CN109234712A - A kind of stainless steel synergistic fluoropolymer coating treatment process - Google Patents
A kind of stainless steel synergistic fluoropolymer coating treatment process Download PDFInfo
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- CN109234712A CN109234712A CN201710564647.0A CN201710564647A CN109234712A CN 109234712 A CN109234712 A CN 109234712A CN 201710564647 A CN201710564647 A CN 201710564647A CN 109234712 A CN109234712 A CN 109234712A
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- 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
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment 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
- B05D3/02—Pretreatment 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
- B05D3/0254—After-treatment
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- 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
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
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- 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
- C23C18/00—Chemical 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
- C23C18/16—Chemical 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
- C23C18/1692—Heat-treatment
- C23C18/1696—Control of atmosphere
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2506/00—Halogenated polymers
- B05D2506/10—Fluorinated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2506/00—Halogenated polymers
- B05D2506/10—Fluorinated polymers
- B05D2506/15—Polytetrafluoroethylene [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 kind of stainless steel synergistic fluoropolymer coating treatment process, the oxidation film of surface of stainless steel is removed first, and nickel preplating is carried out to it to prepare pre-nickel plating, then chemical nickel plating is carried out on pre-nickel plating prepare chemical Ni-plating layer, again using etching solution (by sulfuric acid, phosphoric acid, emulsifier op-10, neopelex, the mixed solution of sodium succinate and glycine composition) chemical Ni-plating layer is etched, in the one or many introducing fluoropolymers of micropore surface after etching, finally carrying out heat treatment under vacuum conditions makes fluoropolymer and chemical Ni-plating layer fusion be formed as one synergism coat.Stainless steel synergism coat bond strength and extreme hardness prepared by the present invention, corrosion resistance and self-lubricating property are good, also there is low temperature anti-adhesion performance simultaneously, even if placing it in -40 DEG C of environment, also have good non-stick, it cannot be only used for storing food in freezer, it may also be used for medical domain stores non-PVC plasma bags.
Description
Technical field
The present invention relates to stainless steel coating processing, specifically a kind of stainless steel synergistic fluoropolymer coating treatment process.
Background technique
Stainless steel material has preferable plasticity and toughness, wearability, and good processing performance has resistance to air, steam, water etc.
The performance of weak corrosive medium corrosion, is widely used in the industries such as chemical industry, food machinery, electromechanics and environmental protection.But stainless steel material
Quickly, even more than ordinary low-carbon steel is unable to satisfy it and gets over corrosion rate when directly contacting with substances such as seawater, soil or carbon steels
Carry out more extensive use demand；It such as needs it with high-corrosion resistance for the stainless steel product in marine environment, is used for machine
Tool transmission precision stainless steel driving member need the performances such as its hardness with superelevation and excellent self-lubrication, for low temperature (-
40 DEG C) stainless steel product that article is stored in environment, stored especially in food stuff refrigerated storage packed food rustless steel container and
The stainless steel disc that medical domain stores non-PVC plasma bags needs it with low temperature anti-adhesion performance.
In the research for improving stainless steel material performance, presently mainly improve stainless steel material by being surface-treated
The performances such as wearability and corrosion resistance, such as surface coloring, plating are carried out after electrochemicial oxidation, Passivation Treatment, Nitrizing Treatment
Organic coating is sprayed after coating treatment and Passivation Treatment.Different from general steel material, stainless steel material belongs to because of surface inertness
Hardly possible plating and difficult material, surface adhesion is very poor, Conventional surface treatment can not greatly improve stainless steel material hardness,
The performances such as intensity and corrosion resistance, and the coating and stainless steel surface binding force that prepare are very poor；Improve metal coating performance and
In surface treatment research, researcher is successfully by means of obtaining the phase in conjunction with the advantages of two or more materials and technical process
Anodic metal oxide film is such as combined with the low friction polymer of control infiltration or lubricant, is led to by the material characteristics iare of prestige
It crosses precision heat treatment to be modified it, finally obtains a kind of fine layers for belonging to metal parts entirety part and (also referred to as assist
Close coating), the performances such as synergism coat hardness with higher, intensity, corrosion resistance and self-lubrication, comprehensive performance is more than one
As composite coating in meaning, there is great application value, have been disclosed that the fluorine of aluminum alloy materials and steel material is poly- at present
Close object technique for treating synergism coat, wherein the tool of steel material synergistic fluoropolymer coating treatment process disclosed in CN1616713A
Body step are as follows: steel material is first carried out to alkali electroless degreasing, electrolytic degreasing or acid-wash activation processing according to a conventional method, is then adopted
With rack plating or method of barrel electroplating in acid chemical plating nickel chemical plating nickel-phosphorus alloy, obtain Ni-based bottom, then use reaming solution
Chemical enlargement processing or electrochemical ac expanding treatment are carried out to Ni-based bottom, are then placed in the steel material after expanding treatment
Fluoropolymer emulsions (the mixing being made of one or more of fluoropolymers such as polytetrafluoroethylene (PTFE), tetrafluoroethene, hexafluoropropene
Liquid) in hot dipping or electrolysis, or using spray coating method after expanding treatment Ni-based bottom surface spraying fluoropolymer emulsions obtain
Fluoropolymer-containing Ni-based coating；Finally Ni-based coating is placed in vacuum heat treatment furnace and is heat-treated, steel fluoropolymer is obtained
Synergism coat.Inventor attempts to prepare using steel material synergistic fluoropolymer coating treatment process disclosed in CN1616713A
Stainless steel synergism coat as a result, it has been found that the synergism coat and stainless steel surface bond strength of preparation are excessively poor, or even can not be formed
Synergism coat.Therefore, exploitation bond strength is good, hardness is high, excellent corrosion-proof performance, is provided simultaneously with the stainless steel of low temperature anti-adhesion performance
Synergism coat is very necessary.
Summary of the invention
To solve problems of the prior art, it is an object of that present invention to provide a kind of paintings of stainless steel fluoropolymer synergism
Layer treatment process.
What the object of the invention was realized in: a kind of stainless steel synergistic fluoropolymer coating treatment process, it is characterised in that:
The oxidation film of surface of stainless steel is removed first, and nickel preplating is carried out to it to prepare pre-nickel plating, then in pre-nickel plating
Upper progress chemical nickel plating prepares chemical Ni-plating layer, is then etched using etching solution to chemical Ni-plating layer, and losing
Fluoropolymer is introduced on chemical Ni-plating layer after quarter, finally carry out vacuum heat treatment make fluoropolymer and chemical Ni-plating layer fusion be
One forms synergism coat；Wherein, etching solution includes sulfuric acid, phosphoric acid, etching homogenizing agent and additive；Etching homogenizing agent is
According to mass ratio=2-5:1 combination solution, additive is sodium succinate and sweet for emulsifier op-10 and neopelex
Propylhomoserin is according to mass ratio=1-3:1 combination solution.
Unless otherwise specified, number of the present invention is parts by weight, and the percentage is mass percent.
Preferably, sulfuric acid content is 10-30% in above-mentioned etching solution, and phosphorus acid content 1-10%, etching homogenizing agent contain
Amount is 0.1-1.0g/L (grams per liter), additive level 10-30g/L；It is highly preferred that sulfuric acid content is 15-25%, phosphoric acid contains
Amount is 3-7%, and etching uniform agent content is 0.3-0.6g/L, additive level 15-20g/L.
Preferably, etch process is etched using Anodic in the present invention, and temperature is room temperature, and current density is
1.0-5.0A/dm2(ampere/square decimeter), time are 1-5 minutes；It is highly preferred that temperature is 25 DEG C, current density 2-4A/
Dm2, time are 2-4 minutes.
For the performance for further enhancing stainless steel material synergism coat of the present invention, make fluorine in vacuum heat treatment in the above method
After polymer and chemical Ni-plating layer fusion are formed as one synergism coat, continue one or many introducing fluorine on synergism coat surface
Polymer simultaneously carries out vacuum heat treatment and fuses fluoropolymer and aforementioned synergism coat being integrated.
For the performance for further enhancing stainless steel material synergism coat, in nickel preplating of the present invention, nickel preplating bath
Composition includes nickel chloride and hydrochloric acid；Wherein, chlorination nickel content be 200-300g/l, content of hydrochloric acid be 200-400ml/l (milliliter/
Rise), technological temperature is room temperature, current density 4-7A/dm2, the time is 3-8 minutes, and pre-nickel plating is (micro- with a thickness of 3-10 μm
Rice)；Preferably, chlorination nickel content is 230-260g/l, and content of hydrochloric acid 280-315ml/l, technological temperature is room temperature, and electric current is close
Degree is 4-6A/dm2, the time is 4-6 minutes, and pre-nickel plating is with a thickness of 5-8 μm.
For the performance for further enhancing stainless steel material synergism coat, the oxidation of surface of stainless steel is removed first
Film, and nickel preplating is carried out to it to prepare pre-nickel plating, chemical nickel plating is then carried out on pre-nickel plating prepares chemical Ni-plating layer,
Then chemical Ni-plating layer is etched using etching solution, and introduces fluoropolymer on chemical Ni-plating layer after the etching
And carrying out vacuum heat treatment makes fluoropolymer and chemical Ni-plating layer fusion be formed as one synergism coat, finally in synergism coat table
Face is introduced back into fluoropolymer and carrying out vacuum heat treatment is integrated fluoropolymer with the fusion of aforementioned synergism coat；
Wherein, it goes in the technique of oxide film dissolving: first stainless steel material being placed in by sodium hydroxide 40-60g/ L, sodium phosphate 15-
Alkaline degreasing is carried out in 25g/L and sodium n-alkylbenzenesulfonate 2-3g/L composition solution, and technological temperature is 55-60 DEG C, and the time is
20-35 minutes；The HLP30-1 for placing it in 3-4% again, which changes, carries out electrolytic degreasing in degreasing agent, process conditions are cathode oil removing,
Temperature is 65-69 DEG C, current density 4-7A/dm2, the time is 4-6 minutes；It is placed it in again by sulfuric acid 8-13%, hydrochloric acid 40-
Acid-wash activation 5-7 minutes in the mixed liquor of 50% and corrosion inhibiter 0.5-1% composition；
In nickel preplating: chlorination nickel content is 231-260g/l, content of hydrochloric acid 280-315ml/l, and pre-plating process temperature is
Room temperature, current density 4-6A/dm2, the time be 4-6 minute, pre-nickel plating thickness control be 5-7 μm；
In nickel chemical plating technology: nickel ion content is 4-8g/l in plating solution, and ortho phosphorous acid salt content is 20-40g/l, and malic acid contains
Amount is 10-20g/l；Lactic acid content is 10-14ml/l, and citric acid content 0.5-2g/l, thiocarbamide content is 1mg/l；Plating solution pH
For 4.5-5.2, the process time is 95-180 minutes, and temperature is 80-90 DEG C, and chemical Ni-plating layer is with a thickness of 20-35 μm；
In etch process: sulfuric acid content 16-22%, phosphorus acid content 4-6%, uniform agent content are 0.4-0.5g/L,
Additive level is 18-20g/L；Etch temperature is 25 DEG C, current density 3-4A/dm2, the time is 2-4 minutes, etch depth
For the 25-44% of chemical Ni-plating layer thickness；
It is introduced into fluoropolymer and carries out in heat treatment process: fluoropolymer microparticles being introduced using hot dipping, fluoropolymer microparticles are dense
Degree is 32-68g/L, and infiltration temperature is 43-79 DEG C, and the infiltration time is 12-39 minutes；The vacuum degree of heat treatment is 17-0.03Pa
(pa), heat treatment temperature are 310-440 DEG C, and heat treatment time is 31-58 minutes；
In the technique that synergism coat surface is introduced back into fluoropolymer and carries out vacuum heat treatment: it is poly- to introduce fluorine using spray coating method
Object particle is closed, fluoropolymer microparticles concentration is 110-290g/L, and coating thickness is 5-8 μm, vacuum degree 4-0.08Pa, heat treatment
Temperature is 330-430 DEG C, and heat treatment time is 35-58 minutes.
Fluoropolymer of the present invention can be using fluoropolymers such as polytetrafluoroethylene (PTFE), tetrafluoroethylene/hexafluoropropylene copolymers
Aqueous emulsion, as Du Pont's Teflon lotion, three Ai Fu company of Shanghai produce FR301 ptfe emulsion and FR463 perfluoroethylene third
Alkene lotion, Shanghai organic chemistry research institute produce P-202, F-203 polytetrafluoroethyldispersion dispersion and FS-46 fluoroplastics dispersion emulsion
Deng.
The invention has the following beneficial effects:
The plating performance difference of middle stainless steel material and the bond strength of coating are excessively poor compared with the existing technology, and coating is caducous
Defect, the present invention adds chemical Ni-plating layer as the basal layer of synergistic fluoropolymer coating using nickel preplating, by removing surface oxidation
Film or passivation layer simultaneously prepare the plating performance and bond strength that pre-nickel plating increases chemical Ni-plating layer using the pre- coating technology of high current,
It in conjunction with specific chemical etching solution and technique, solves the problems, such as that stainless steel surface is difficult to plating, is suitable for martensite not
The surface coated treatment of the stainless steel materials such as rust steel, austenitic stainless steel and ferritic stainless steel.Chemical Ni-plating layer knot of the present invention
Good with joint efforts, wearability is better than electroplated layer；One step of etching process of chemical Ni-plating layer is completed simultaneously, technological operation is simple, is easy to
Control, uniformly, hole depth and density domination are preferable for etching, and etching rear surface does not play ash, does not fall film, and etched treated changes
Nickel coating hole depth and uniform pore diameter, porosity 8-10% are learned, micropore average equivalent diameter is 290-325nm.The present invention
By the synergistic effect of series of parameters, workpiece is easily-deformable during solving precision heat treatment, and fluoropolymer is easily carbonized decomposition,
Moisture, air or impurity in basal layer micropore are not easy thoroughly to exclude, and fluoropolymer is difficult to the effectively skills such as filling in micropore
The synergism coat surface of art problem, preparation is not oxidizable and contaminated, and appearance of coat quality and consistency are good.It is prepared by the present invention
Stainless steel synergism coat bond strength is good, extreme hardness, and wearability and compactness are very good, and water-proof and oil-proof performances are excellent；Through surveying
Examination, bond strength are greater than 20Mpa, Vickers hardness 800-950HV；Stainless steel synergism coat corrosion resistance prepared by the present invention
Very good with self-lubrication, the Corrosion protection grade after 5% neutral salt spray test 500 hours is 7-8 grades, and dynamic friction coefficient value is
0.08-0.20.Stainless steel synergism coat prepared by the present invention also has low temperature anti-adhesion performance, even if stainless steel synergism coat is set
In -40 DEG C of environment, it may have it is good non-stick, it can be not only used for freezing field storage food, it can also be used to medical domain
Store non-PVC plasma bags.Stainless steel synergism coat prepared by the present invention also has high temperature antiplastering performance, can be used for non-PVC weldering
The surface treatment of part mold is particularly suitable for the treatment of non-PVC bag making production line particular manufacturing craft, non-PVC system is substantially improved
The working efficiency of bag production.
Specific embodiment
The present invention is specifically described below by specific embodiment, it is pointed out here that following embodiment is served only for this hair
It is bright to be further described, it should not be understood as limiting the scope of the invention, those of ordinary skill in the art are according to right
The present invention makes some nonessential modifications and adaptations, all falls in the scope of protection of the present invention.All raw materials of the present invention and reagent are equal
The commercial product known for those of ordinary skill in the art.
Embodiment 1
It selects 304 (06Cr19Ni10) the stainless steel test plate (panel)s that specification is 50*50*2mm as exemplar, is polished to rough surface
Degree is Ra1.6, then is prepared according to the following steps stainless steel synergism coat:
Step 1, alkaline degreasing is handled: stainless steel test plate (panel) being placed in alkaline degreasing liquid, constant temperature 20 minutes after being warming up to 60 DEG C；Its
In, alkaline degreasing liquid is mainly made of sodium hydroxide 30g/l, sodium phosphate 10g/l and sodium n-alkylbenzenesulfonate 1g/l；
Step 2, the stainless steel test plate (panel) after aforementioned oil removal treatment electrolytic degreasing ungrease treatment: is placed in 1% degreasing agent (Chongqing five
The production of nine sufacing Engineering Co., Ltd, model HLP30-1 changes) in carry out electrolytic degreasing；Wherein, the technique item of electrolytic degreasing
Part is cathode oil removing, and temperature is 60 DEG C, current density 3A/dm2, the time is 1 minute；
Step 3, acid-wash activation handle: at normal temperature by the stainless steel test plate (panel) after aforementioned electrolytic degreasing be placed in by sulfuric acid, hydrochloric acid and
Acid-wash activation 3 minutes in the mixed liquor of corrosion inhibiter composition；Wherein, sulfuric acid content 5%, content of hydrochloric acid 30%, corrosion inhibiter contains
Amount is 0.3%；
Step 4, nickel preplating is handled: the stainless steel test plate (panel) after aforementioned acid-wash activation is placed in pre-nickel plating solution (nickel chloride 200g/
L, hydrochloric acid be 200ml/l) in 4A/dm2Current density under preplating 3 minutes, and by pre-nickel plating thickness control be 3-4 μm,
Stainless steel pre-nickel plating is obtained, and is washed with water rear cold wind drying；
Step 5, chemical nickel plating is handled: aforementioned stainless steel pre-nickel plating being placed in the chemical nickel-plating solution of pH=4.8, heating is simultaneously
88 ± 2 DEG C constant temperature plating 60 minutes, obtain chemical Ni-plating layer (chemical Ni-plating layer thickness control be 22 μm)；Wherein, chemical plating
Nickel ion content is 4g/l (selecting NiSO47H2O), hypophosphite (NaH in nickel solution2PO2·H2O) content is 10g/l,
Malic acid content is 6g/l, lactic acid content 6ml/l, citric acid content 0.5g/l, and thiocarbamide content is 1mg/l；
Step 6, etching process: the stainless steel test plate (panel) after afore mentioned chemical nickel plating is placed in etching solution, carries out electricity at room temperature
Chemical etching processing the 22% of chemical Ni-plating layer thickness (depth of etching be), and tap water rinse 30S is used, flowing water cleaning 15S
It is dried up by cold wind；Wherein, etching homogenizing agent be emulsifier op-10 and neopelex in mass ratio=4:1 answers
With solution, additive be sodium succinate and glycine in mass ratio=combination solution of 2:1, sulfuric acid content 10%, phosphoric acid contains
Amount is 1%, the uniform agent content of etching is 0.1g/L, additive level 10g/L；Etch process current density is 1A/dm2, when
Between be 1min；
Step 7, it introduces fluoropolymer and is heat-treated: the stainless steel test plate (panel) after aforementioned etching process is placed in the poly- of 32g/l
It is dried after hot dipping 15 minutes in tetrafluoroethene emulsion solution in 45 DEG C, the exemplar after drying is placed in vacuum drying oven, is evacuated to
15Pa is heat-treated 35 minutes in 385 DEG C, closes vacuum system after being cooled to 150 DEG C, obtain stainless steel synergism coat.
Embodiment 2:
Select 316L (00Cr17Ni14Mo2) stainless steel disc as exemplar, being polished to surface roughness is Ra1.6, then is pressed
Following step prepares stainless steel synergism coat:
Step 1, alkaline degreasing is handled: stainless steel exemplar being placed in alkaline degreasing liquid, constant temperature 25 minutes after being warming up to 70 DEG C；Its
In, alkaline degreasing liquid is mainly made of sodium hydroxide 100g/l, sodium phosphate 35g/l and sodium n-alkylbenzenesulfonate 5g/l；
Step 2, the stainless steel exemplar after aforementioned oil removal treatment electrolytic degreasing ungrease treatment: is placed in 5% degreasing agent (Chongqing five
The production of nine sufacing Engineering Co., Ltd, model HLP30-1 changes) in carry out electrolytic degreasing；Wherein, the technique item of electrolytic degreasing
Part is cathode oil removing, and temperature is 80 DEG C, current density 10A/dm2, the time is 10 minutes；
Step 3, acid-wash activation handle: at normal temperature by the stainless steel exemplar after aforementioned electrolytic degreasing be placed in by sulfuric acid, hydrochloric acid and
Acid-wash activation 10 minutes in the mixed liquor of corrosion inhibiter composition；Wherein, sulfuric acid content 20%, content of hydrochloric acid 60%, corrosion inhibiter
Content is 2%；
Step 4, nickel preplating is handled: the stainless steel exemplar after aforementioned acid-wash activation is placed in pre-nickel plating solution (nickel chloride 300g/
L, hydrochloric acid be 400ml/l) in 8A/dm2Current density under preplating 8 minutes, and by pre-nickel plating thickness control be 10 μm, obtain
To stainless steel pre-nickel plating, and washed with water rear cold wind drying；
Step 5, chemical nickel plating is handled: aforementioned stainless steel pre-nickel plating being placed in the chemical nickel-plating solution of pH=5.0, heating is simultaneously
88 ± 2 DEG C constant temperature plating 238 minutes, obtain chemical Ni-plating layer (chemical Ni-plating layer thickness control be 45 μm)；Wherein, chemical plating
Nickel ion content is 10g/l (selecting NiSO47H2O), hypophosphite (NaH in nickel solution2PO2·H2O) content is 58g/
L, malic acid content 29g/l, lactic acid content 19ml/l, citric acid content 4.8g/l, thiocarbamide content are 1mg/l；
Step 6, etching process: the stainless steel exemplar after afore mentioned chemical nickel plating is placed in etching solution, carries out electricity at room temperature
Chemical etching processing (depth of etching is the 48% of chemical Ni-plating layer thickness), and with tap water rinse 28 seconds, flowing water cleans 12
It is dried up after second through cold wind；Wherein, etching homogenizing agent be emulsifier op-10 and neopelex in mass ratio=4:1
Combination solution, additive be sodium succinate and glycine in mass ratio=combination solution of 2:1, sulfuric acid content 30%, phosphoric acid
Content is 10%, the uniform agent content of etching is 1.0g/L, additive level 30g/L；Etch process current density is 5.0A/
dm2, time 5min；
Step 7, it introduces fluoropolymer and is heat-treated: the stainless steel exemplar after aforementioned etching process is placed in the poly- of 68g/l
It is dried after hot dipping 39 minutes in tetrafluoroethene emulsion solution in 79 DEG C, the exemplar after drying is placed in vacuum drying oven, is evacuated to
0.03Pa is heat-treated 57 minutes in 420 DEG C, closes vacuum system after being cooled to 150 DEG C, obtain stainless steel synergism coat (first
Secondary modification)；
Step 8, it is introduced back into fluoropolymer on aforementioned stainless steel synergism coat surface, while carrying out vacuum heat treatment modification to make fluorine
Polymer and the fusion of the synergism coat of formation are integrated, and obtain second of modified stainless steel synergism coat；It is adopted in the step
Fluoropolymer is introduced with spray coating method, fluoropolymer microparticles concentration is 290g/L, and coating thickness is 8 μm, vacuum degree 0.05Pa, heat
Treatment temperature is 420 DEG C, and heat treatment time is 50 minutes.
Embodiment 3, embodiment 4: referring to the step of embodiment 2, stainless steel fluoropolymer is prepared according to technological parameter in table 1
Synergism coat；Wherein, the etching homogenizing agent of embodiment 3 be emulsifier op-10 and neopelex in mass ratio=2:1
Combination solution, additive be sodium succinate and glycine in mass ratio=combination solution of 1:1.
Embodiment 5 and embodiment 6: referring to the step of embodiment 1, the polymerization of stainless steel fluorine is prepared according to technological parameter in table 1
Object synergism coat；Wherein, the etching homogenizing agent of embodiment 5 be emulsifier op-10 and neopelex in mass ratio=
The combination solution of 5:1, additive be sodium succinate and glycine in mass ratio=combination solution of 3:1.
Embodiment 7: referring to the step of embodiment 2, according to second of modified stainless steel fluorine of technological parameter preparation in table 1
Polymer synergism coat is re-introduced into fluoropolymer on aforementioned second of modified stainless steel synergistic fluoropolymer coating surface,
Carrying out vacuum heat treatment modification simultaneously is integrated fluoropolymer with synergism coat fusion, obtains the modified stainless steel of third time
Synergism coat；Fluoropolymer is introduced using hot dipping in the step, fluoropolymer microparticles concentration is 45g/L, emulsion temperature 45
DEG C, the hot dipping time is 15 minutes, vacuum degree 1Pa, and heat treatment temperature is 382 DEG C, and heat treatment time is 45 minutes.
The technological parameter of 1 embodiment 3-7 of table
Performance test: before the step 5 of operation embodiment 1-7, sampling part first observes the color of pre-nickel plating, and passes through
The thickness of micro- metallographic method test pre-nickel plating, obtained data result are shown in Table 2；Before the step 7 of operation embodiment 1-7,
SEM image processing first is carried out to the exemplar after etching process with ImageJ software and statisticallys analyze Ni-P alloy surface layer hole
Rate, number of apertures and equivalent diameter, obtained data result are shown in Table 2；The stainless steel synergism coat exemplar of Example 1-7 preparation
With common 316L stainless steel exemplar, sample surface is observed, is tested for the property respectively according to code requirement: by the rule of GB6462
It is fixed, synergism coat thickness is tested with micro- metallographic method；By the regulation of GB9790, synergism coat hardness is tested with micro- metallographic method；
It by the regulation of ASTMB117, after carrying out 500 hours 5% neutral salt spray tests, is provided by ASTMD1654, corrosion is carried out to it and is commented
Grade；Its dynamic friction coefficient is tested by the regulation of GB12444.1；The stainless steel exemplar and common 316L of another Example 1-7 preparation
Stainless steel exemplar carries out low temperature antiplastering test, and non-PVC plasma bags are placed on stainless steel exemplar and store 24 in -40 DEG C of environment
Hour, stainless steel coating adhesive and plasma bags rupture event are observed, 60-90 DEG C is then to slowly warm up to and takes out non-PVC blood plasma
Bag observes stainless steel coating adhesive and plasma bags rupture event, and blood shape is observed after non-PVC plasma bags are restored to room temperature
State repeats aforementioned process 10 times, observes coating adhesive and plasma bags rupture event, test result are shown in Table 2.
2 stainless steel synergistic fluoropolymer coating test result of table
As shown in Table 2, the etching layer porosity of stainless steel synergistic fluoropolymer coating of the present invention is 8-10%, micropore size
Uniformly, average equivalent diameter 290-325nm；Stainless steel synergistic fluoropolymer coating prepared by the present invention is in homogeneous metal color
Or it is light yellow, surface hydrophobic hates oil, feel lubrication, chemical Ni-plating layer with a thickness of 22-25 μm, uniformity is very good, and Vickers is hard
Degree is 800-950HV, and extreme hardness, Corrosion protection grade is 8 grades, and rubbing and examining coefficient value is 0.08-0.14, and plasma bags after tested are without broken
Situation is split, non-stick good within -40 DEG C, compared with prior art, comprehensive performance is increased dramatically.
Claims (10)
1. a kind of stainless steel synergistic fluoropolymer coating treatment process, it is characterised in that: remove surface of stainless steel first
Oxidation film, and nickel preplating is carried out to it to prepare pre-nickel plating, chemical nickel plating is then carried out on pre-nickel plating prepares chemical plating
Then nickel layer is etched chemical Ni-plating layer using etching solution, and introduces fluorine on chemical Ni-plating layer after the etching
Polymer, finally carrying out vacuum heat treatment makes fluoropolymer and chemical Ni-plating layer fusion be formed as one synergism coat；Wherein, it loses
Etching solution includes sulfuric acid, phosphoric acid, etching homogenizing agent and additive；Aforementioned etching homogenizing agent is emulsifier op-10 and dodecyl
For benzene sulfonic acid sodium salt according to mass ratio=2-5:1 combination solution, additive is sodium succinate and glycine according to mass ratio=1-3:1
Combination solution.
2. stainless steel synergistic fluoropolymer coating treatment process according to claim 1, it is characterised in that: the etching is molten
Sulfuric acid content is 10-30%, phosphorus acid content range 1-10% in liquid, and etching uniform agent content is 0.1-1.0g/L(grams per liter), addition
Agent content is 10-30g/L.
3. stainless steel synergistic fluoropolymer coating treatment process according to claim 1, it is characterised in that: the etching is molten
Sulfuric acid content is 15-25%, phosphorus acid content 3-7% in liquid, and etching uniform agent content is 0.3-0.6g/L, and additive level is
15-20g/L。
4. stainless steel synergistic fluoropolymer coating treatment process according to claim 1,2 or 3, it is characterised in that: described
It is etched in etch process using Anodic, technological temperature is room temperature, current density 1.0-5.0A/dm2, the time is
1-5 minutes.
5. stainless steel synergistic fluoropolymer coating treatment process according to claim 1,2 or 3, it is characterised in that: described
It is etched in etch process using Anodic, technological temperature is 25 DEG C, current density 2-4A/dm2, time 2-4
Minute.
6. stainless steel synergistic fluoropolymer coating treatment process according to claim 4, it is characterised in that: at Vacuum Heat
After reason makes fluoropolymer and chemical Ni-plating layer fusion be formed as one synergism coat, continue one or many on synergism coat surface
It introduces fluoropolymer and carrying out vacuum heat treatment is integrated fluoropolymer with synergism coat fusion.
7. stainless steel synergistic fluoropolymer coating treatment process according to claim 6, it is characterised in that: described to be repeatedly
Twice or thrice.
8. stainless steel synergistic fluoropolymer coating treatment process according to claim 7, it is characterised in that: the nickel preplating
In technique, the composition of nickel preplating bath includes nickel chloride and hydrochloric acid；Wherein, chlorination nickel content is 200-300g/l, content of hydrochloric acid is
200-400ml/l, technological temperature are room temperature, current density 4-7A/dm2, the time is 3-8 minutes, and pre-nickel plating is with a thickness of 3-
10μm。
9. stainless steel synergistic fluoropolymer coating treatment process according to claim 8, it is characterised in that: chlorination nickel content
For 230-260g/l, content of hydrochloric acid 280-315ml/l, technological temperature is room temperature, current density 4-6A/dm2, time 4-
6 minutes, pre-nickel plating was with a thickness of 5-8 μm.
10. stainless steel synergistic fluoropolymer coating treatment process according to claim 1, it is characterised in that: remove first
The oxidation film of surface of stainless steel, and nickel preplating is carried out to prepare pre-nickel plating to it, then changed on pre-nickel plating
It learns nickel plating and prepares chemical Ni-plating layer, then chemical Ni-plating layer is etched using etching solution, and change after the etching
It learns introducing fluoropolymer on nickel coating and carrying out vacuum heat treatment makes fluoropolymer and chemical Ni-plating layer fusion be formed as one association
Coating is closed, being finally introduced back into fluoropolymer on synergism coat surface and carry out vacuum heat treatment makes fluoropolymer and aforementioned synergism
Coatings fuse is integrated；
Wherein, it goes in the technique of oxide film dissolving: first stainless steel material being placed in by sodium hydroxide 40-60g/L, sodium phosphate 15-
Alkaline degreasing is carried out in 25g/L and sodium n-alkylbenzenesulfonate 2-3g/L composition solution, and technological temperature is 55-60 DEG C, and the time is
20-35 minutes；The HLP30-1 for placing it in 3-4% again, which changes, carries out electrolytic degreasing in degreasing agent, process conditions are cathode oil removing, temperature
Degree is 65-69 DEG C, current density 4-7A/dm2, the time is 4-6 minutes；It is placed it in again by sulfuric acid 8-13%, hydrochloric acid 40-50%
Acid-wash activation 5-7 minutes in the mixed liquor formed with corrosion inhibiter 0.5-1%；
In nickel preplating: chlorination nickel content is 231-260g/l, content of hydrochloric acid 280-315ml/l, and pre-plating process temperature is
Room temperature, current density 4-6A/dm2, the time be 4-6 minute, pre-nickel plating thickness control be 5-7 μm；
In nickel chemical plating technology: nickel ion content is 4-8g/l in plating solution, and ortho phosphorous acid salt content is 20-40g/l, and malic acid contains
Amount is 10-20g/l；Lactic acid content is 10-14ml/l, and citric acid content 0.5-2g/l, thiocarbamide content is 1mg/l；Plating solution PH
For 4.5-5.2, electroless plating time is 95-180 minutes, and temperature is 80-90 DEG C, and chemical Ni-plating layer is with a thickness of 22-25 μm；
In etch process: sulfuric acid content 16-22%, phosphorus acid content 4-6%, uniform agent content are 0.4-0.5g/L, are added
Adding agent content is 18-20g/L；Etch temperature is 25 DEG C, current density 3-4A/dm2, the time is 2-4 minutes, and etch depth is
The 25-44% of chemical Ni-plating layer thickness；
It is introduced into fluoropolymer and carries out in heat treatment process: fluoropolymer microparticles being introduced using hot dipping, fluoropolymer microparticles are dense
Degree is 32-68g/L, and infiltration temperature is 43-79 DEG C, and the infiltration time is 12-39 minutes；The vacuum degree of heat treatment is 17-0.03Pa, heat
Treatment temperature is 310-440 DEG C, and heat treatment time is 31-58 minutes；
In the technique that synergism coat surface is introduced back into fluoropolymer and carries out vacuum heat treatment: it is poly- to introduce fluorine using spray coating method
Object particle is closed, fluoropolymer microparticles concentration is 110-290g/L, and coating thickness is 5-8 μm, vacuum degree 4-0.08Pa, heat treatment
Temperature is 330-430 DEG C, and heat treatment time is 35-58 minutes.
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