506/10Fluorinated polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2506/00Halogenated polymers
    • B05D2506/10Fluorinated polymers
    • B05D2506/15Polytetrafluoroethylene [PTFE]

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemically Coating (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The invention discloses a treatment process of a stainless steel fluoropolymer synergistic coating, which comprises the steps of firstly removing an oxide film on the surface of a stainless steel material, carrying out nickel pre-plating on the oxide film to prepare a nickel pre-plating layer, then carrying out chemical nickel plating on the nickel pre-plating layer to prepare a chemical nickel plating layer, then carrying out etching treatment on the chemical nickel plating layer by adopting an etching solution (a mixed solution consisting of sulfuric acid, phosphoric acid, an emulsifier OP-10, sodium dodecyl benzene sulfonate, sodium succinate and glycine), introducing fluoropolymer on the surface of a micropore one time or a plurality of times after etching, and finally carrying out heat treatment in a vacuum state to fuse the fluoropolymer and the chemical nickel plating layer into an integrated synergistic coating. The stainless steel synergistic coating prepared by the invention has extremely high bonding strength and hardness, good corrosion resistance and self-lubricating property, and simultaneously has low-temperature anti-sticking property, has good non-sticking property even if being placed in an environment of-40 ℃, and can be used for storing food in a refrigeration house and storing non-PVC plasma bags in the medical field.

Description

Treatment process of stainless steel fluoropolymer synergistic coating
Technical Field
The invention relates to stainless steel coating treatment, in particular to a treatment process of a stainless steel fluoropolymer synergistic coating.
Background
The stainless steel material has good plasticity and toughness, wear resistance, good processing performance and resistance to corrosion of weak corrosive media such as air, steam, water and the like, and is widely applied to the industries of chemical engineering, food machinery, electromechanics, environmental protection and the like. However, the corrosion rate of the stainless steel material is fast when the stainless steel material is directly contacted with substances such as seawater, soil or carbon steel, and the like, and even exceeds that of common low-carbon steel, so that the increasingly wide use requirements of the stainless steel material cannot be met; for example, stainless steel products used in marine environments need to have high corrosion resistance, stainless steel precision transmission parts used in mechanical transmission need to have ultrahigh hardness, excellent self-lubricating property and other properties, and stainless steel products used for storing articles in low-temperature (-40 ℃) environments, in particular stainless steel containers used for storing bagged food in food cold storages and stainless steel discs used for storing non-PVC plasma bags in the medical field need to have low-temperature anti-sticking property.
In the research on the improvement of the properties of stainless steel materials, the properties such as wear resistance and corrosion resistance of stainless steel materials are mainly improved by surface treatment, such as electrochemical oxidation treatment, passivation treatment, nitriding treatment followed by surface coloring, electroplating treatment, and passivation treatment followed by spraying of organic coating. Different from common steel materials, stainless steel materials belong to materials difficult to plate and treat due to surface inertia, the surface adhesion is very poor, the conventional surface treatment method cannot greatly improve the performances of the stainless steel materials such as hardness, strength, corrosion resistance and the like, and the prepared coating has very poor binding force with the surface of the stainless steel; in the research of improving the properties of metal coatings and surface treatments, researchers have succeeded in obtaining desired material property characteristics by combining the advantages of two or more materials and processes, such as combining a metal anodic oxide film with a low friction polymer or lubricant for controlling infiltration, and modifying the film by precision heat treatment to finally obtain a precision coating (also called a co-coating) which is an integral part of a metal part, wherein the co-coating has high hardness, strength, corrosion resistance, self-lubricity and other properties, and the combination of the properties exceeds that of a composite coating in a general sense, and has great application value, and a fluoropolymer co-coating treatment process for aluminum alloy materials and steel materials has been disclosed, wherein CN1616713A discloses a fluoropolymer co-coating treatment process for steel materials, which comprises the specific steps of: carrying out alkaline chemical degreasing, electrolytic degreasing or acid pickling activation treatment on a steel material according to a conventional method, then carrying out chemical nickel-phosphorus alloy plating in acidic chemical nickel plating by adopting a rack plating or barrel plating method to obtain a nickel substrate layer, then carrying out chemical pore-enlarging treatment or electrochemical alternating current pore-enlarging treatment on the nickel substrate layer by adopting a pore-enlarging solution, and then placing the steel material subjected to pore-enlarging treatment in a fluoropolymer emulsion (a mixed solution consisting of one or more fluoropolymers such as polytetrafluoroethylene, tetrafluoroethylene, hexafluoropropylene and the like) for hot dipping or electrolysis, or spraying the fluoropolymer emulsion on the surface of the nickel substrate layer subjected to pore-enlarging treatment by adopting a spraying method to obtain a fluoropolymer nickel-based coating; and finally, placing the nickel-based coating in a vacuum heat treatment furnace for heat treatment to obtain the steel fluoropolymer synergistic coating. The inventor tries to prepare the stainless steel synergistic coating by adopting the fluoropolymer synergistic coating treatment process disclosed in CN1616713A, and as a result, the prepared synergistic coating has very poor bonding strength with the surface of the stainless steel and even cannot form the synergistic coating. Therefore, it is necessary to develop a stainless steel synergistic coating with good bonding strength, high hardness, excellent corrosion resistance and low-temperature anti-sticking performance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a treatment process of a stainless steel fluoropolymer synergistic coating.
The purpose of the invention is realized as follows: a treatment process of a stainless steel fluoropolymer synergistic coating is characterized in that: firstly, removing an oxide film on the surface of a stainless steel material, carrying out nickel pre-plating on the oxide film to prepare a nickel pre-plating layer, then carrying out chemical nickel plating on the nickel pre-plating layer to prepare a chemical nickel plating layer, then carrying out etching treatment on the chemical nickel plating layer by adopting an etching solution, introducing a fluorine polymer on the etched chemical nickel plating layer, and finally carrying out vacuum heat treatment to fuse the fluorine polymer and the chemical nickel plating layer into a whole to form a synergistic coating; wherein, the etching solution comprises sulfuric acid, phosphoric acid, an etching homogenizing agent and an additive; the etching uniformity agent is a compound solution of an emulsifier OP-10 and sodium dodecyl benzene sulfonate according to the mass ratio of 2-5:1, and the additive is a compound solution of sodium succinate and glycine according to the mass ratio of 1-3: 1.
Except for special description, the parts are parts by weight, and the percentages are mass percentages.
Preferably, the etching solution contains 10-30% of sulfuric acid, 1-10% of phosphoric acid, 0.1-1.0g/L (g/L) of etching homogenizing agent and 10-30g/L of additive; more preferably, the content of sulfuric acid is 15-25%, the content of phosphoric acid is 3-7%, the content of etching uniformity agent is 0.3-0.6g/L, and the content of additive is 15-20 g/L.
Preferably, the etching treatment process of the invention adopts electrochemical anode etching, the temperature is room temperature, and the current density is 1.0-5.0A/dm2(amperes/square decimeter) for 1-5 minutes; more preferably, the temperature is 25 ℃ and the current density is 2-4A/dm2 for a period of 2-4 minutes.
In order to further enhance the performance of the synergistic coating of the stainless steel material, after the vacuum heat treatment is carried out to fuse the fluoropolymer and the electroless nickel plating layer into an integrated synergistic coating, the fluoropolymer is continuously introduced into the surface of the synergistic coating one or more times and the vacuum heat treatment is carried out to fuse the fluoropolymer and the synergistic coating into an integrated body.
In order to further enhance the performance of the synergistic coating of the stainless steel material, in the nickel pre-plating process, the components of the nickel pre-plating bath comprise nickel chloride and hydrochloric acid; wherein the nickel chloride content is 200-300g/l, the hydrochloric acid content is 200-400ml/l, the process temperature is normal temperature, and the current density is 4-7A/dm2The time is 3-8 minutes, and the thickness of the nickel preplating layer is 3-10 mu m (micrometer); preferably, the nickel chloride content is 230-260g/l, the hydrochloric acid content is 280-315ml/l, the process temperature is normal temperature, and the current density is 4-6A/dm2The time is 4-6 minutes, and the thickness of the nickel preplating layer is 5-8 mu m.
In order to further enhance the performance of the synergistic coating of the stainless steel material, firstly removing an oxide film on the surface of the stainless steel material, carrying out nickel pre-plating on the oxide film to prepare a nickel pre-plating layer, then carrying out chemical nickel plating on the nickel pre-plating layer to prepare a chemical nickel plating layer, then carrying out etching treatment on the chemical nickel plating layer by adopting an etching solution, introducing fluoropolymer on the etched chemical nickel plating layer and carrying out vacuum heat treatment to fuse the fluoropolymer and the chemical nickel plating layer into an integral synergistic coating, and finally introducing the fluoropolymer again on the surface of the synergistic coating and carrying out vacuum heat treatment to fuse the fluoropolymer and the synergistic coating into an integral body;
wherein, in the process of removing the oxidation film: firstly, stainless steel material is placed in 40-60 portions of sodium hydroxidegAlkaline degreasing is carried out in solution composed of/L, 15-25g/L sodium phosphate and 2-3g/L linear alkyl benzene sulfonate, the process temperature is 55-60 ℃, and the time is 20-35 minutes; placing it at 3-4%The HLP30-1 modified degreasing agent is used for electrolytic degreasing under the process conditions of cathode degreasing, the temperature is 65-69 ℃, and the current density is 4-7A/dm2The time is 4-6 minutes; then placing the mixture into a mixed solution consisting of 8 to 13 percent of sulfuric acid, 40 to 50 percent of hydrochloric acid and 0.5 to 1 percent of corrosion inhibitor for acid cleaning and activation for 5 to 7 minutes;
the nickel preplating process comprises the following steps: the nickel chloride content is 231-260g/l, the hydrochloric acid content is 280-315ml/l, the pre-plating process temperature is normal temperature, and the current density is 4-6A/dm2The time is 4-6 minutes, and the thickness of the nickel preplating layer is controlled to be 5-7 mu m;
the chemical nickel plating process comprises the following steps: the content of nickel ions in the plating solution is 4-8g/l, the content of hypophosphite is 20-40g/l, and the content of malic acid is 10-20 g/l; the content of lactic acid is 10-14ml/l, the content of citric acid is 0.5-2g/l, and the content of thiourea is 1 mg/l; the pH value of the plating solution is 4.5-5.2, the process time is 95-180 minutes, the temperature is 80-90 ℃, and the thickness of the chemical nickel plating layer is 20-35 mu m;
in the etching treatment process: the content of sulfuric acid is 16-22%, the content of phosphoric acid is 4-6%, the content of homogenizing agent is 0.4-0.5g/L, and the content of additive is 18-20 g/L; the etching temperature is 25 ℃, and the current density is 3-4A/dm2The time is 2-4 minutes, and the etching depth is 25-44% of the thickness of the chemical nickel plating layer;
introducing the fluorine polymer and carrying out a heat treatment process: introducing fluoropolymer particles by a hot dipping method, wherein the concentration of the fluoropolymer particles is 32-68g/L, the impregnation temperature is 43-79 ℃, and the impregnation time is 12-39 minutes; the vacuum degree of the heat treatment is 17-0.03Pa (Pa), the heat treatment temperature is 310-440 ℃, and the heat treatment time is 31-58 minutes;
in the process of introducing the fluorine polymer again on the surface of the synergistic coating and carrying out vacuum heat treatment: introducing fluoropolymer particles by a spraying method, wherein the concentration of the fluoropolymer particles is 110-290g/L, the spraying thickness is 5-8 μm, the vacuum degree is 4-0.08Pa, the heat treatment temperature is 330-430 ℃, and the heat treatment time is 35-58 minutes.
The fluorine polymer of the invention can adopt the water emulsion of fluorine polymers such as polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer and the like, such as DuPont Teflon emulsion, FR301 polytetrafluoroethylene emulsion and FR463 polyfluorinated ethylene propylene emulsion produced by Shanghai Sanaifu company, P-202 and F-203 polytetrafluoroethylene dispersion and FS-46 fluoroplastic dispersion emulsion produced by Shanghai organic chemistry research institute and the like.
The invention has the following beneficial effects:
compared with the defects of poor plating property, very poor bonding strength of a plating layer and easy shedding of the plating layer in the prior art, the method takes the nickel preplating layer and the chemical nickel plating layer as the substrate layer of the fluoropolymer synergistic coating, increases the plating property and the bonding strength of the chemical nickel plating layer by removing the surface oxidation film or the passivation layer and preparing the nickel preplating layer by adopting a high-current preplating technology, and solves the problem that the surface of the stainless steel is difficult to plate by combining a specific electrochemical etching solution and a specific electrochemical etching process, thereby being suitable for surface coating treatment of stainless steel materials such as martensitic stainless steel, austenitic stainless steel, ferritic stainless steel and the like. The chemical nickel plating layer has good binding force and better wear resistance than the electroplated layer; meanwhile, the etching treatment of the chemical nickel plating layer is completed in one step, the process operation is simple, the control is easy, the etching is uniform, the control on the depth and the density of the pores is better, the surface is not dusty and the membrane is not dropped after the etching, the depth and the pore diameter of the pores of the chemical nickel plating layer after the etching treatment are uniform, the porosity is 8-10 percent, and the average equivalent diameter of the micropores is 290-325 nm. The invention solves the technical problems that the workpiece is easy to deform, the fluoropolymer is easy to be carbonized and decomposed, the moisture, air or impurities in the micropores of the substrate layer are difficult to completely remove, the fluoropolymer is difficult to effectively fill in the micropores and the like in the precision heat treatment process through the synergistic action of a series of parameters, the surface of the prepared synergistic coating is difficult to oxidize and pollute, and the appearance quality and the consistency of the coating are good. The stainless steel synergistic coating prepared by the invention has the advantages of good bonding strength, extremely high hardness, very good wear resistance and compactness, and excellent water and oil resistance; through tests, the bonding strength is more than 20Mpa, and the Vickers hardness is 800-; the stainless steel synergistic coating prepared by the invention has very good corrosion resistance and self-lubricating property, the corrosion rating after 500 hours of 5% neutral salt spray test is 7-8 grades, and the coefficient of dynamic friction is 0.08-0.20. The stainless steel synergistic coating prepared by the invention also has low-temperature anti-sticking performance, has good non-sticking performance even if the stainless steel synergistic coating is placed in an environment with the temperature of-40 ℃, and can be used for storing food in the freezing field and storing non-PVC plasma bags in the medical field. The stainless steel synergistic coating prepared by the invention also has high-temperature anti-adhesion performance, can be used for surface treatment of non-PVC weldment molds, is particularly suitable for surface treatment of special molds for non-PVC bag-making production lines, and greatly improves the working efficiency of non-PVC bag-making production.
Detailed Description
The present invention is described in detail below with reference to specific examples, which are provided for further illustration only and are not to be construed as limiting the scope of the present invention, and many insubstantial modifications and adaptations of the invention may occur to those skilled in the art without departing from the scope of the present invention. All starting materials and reagents of the present invention are commercially available products known to those of ordinary skill in the art.
Example 1
A304 (06Cr19Ni10) stainless steel test plate with the specification of 50X 2mm is selected as a sample, the sample is polished to the surface roughness of Ra1.6, and then the stainless steel synergistic coating is prepared according to the following steps:
step 1, alkaline degreasing treatment: placing a stainless steel test plate in alkaline degreasing liquid, heating to 60 ℃, and keeping the temperature for 20 minutes; wherein the alkaline deoiling liquid mainly comprises 30g/l of sodium hydroxide, 10g/l of sodium phosphate and 1g/l of linear alkyl benzene sulfonate;
step 2, electrolytic degreasing treatment: placing the stainless steel test plate subjected to oil removal treatment in a 1% degreasing agent (produced by Chongqing Wujiu surface technology engineering Co., Ltd., modified by model number HLP 30-1) for electrolytic degreasing; wherein the electrolytic degreasing process conditions are cathode degreasing at 60 ℃ and at a current density of 3A/dm2For 1 minute;
step 3, acid washing and activating treatment: placing the stainless steel test plate subjected to electrolytic degreasing in a mixed solution composed of sulfuric acid, hydrochloric acid and a corrosion inhibitor at normal temperature for pickling and activating for 3 minutes; wherein, the content of sulfuric acid is 5 percent, the content of hydrochloric acid is 30 percent, and the content of corrosion inhibitor is 0.3 percent;
step 4, nickel preplating: the stainless steel test plate after acid cleaning and activation is placed in a nickel preplating solution (nickel chloride is 200g/l,Hydrochloric acid 200ml/l) at 4A/dm2Pre-plating for 3 minutes under the current density, controlling the thickness of the pre-plated nickel layer to be 3-4 mu m to obtain a stainless steel pre-plated nickel layer, cleaning the stainless steel pre-plated nickel layer by water, and drying the stainless steel pre-plated nickel layer by cold air;
and step 5, chemical nickel plating treatment: placing the stainless steel nickel preplating layer in an electroless nickel plating solution with the pH value of 4.8, heating and plating at the constant temperature of 88 +/-2 ℃ for 60 minutes to obtain an electroless nickel plating layer (the thickness of the electroless nickel plating layer is controlled to be 22 mu m); wherein the chemical nickel plating solution contains nickel ion 4g/l (NiSO 4 & 7H2O), and hypophosphite (NaH)2PO2·H2O) content is 10g/l, malic acid content is 6g/l, lactic acid content is 6ml/l, citric acid content is 0.5g/l, and thiourea content is 1 mg/l;
step 6, etching treatment: placing the stainless steel test plate subjected to chemical nickel plating in an etching solution, performing electrochemical etching treatment at room temperature (the etching depth is 22% of the thickness of the chemical nickel plating layer), rinsing with tap water for 30 seconds, washing with running water for 15 seconds, and drying with cold air; wherein the etching homogenizing agent is a compound solution of an emulsifier OP-10 and sodium dodecyl benzene sulfonate in a mass ratio of 4:1, the additive is a compound solution of sodium succinate and glycine in a mass ratio of 2:1, the content of sulfuric acid is 10%, the content of phosphoric acid is 1%, the content of the etching homogenizing agent is 0.1g/L, and the content of the additive is 10 g/L; the current density of the etching process is 1A/dm2For 1 min;
step 7, introducing a fluoropolymer and carrying out heat treatment: and (3) placing the etched stainless steel test plate in a 32g/l polytetrafluoroethylene emulsion solution, carrying out hot dipping for 15 minutes at 45 ℃, airing, placing the dried sample in a vacuum furnace, vacuumizing to 15Pa, carrying out heat treatment at 385 ℃ for 35 minutes, cooling to 150 ℃, and closing a vacuum system to obtain the stainless steel synergistic coating.
Example 2:
A316L (00Cr17Ni14Mo2) stainless steel disc is selected as a sample, polished until the surface roughness is Ra1.6, and then a stainless steel synergistic coating is prepared according to the following steps:
step 1, alkaline degreasing treatment: placing the stainless steel sample in alkaline degreasing fluid, heating to 70 ℃, and keeping the temperature for 25 minutes; wherein the alkaline deoiling liquid mainly comprises 100g/l of sodium hydroxide, 35g/l of sodium phosphate and 5g/l of linear alkyl benzene sulfonate;
step 2, electrolytic degreasing treatment: placing the stainless steel sample subjected to oil removal treatment in a 5% degreasing agent (produced by Chongqing Wujiu surface technology engineering Co., Ltd., modified by model number HLP 30-1) for electrolytic degreasing; wherein the electrolytic degreasing process conditions are cathode degreasing at 80 ℃ and with a current density of 10A/dm2For 10 minutes;
step 3, acid washing and activating treatment: placing the stainless steel sample subjected to electrolytic degreasing in a mixed solution composed of sulfuric acid, hydrochloric acid and a corrosion inhibitor at normal temperature for pickling and activating for 10 minutes; wherein, the content of the sulfuric acid is 20 percent, the content of the hydrochloric acid is 60 percent, and the content of the corrosion inhibitor is 2 percent;
step 4, nickel preplating: the stainless steel sample after acid cleaning and activation is placed in a nickel preplating solution (300 g/l of nickel chloride and 400ml/l of hydrochloric acid) at the concentration of 8A/dm2Pre-plating for 8 minutes under the current density, controlling the thickness of the pre-nickel plating layer to be 10 mu m to obtain a stainless steel pre-nickel plating layer, cleaning the stainless steel pre-nickel plating layer by water, and drying the stainless steel pre-nickel plating layer by cold air;
and step 5, chemical nickel plating treatment: placing the stainless steel nickel preplating layer in an electroless nickel plating solution with the pH value of 5.0, heating and plating at the constant temperature of 88 +/-2 ℃ for 238 minutes to obtain an electroless nickel plating layer (the thickness of the electroless nickel plating layer is controlled to be 45 mu m); wherein the chemical nickel plating solution contains nickel ion 10g/l (NiSO 4 & 7H2O), and hypophosphite (NaH)2PO2·H2O) content of 58g/l, malic acid content of 29g/l, lactic acid content of 19ml/l, citric acid content of 4.8g/l, thiourea content of 1 mg/l;
step 6, etching treatment: placing the stainless steel sample subjected to chemical nickel plating in an etching solution, performing electrochemical etching treatment at room temperature (the etching depth is 48% of the thickness of the chemical nickel plating layer), rinsing with tap water for 28 seconds, cleaning with running water for 12 seconds, and drying with cold air; wherein, the etching uniform agent is a compound solution of an emulsifier OP-10 and sodium dodecyl benzene sulfonate according to the mass ratio of 4:1, the additive is a compound solution of sodium succinate and glycine according to the mass ratio of 2:1, the content of sulfuric acid is 30 percent,the content of phosphoric acid is 10 percent, the content of etching uniformity agent is 1.0g/L, and the content of additive is 30 g/L; the current density of the etching process is 5.0A/dm2The time is 5 min;
step 7, introducing a fluoropolymer and carrying out heat treatment: placing the etched stainless steel sample in 68g/l polytetrafluoroethylene emulsion solution, hot-dipping at 79 ℃ for 39 minutes, drying, placing the dried sample in a vacuum furnace, vacuumizing to 0.03Pa, performing heat treatment at 420 ℃ for 57 minutes, cooling to 150 ℃, and closing a vacuum system to obtain a stainless steel synergistic coating (first modification);
step 8, introducing the fluoropolymer again on the surface of the stainless steel synergistic coating, and simultaneously carrying out vacuum heat treatment modification to fuse the fluoropolymer and the formed synergistic coating into a whole so as to obtain a stainless steel synergistic coating after secondary modification; in the step, a spraying method is adopted to introduce the fluoropolymer, the concentration of fluoropolymer particles is 290g/L, the spraying thickness is 8 mu m, the vacuum degree is 0.05Pa, the heat treatment temperature is 420 ℃, and the heat treatment time is 50 minutes.
Example 3, example 4: referring to the procedure of example 2, a stainless steel fluoropolymer synergistic coating was prepared according to the process parameters in table 1; the etching uniformity agent of the embodiment 3 is a compound solution of an emulsifier OP-10 and sodium dodecyl benzene sulfonate in a mass ratio of 2:1, and the additive is a compound solution of sodium succinate and glycine in a mass ratio of 1: 1.
Example 5 and example 6: with reference to the procedure of example 1, a stainless steel fluoropolymer synergistic coating was prepared according to the process parameters in table 1; the etching uniformity agent of example 5 is a compound solution of an emulsifier OP-10 and sodium dodecylbenzenesulfonate in a mass ratio of 5:1, and the additive is a compound solution of sodium succinate and glycine in a mass ratio of 3: 1.
Example 7: referring to the steps of example 2, preparing a second modified stainless steel fluoropolymer synergistic coating according to the process parameters in table 1, introducing a fluoropolymer on the surface of the second modified stainless steel fluoropolymer synergistic coating, and simultaneously performing vacuum heat treatment modification to fuse the fluoropolymer and the synergistic coating into a whole to obtain a third modified stainless steel synergistic coating; in the step, a hot dipping method is adopted to introduce the fluoropolymer, the concentration of fluoropolymer particles is 45g/L, the emulsion temperature is 45 ℃, the hot dipping time is 15 minutes, the vacuum degree is 1Pa, the heat treatment temperature is 382 ℃, and the heat treatment time is 45 minutes.
TABLE 1 Process parameters for examples 3-7
Figure BDA0001346049010000081
And (3) performance testing: before the operation of step 5 of examples 1 to 7, the sample was observed for the color of the nickel pre-plating layer and the thickness of the nickel pre-plating layer was measured by the microscopic metallographic method, and the data results obtained are shown in table 2; before the operation of step 7 of examples 1 to 7, the sample after etching treatment was subjected to SEM image processing using ImageJ software and statistically analyzed for porosity, number of pores and equivalent diameter of the Ni — P alloy surface layer, and the obtained data results are shown in table 2; taking the stainless steel synergistic coating sample prepared in the examples 1-7 and a common 316L stainless steel sample, observing the surface of the sample, and respectively carrying out performance test according to the specification requirements: testing the thickness of the synergistic coating by using a microscopic metallographic method according to the specification of GB 6462; according to the regulation of GB9790, the hardness of the synergistic coating is tested by a microscopic metallographic method; after a 500 hour 5% neutral salt spray test as specified in astm b117, the corrosion rating was performed as specified in astm d 1654; testing the coefficient of dynamic friction according to the specification of GB 12444.1; the stainless steel sample prepared in examples 1 to 7 and a common 316L stainless steel sample were subjected to a low-temperature blocking test, a non-PVC plasma bag was placed on the stainless steel sample and stored at-40 ℃ for 24 hours, the adhesion of the stainless steel coating and the rupture of the plasma bag were observed, then the temperature was slowly raised to 60 to 90 ℃ to take out the non-PVC plasma bag, the adhesion of the stainless steel coating and the rupture of the plasma bag were observed, the blood state was observed after the non-PVC plasma bag was returned to room temperature, the above process was repeated 10 times, the adhesion of the coating and the rupture of the plasma bag were observed, and the test results are shown in Table 2.
Table 2 stainless steel fluoropolymer synergistic coating test results
Figure BDA0001346049010000091
As can be seen from Table 2, the stainless steel fluoropolymer synergistic coating of the invention has an etching layer porosity of 8-10%, uniform pore size of micropores, and an average equivalent diameter of 290-325 nm; the stainless steel fluoropolymer synergistic coating prepared by the invention is uniform metallic color or light yellow, hydrophobic and oleophobic on the surface, smooth in hand feeling, 22-25 mu m thick in chemical nickel plating layer, very good in uniformity, 800-950HV in Vickers hardness, extremely high in hardness, 8-grade in corrosion rating, 0.08-0.14 in coefficient of friction value, good in non-adhesiveness within-40 ℃ and greatly improved in comprehensive performance compared with the prior art, and the tested plasma bag has no rupture condition.

Claims (6)

1. A treatment process of a stainless steel fluoropolymer synergistic coating is characterized in that: firstly, removing an oxide film on the surface of a stainless steel material, carrying out nickel pre-plating on the oxide film to prepare a nickel pre-plating layer, then carrying out chemical nickel plating on the nickel pre-plating layer to prepare a chemical nickel plating layer, then carrying out etching treatment on the chemical nickel plating layer by adopting an etching solution, introducing a fluorine polymer on the etched chemical nickel plating layer, and finally carrying out vacuum heat treatment to fuse the fluorine polymer and the chemical nickel plating layer into an integrated cooperative coating; wherein, the etching solution comprises sulfuric acid, phosphoric acid, an etching homogenizing agent and an additive; the etching homogenizing agent is a compound solution of an emulsifier OP-10 and sodium dodecyl benzene sulfonate according to the mass ratio of 2-5:1, and the additive is a compound solution of sodium succinate and glycine according to the mass ratio of 1-3: 1;
the content of sulfuric acid in the etching solution is 10-30%, the content of phosphoric acid is 1-10%, the content of an etching homogenizing agent is 0.1-1.0g/L, and the content of an additive is 10-30 g/L;
the etching treatment process adopts electrochemical anode etching, the process temperature is room temperature, and the current density is 1.0-5.0A/dm2For 1-5 minutes;
after the fluoropolymer and the chemical nickel plating layer are fused into an integrated synergistic coating through vacuum heat treatment, the fluoropolymer is continuously introduced into the surface of the synergistic coating for one or more times and vacuum heat treatment is carried out to fuse the fluoropolymer and the synergistic coating into an integrated body;
in the nickel pre-plating process, the components of the nickel pre-plating bath comprise nickel chloride and hydrochloric acid; wherein the nickel chloride content is 200-300g/l, the hydrochloric acid content is 200-400ml/l, the process temperature is normal temperature, and the current density is 4-7A/dm2The time is 3-8 minutes, and the thickness of the nickel preplating layer is 3-10 mu m.
2. The process of claim 1 for the treatment of stainless steel fluoropolymer synergistic coatings, wherein: the etching solution contains 15-25% of sulfuric acid, 3-7% of phosphoric acid, 0.3-0.6g/L of etching homogenizing agent and 15-20g/L of additive.
3. The process of claim 2 for the treatment of stainless steel fluoropolymer synergistic coatings, wherein: the etching treatment process adopts electrochemical anode etching, the process temperature is 25 ℃, and the current density is 2-4A/dm2The time is 2-4 minutes.
4. The stainless steel fluoropolymer synergistic coating treatment process according to claim 1, 2 or 3, characterized in that: the multiple times are two or three times.
5. The process of claim 4 for the treatment of stainless steel fluoropolymer synergistic coatings, wherein: the nickel chloride content is 230-260g/l, the hydrochloric acid content is 280-315ml/l, the process temperature is normal temperature, and the current density is 4-6A/dm2The time is 4-6 minutes, and the thickness of the nickel preplating layer is 5-8 mu m.
6. The process of claim 1 for the treatment of stainless steel fluoropolymer synergistic coatings, wherein: firstly removing an oxide film on the surface of a stainless steel material, carrying out nickel pre-plating on the oxide film to prepare a nickel pre-plating layer, then carrying out chemical nickel plating on the nickel pre-plating layer to prepare a chemical nickel plating layer, then carrying out etching treatment on the chemical nickel plating layer by adopting etching solution, introducing fluoropolymer on the etched chemical nickel plating layer and carrying out vacuum heat treatment to fuse the fluoropolymer and the chemical nickel plating layer into an integrated cooperative coating, and finally introducing the fluoropolymer on the surface of the cooperative coating again and carrying out vacuum heat treatment to fuse the fluoropolymer and the cooperative coating into an integrated body;
wherein, in the process of removing the oxidation film: firstly, stainless steel materials are put into solution consisting of 40-60g/L of sodium hydroxide, 15-25g/L of sodium phosphate and 2-3g/L of linear alkyl benzene sulfonate for alkaline degreasing, the process temperature is 55-60 ℃, and the time is 20-35 minutes; then placing the mixture into a 3-4% HLP30-1 degreasing agent for electrolytic degreasing, wherein the process conditions are that the cathode degreases, the temperature is 65-69 ℃, and the current density is 4-7A/dm2The time is 4-6 minutes; then placing the mixture into a mixed solution consisting of 8 to 13 percent of sulfuric acid, 40 to 50 percent of hydrochloric acid and 0.5 to 1 percent of corrosion inhibitor for acid cleaning and activation for 5 to 7 minutes;
the nickel preplating process comprises the following steps: the nickel chloride content is 231-260g/l, the hydrochloric acid content is 280-315ml/l, the pre-plating process temperature is normal temperature, and the current density is 4-6A/dm2The time is 4-6 minutes, and the thickness of the nickel preplating layer is controlled to be 5-7 mu m;
the chemical nickel plating process comprises the following steps: the content of nickel ions in the plating solution is 4-8g/l, the content of hypophosphite is 20-40g/l, and the content of malic acid is 10-20 g/l; the content of lactic acid is 10-14ml/l, the content of citric acid is 0.5-2g/l, and the content of thiourea is 1 mg/l; the PH value of the plating solution is 4.5-5.2, the chemical plating time is 95-180 minutes, the temperature is 80-90 ℃, and the thickness of the chemical nickel plating layer is 22-25 mu m;
in the etching treatment process: the content of sulfuric acid is 16-22%, the content of phosphoric acid is 4-6%, the content of homogenizing agent is 0.4-0.5g/L, and the content of additive is 18-20 g/L; the etching temperature is 25 ℃, and the current density is 3-4A/dm2The time is 2-4 minutes, and the etching depth is 25-44% of the thickness of the chemical nickel plating layer;
introducing the fluorine polymer and carrying out a heat treatment process: introducing fluoropolymer particles by a hot dipping method, wherein the concentration of the fluoropolymer particles is 32-68g/L, the impregnation temperature is 43-79 ℃, and the impregnation time is 12-39 minutes; the vacuum degree of the heat treatment is 17-0.03Pa, the heat treatment temperature is 310-440 ℃, and the heat treatment time is 31-58 minutes;
in the process of introducing the fluorine polymer again on the surface of the synergistic coating and carrying out vacuum heat treatment: introducing fluoropolymer particles by a spraying method, wherein the concentration of the fluoropolymer particles is 110-290g/L, the spraying thickness is 5-8 μm, the vacuum degree is 4-0.08Pa, the heat treatment temperature is 330-430 ℃, and the heat treatment time is 35-58 minutes.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1222585A (en) * 1997-11-14 1999-07-14 游天来 Metal surface treating method
CN1616713A (en) * 2004-09-13 2005-05-18 中国兵器工业第五九研究所 Fluoro polymer synergistic coating treatment process for iron and steel material
CN1687488A (en) * 2005-03-18 2005-10-26 中国兵器工业第五九研究所 Technique for treating synergism coat of aluminium alloy material and fluorine polymer
CN102234806A (en) * 2010-04-23 2011-11-09 比亚迪股份有限公司 Stainless steel etching solution and etching method
CN103668386A (en) * 2013-12-17 2014-03-26 广西理工职业技术学院 Aluminum and aluminum alloy surface treatment method
CN104313556A (en) * 2014-09-25 2015-01-28 东莞劲胜精密组件股份有限公司 Metal treating agent and composite material and preparation method thereof
CN105500600A (en) * 2014-09-24 2016-04-20 比亚迪股份有限公司 Surface treatment method for metal substrate, the metal substrate, and metal-resin composite and production method of same
CN106757264A (en) * 2016-11-23 2017-05-31 南昌航空大学 A kind of aluminum alloy environment-friendly type temperature anodic oxidation electrolyte wide and method for oxidation

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1222585A (en) * 1997-11-14 1999-07-14 游天来 Metal surface treating method
CN1616713A (en) * 2004-09-13 2005-05-18 中国兵器工业第五九研究所 Fluoro polymer synergistic coating treatment process for iron and steel material
CN1687488A (en) * 2005-03-18 2005-10-26 中国兵器工业第五九研究所 Technique for treating synergism coat of aluminium alloy material and fluorine polymer
CN102234806A (en) * 2010-04-23 2011-11-09 比亚迪股份有限公司 Stainless steel etching solution and etching method
CN103668386A (en) * 2013-12-17 2014-03-26 广西理工职业技术学院 Aluminum and aluminum alloy surface treatment method
CN105500600A (en) * 2014-09-24 2016-04-20 比亚迪股份有限公司 Surface treatment method for metal substrate, the metal substrate, and metal-resin composite and production method of same
CN104313556A (en) * 2014-09-25 2015-01-28 东莞劲胜精密组件股份有限公司 Metal treating agent and composite material and preparation method thereof
CN106757264A (en) * 2016-11-23 2017-05-31 南昌航空大学 A kind of aluminum alloy environment-friendly type temperature anodic oxidation electrolyte wide and method for oxidation

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