CN107779833A - A kind of composite film coating technique - Google Patents

A kind of composite film coating technique Download PDF

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Publication number
CN107779833A
CN107779833A CN201711083492.5A CN201711083492A CN107779833A CN 107779833 A CN107779833 A CN 107779833A CN 201711083492 A CN201711083492 A CN 201711083492A CN 107779833 A CN107779833 A CN 107779833A
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China
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vacuum
plating
composite film
temperature
film coating
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CN201711083492.5A
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孙德恩
何倩
李静
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Chongqing University
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Chongqing University
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Priority to CN201711083492.5A priority Critical patent/CN107779833A/en
Publication of CN107779833A publication Critical patent/CN107779833A/en
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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • 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
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt

Abstract

The invention provides a kind of composite film coating technique, including：Vacuum Deposition depositing Ti/Cu binder courses are used in substrate surface；The vacuum of the vacuum chamber is less than 5 × 10‑4Pa, temperature are 400~420 DEG C；Functional layer is prepared using electrolysis electronickelling and/or chemical-electrical nickel plating on the binder course, obtains composite film coating.Composite film coating technique provided by the invention uses the vacuum depositing process of the electroplating technology combination special process of special parameter, and its coating of the composite membrane being finally prepared is combined excellent, no demoulding with base material, and adhesion is high.

Description

A kind of composite film coating technique
Technical field
The present invention relates to alloy firm preparation field, more particularly, to a kind of composite film coating technique.
Background technology
Surface engineering technology refer to by various physics, chemistry, machinery or it is compound the methods of change the change of matrix surface Study point, institutional framework, stress state, so that matrix surface obtains certain property, such as wear-resistant, corrosion-resistant, resistance to height A kind of technology of the performances such as warm and excellent optics, magnetics, electricity, calorifics.Plating is surface engineering technology neck with Vacuum Deposition The big main technique technology in domain two.Electroplating technology is broadly divided into electrolysis plating and electroless plating.Electrolysis plating refers in impressed current In the case of, reduce the chemical substance in plating solution and be deposited on the method that workpiece surface forms coating.In order to which electroplating process is suitable Profit is carried out, it is desirable to which workpiece must be conductive.Electroless plating need not be powered, and to workpiece electric conductivity without particular/special requirement.Pre-electroplating treatment Process is relative complex, and faint van der Waals interaction is only leaned between coating process floating coat and matrix, thus coating and matrix Adhesion it is weaker.For electroplated coating common thickness scope between 2~1000 μm, electroplating process has leveling effect, Ke Yigai Kind matrix surface finish, coating have excellent Corrosion Protection.Vacuum Deposition, also referred to as physical vapour deposition (PVD), refer in vacuum By evaporation source heating evaporation or ion sputtering solid material in container, these materials for evaporating and sputtering are made to deposit to base material table Face is so as to forming coating.Such as evaporate plating, ion plating and sputtering.Technique for vacuum coating has the advantages of green, no waste water Waste gas discharges, and product is nontoxic.Easily it can be coated in metal and nonmetallic surface.Coating and matrix prepared by Vacuum Deposition With good adhesion, film layer structure is fine and close, and hardness is higher, has excellent abrasion resistance properties.The common thickness of vacuum plating coating Scope is spent between 0.1~10 μm, and coating is close to matrix surface, and leveling effect is poor, and vacuum plating coating can not improve matrix table Face finish.
Although electroplating technology has the challenges such as wastewater treatment, electroplating technology has leveling effect, can prepared Thick film, and the advantage of lower cost of electroplating technology processing workpiece.In a short time, Vacuum Deposition is difficult complete substitution plating.Existing skill Composite film coating technique disclosed in art due in coating process to the requirement of the adhesion, wearability and Corrosion Protection of film compared with It is low, therefore the requirement of field of surface treatment can not be met to a certain extent.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of composite film coating technique, provided by the invention The composite membrane that composite film coating technique is prepared, its coating are combined excellent, no demoulding with base material, and adhesion is high.
The invention provides a kind of composite film coating technique, including：
Vacuum Deposition depositing Ti/Cu binder courses are used in substrate surface；The vacuum of the vacuum chamber is less than 5 × 10- 4Pa, temperature are 400~420 DEG C；
Functional layer is prepared using electrolysis electronickelling and/or chemical-electrical nickel plating on the binder course, obtains composite film coating.
Preferably, the base material is titanium, tungsten, molybdenum, tantalum, ceramics, glass or ferrite.
Preferably, it is described electrolysis electronickelling be specially：
Pre-processed, electronickelling, dried using the one or more in bronsted lowry acids and bases bronsted lowry；The plating is flash；The flash Film thickness is 0.3 μm；The temperature of the flash is 45~55 DEG C；The current density of the flash is 3~5A；The temperature of the drying Spend for 80~100 DEG C, the dry time is 800~1000s.
Preferably, the chemical nickel plating is specially：
Pre-processed using the one or more in bronsted lowry acids and bases bronsted lowry, be 8.5~9 progress chemical nickel platings in 85~90 DEG C, pH value, do It is dry；The plating solution of the chemical nickel plating is nickel sulfate or the nickel sulfate for adding Teflon.
Preferably, the Vacuum Deposition is magnetron sputtering, and the vacuum of the magnetron sputtering is 0.1~1Pa, and the magnetic control splashes The gas penetrated is argon gas；The bias value of institute's magnetron sputtering is -20~-200V；The sputtering target power density of the magnetron sputtering is Less than 8W/cm2；The joint thickness is 0.02~1 μm.
Preferably, 0.02~0.3 μm of metal Ti thickness degree, Ni metal thickness degree in the binder course>0.3μm.
Preferably, described be surface-treated is specially：Base material is by alkalilye degreasing, pure water rinsing, dehydration, 80~120 DEG C of warm Wind is dried.
The invention provides a kind of composite film coating technique, including：
Bottom is prepared using sulfuric acid nickel electrowinning plating in substrate surface；The temperature of the electrolysis plating is 25~35 DEG C；Institute It is 0.5~1.2A/dm to state current density2；
Functional layer is prepared using Vacuum Deposition on the bottom；The Vacuum Deposition is specially：It is less than 5 × 10 in vacuum- 4Pa, temperature are deposited metal binder course Ti layers in 130~140 DEG C of vacuum chamber, then on binder course titanium deposition carbide Functional layer；Wherein, deposition process vacuum is 0.1~1Pa.
Preferably, the base material is aluminium, stainless steel, brass.
Preferably, the underlayer thickness>5 μm, functional layer thickness is 0.5~2 μm.
Compared with prior art, the invention provides a kind of composite film coating technique, including：Vacuum Deposition is used in substrate surface Depositing Ti/Cu binder courses；The vacuum of the vacuum chamber is less than 5 × 10-4Pa, temperature are 400~420 DEG C；In the knot Close and functional layer is prepared using electrolysis electronickelling and/or chemical-electrical nickel plating on layer, obtain composite film coating.Composite Coatings provided by the invention Membrane process using special parameter electroplating technology combination special process vacuum depositing process, the composite membrane being finally prepared its Coating is combined excellent, no demoulding with base material, and adhesion is high.
Brief description of the drawings
Observation by light microscope figure after the surface treatment of Fig. 1 titanium-based matter workpiece different process.
Embodiment
The invention provides a kind of composite film coating technique, those skilled in the art can use for reference present disclosure, be suitably modified Technological parameter is realized.In particular, all similar replacements and change be for a person skilled in the art it is aobvious and It is clear to, they belong to the scope of protection of the invention.The method of the present invention and application are carried out by preferred embodiment Description, related personnel can substantially not depart from present invention, methods herein and application are being modified in spirit and scope Or suitably change with combining, to realize and using the technology of the present invention.
The invention provides a kind of composite film coating technique, including：
Vacuum Deposition depositing Ti/Cu binder courses are used in substrate surface；The vacuum of the vacuum chamber is less than 5 × 10-4Pa, Temperature is 400~420 DEG C；
Functional layer is prepared using electrolysis electronickelling and/or chemical-electrical nickel plating on the binder course, obtains composite film coating.
Composite film coating technique provided by the invention uses Vacuum Deposition depositing Ti/Cu binder courses in substrate surface first.
Base material of the present invention is preferably titanium, tungsten, molybdenum, tantalum, ceramics, glass or ferrite.
The present invention carries out pre-treatment to above-mentioned substrate surface first；It is preferred that it is specially：
Base material is by alkalilye degreasing, pure water rinsing, dehydration, 80~120 DEG C of hot-air seasonings.
Alkali lye of the present invention is preferably sodium hydroxide.The concentration of the alkali is preferably 10wt%.The alkali process Temperature is room temperature (25 DEG C).Time is 30~40s.
The pure water rinsing is preferably 2~3 times；The present invention is for the rinsing, dehydration without restriction, art technology Personnel are known.
80~120 DEG C of hot-air seasonings of the present invention preferably can be 90~110 DEG C of hot-air seasonings.
The stains such as rusty stain on workpiece, oil stain can be removed by above-mentioned surface treatment.
On above-mentioned treated base material, the present invention uses method depositing Ti/Cu binder courses of Vacuum Deposition first.
Vacuum Deposition of the present invention is carried out preferably in vacuum coating equipment；It is preferred that workpiece to be plated is put into drum-type vacuum plating In the metal net mask of film machine, and the metal net mask is placed in vacuum chamber.
The Vacuum Deposition is preferably specially：
A) vacuum chamber vacuumizes, and heating, vacuum chamber simultaneously.
Heating-up temperature is kept at 420~450 DEG C.When the vacuum of vacuum chamber is less than 5 × 10-4After Pa, vacuum chamber is adjusted Room temperature and stably at 400~420 DEG C；
B) vacuum chamber is passed through argon gas, runs anode layer ion source under high voltage low current discharge mode, produce argon from Son；Meanwhile grid bias power supply is opened, bias value is set between -1200~-3000V, plasma glow is carried out to workpiece to be plated 30~60min is cleaned, wherein grid bias power supply can be dc source or the pulse power.
C) binder course is prepared using vacuum coating technology.
The Vacuum Deposition is preferably magnetron sputtering, and the vacuum of the magnetron sputtering is preferably 0.1~1Pa, the magnetic control The gas of sputtering is argon gas；The bias value of institute's magnetron sputtering is preferably -20~-200V；The sputtering target power output of the magnetron sputtering Density is less than 8W/cm2；Preferably 6~8W/cm2；The joint thickness is 0.02~1 μm.Specifically, in the binder course Preferably 0.02~0.3 μm of metal Ti thickness degree, Ni metal thickness degree is preferably greater than 0.3 μm.
Binder course of the present invention is often lamination layer structure, includes layer of metal titanium layer, and layer of metal layers of copper.Pass through regulation Sedimentation time controls metal bonding layer thickness.Grid bias power supply can be dc source or the pulse power.
Vacuum coating technology prepares binder course and finished, and stops the driving of drum-type work rest, and matrix workpiece temperature is cooled to 100 DEG C Below；Vacuum chamber is filled with dry air；Blow-on door, plated titanium-based matter workpiece are come out of the stove.
Functional layer is prepared using electrolysis electronickelling and/or chemical-electrical nickel plating on the binder course, obtains composite film.
As, function can be prepared by the way of electrolysis electronickelling and chemical-electrical nickel plating combine on the binder course Layer, obtains composite film.
Can also be that functional layer is prepared using chemical-electrical nickel plating on the binder course, obtains composite film.
Wherein, it is described electrolysis electronickelling be specially：
Pre-processed, electronickelling, dried using the one or more in bronsted lowry acids and bases bronsted lowry.
It is preferred that it is specially：Alkali cleaning, pickling, flash nickel, chemical nickel plating (EN), Teflon chemical nickel (Ni-PTFE), drying.
The alkali is preferably sodium hydroxide；The acid can be sulfuric acid or hydrochloric acid；The alkali or sour concentration are preferably 10wt.%~25wt.%；The plating is flash；The film thickness of the flash is 0.3 μm；The temperature of the flash be 45~ 55℃；The current density of the flash is 3~5A.The drying temperature is 80~100 DEG C, and drying time is 800~1000s.
Wherein, the chemical nickel plating is specially：
Pre-processed using the one or more in bronsted lowry acids and bases bronsted lowry, be 8.5~9 progress chemical nickel platings in 85~90 DEG C, pH value, do It is dry；The plating solution of the chemical nickel plating includes nickel sulfate or adds the nickel sulfate of Teflon；Can more preferably include nickel sulfate, Sodium dihydrogen phosphate, Na3C6H5O7, ammonium chloride.
It is preferred that it is specially：Pickling, water rinsing, pickling, water rinsing, palladium activation, water rinsing, chemical nickel plating, water are rinsed, dried Obtain.
Wherein, the acid can be sulfuric acid or hydrochloric acid；The concentration of the alkali or acid is preferably 10wt.%~25wt.%；Institute It is preferably 15~20s to state the acid treatment time；The water rinsing is preferably deionized water rinsing；The rinsing times are preferably 2~3 It is secondary；The rinsing time is preferably 20~40s；The palladium soak time is preferably 15~20s；The drying temperature be 80~ 100 DEG C, drying time is 800~1000s.
With the ceramic substrate workpiece of above-mentioned " Vacuum Deposition+plating " composite film coating PROCESS FOR TREATMENT, observation by light microscope, its table Face flawless, stain, collapse the defects of angle, flowing water line, also without fusion line, sand hole, shrink trace, clamping line the defects of.Chemical-electrical It is uniform to plate functional layer thickness, without impressed current.Sample surface coating without bulge, come off, it is functional.Surface is without discoloration, nothing Corrode particle.
Present invention also offers the composite film coating being prepared by above-mentioned composite film coating technique.
The invention provides a kind of composite film coating technique, including：
Bottom is prepared using sulfuric acid nickel electrowinning plating in substrate surface；The temperature of the electrolysis plating is 25~35 DEG C；Institute It is 0.5~1.2A/dm to state current density2；
Functional layer is prepared using Vacuum Deposition on the bottom；The Vacuum Deposition is specially：It is less than 5 × 10 in vacuum- 4Pa, temperature are deposited metal binder course Ti layers in 130~140 DEG C of vacuum chamber, then on binder course titanium deposition carbide Functional layer；Wherein, deposition process vacuum is 0.1~1Pa.
Base material of the present invention is preferably aluminium, stainless steel, brass.
The present invention prepares bottom in above-mentioned substrate surface using sulfuric acid nickel electrowinning plating.
The electrolysis plating includes：Pretreatment, electronickelling and baking.
Wherein, above-mentioned base material is pre-processed first, the pretreatment is specially：Mechanical polishing, electrochemical deoiling, acidleach Erosion.
Specifically, the electrochemical deoiling uses mass concentration as 20g/L sodium carbonate, mass concentration is 30g/L sodium phosphates, In 30~60 DEG C of temperature, time 10min carries out oil removing.The acid etch oxide layer preferably use hydrofluoric acid and water volume ratio for 1：1, room temperature, 30~120s of time.
The plating solution of the electronickelling preferably includes the nickel sulfate that mass concentration is 280g/L, mass concentration is 30~40g/L Boric acid, mass concentration be 2~10g/L sodium chloride, 25~35 DEG C of the temperature of the plating, 0.5~1.2A/ of current density dm2.80 DEG C~100 DEG C of baking temperature, 800~900s of time.
Plating obtains bottom, wherein the underlayer thickness is more than 5 μm, functional layer thickness is 0.5~2 μm.
Functional layer is prepared using Vacuum Deposition on the bottom.
The Vacuum Deposition is specially：It is less than 5 × 10 in vacuum-4Pa, temperature are heavy in 130~140 DEG C of vacuum chamber Product metal bonding layer Ti layers, then on binder course titanium deposition carbide functional layer；Wherein, deposition process vacuum be 0.1~ 1Pa。
The Vacuum Deposition is preferably specially：
A) vacuum chamber vacuumizes, and heating, vacuum chamber simultaneously.
Heating-up temperature is kept at 140~150 DEG C.When the vacuum of vacuum chamber is better than 5 × 10-4After Pa, vacuum chamber is adjusted Room temperature and stably at 130~140 DEG C；
B) vacuum chamber is passed through argon gas, runs anode layer ion source under high voltage low current discharge mode, produce argon from Son；Meanwhile grid bias power supply is opened, bias value is set between -1200~-3000V, plasma glow is carried out to workpiece to be plated 30~60min is cleaned, wherein grid bias power supply can be dc source or the pulse power.
C) binder course is prepared using vacuum coating technology.The joint thickness is 0.02~1 μm.Specifically, the combination Preferably 0.01~0.3 μm of metal Ti thickness degree in layer, Ni metal thickness degree is preferably greater than 0.3 μm.
It is preferred that the magnetically controlled sputter method deposit functional layers of the vacuum coating technology, for black functional layer, it is preferred to use titanium Carbide.Acetylene gas is passed through as reacting gas, is passed through argon gas as working gas, vacuum is preferably in coating process 0.1~1Pa.The Vacuum Deposition is preferably magnetron sputtering, and the sputtered titanium target power density is less than 8W/cm2；More preferably 6~ 8W/cm2.Grid bias power supply is arranged between -20~-200V in deposition process, and grid bias power supply can be dc source or pulse Power supply, preferred pulse grid bias power supply；Adjust vacuum chamber temperature and stably at 130~140 DEG C；Thicknesses of layers is deposited by controlling Time control.
Vacuum coating technology prepares functional layer and finished, and stops work rest driving, and aluminum matrix workpiece temperature is cooled to less than 90 DEG C； Vacuum chamber is filled with dry air；Blow-on door, plated aluminum matrix workpiece are come out of the stove.
Using the aluminum matrix workpiece of above-mentioned " plating+Vacuum Deposition " composite film coating PROCESS FOR TREATMENT, observation by light microscope, its table Face flawless, stain, collapse the defects of angle, flowing water line, also without fusion line, sand hole, shrink trace, clamping line the defects of.Aluminum matrix Workpiece hardness 135Hv, 9~10 μm of electroless nickel layer thickness, nickel layer hardness is between 740Hv, 1~1.5 μm of Vacuum Deposition functional layer thickness, Vacuum Deposition functional layer hardness 1050Hv.Plating piece surface color is black, wherein L values (characterize blackness, numerical value is smaller, more black) between 35~38.Hundred lattice test results show that coating is combined excellent, no demoulding with base material, and adhesion is up to more than 95%.
The invention provides a kind of composite film coating technique, including：Combined in substrate surface using Vacuum Deposition depositing Ti/Cu Layer；The vacuum of the vacuum chamber is less than 5 × 10-4Pa, temperature are 400~420 DEG C；Using electrolysis on the binder course Electronickelling and/or chemical-electrical nickel plating prepare functional layer, obtain composite film coating.Composite film coating technique provided by the invention is using specific The vacuum depositing process of the electroplating technology combination special process of parameter, its coating for the composite membrane being finally prepared are combined with base material It is excellent, no demoulding, adhesion height.
In order to further illustrate the present invention, composite film coating technique provided by the invention is carried out with reference to embodiments detailed Description.
Embodiment 1
(1) pre-treatment
(a) titanium-based matter workpiece to be plated passes through alkalilye degreasing NaOH (10wt%), and temperature is room temperature (25 DEG C), the time 30 ~40s.(80~120 DEG C) of pure water rinsing, dehydration and hot blast are dried, stain (the workpiece outward appearance such as rusty stain, oil stain on removal workpiece Referring to Fig. 1 a)；
(b) workpiece to be plated by process (a) processing is put into the metal net mask of drum-type vacuum coating machine, and should Metal net mask is placed in vacuum chamber；
(c) vacuum chamber vacuumizes, and heating, vacuum chamber simultaneously.Heating-up temperature is kept at 420~450 DEG C.Work as vacuum The vacuum of chamber is less than 5 × 10-4After Pa, vacuum chamber temperature is adjusted and stably at 400~420 DEG C；
(d) vacuum chamber is passed through argon gas, runs anode layer ion source under high voltage low current discharge mode, produce argon from Son；Meanwhile grid bias power supply is opened, bias value is set between -1200~-3000V, titanizing matrix workpiece is treated and carries out plasma Body aura cleans 30~60min, and wherein grid bias power supply can be dc source or the pulse power；
(2) binder course is prepared using vacuum coating technology
It is preferred that the magnetically controlled sputter method deposited metal binder course of vacuum coating technology, the joint thickness is at 0.02~1 μm；Should Binder course is often lamination layer structure, comprising layer of metal titanium layer, 0.02~0.3 μm of thickness, and layer of metal layers of copper.Pass through tune Save sedimentation time control metal bonding layer thickness.Grid bias power supply is arranged between -20~-200V in deposition process, grid bias power supply Can be dc source or the pulse power；Sputtering target power density is less than 8W/cm2；In coating process vacuum be 0.1~ 1Pa, adjust vacuum chamber temperature and stably at 400~420 DEG C；
(3) vacuum coating technology prepares binder course and finished, and stops the driving of drum-type work rest, and titanium-based matter workpiece temperature is cooled to Less than 100 DEG C；Vacuum chamber is filled with dry air；Blow-on door, plated titanium-based matter workpiece are come out of the stove；The titanium-based of Vacuum Deposition technical finesse For matter workpiece outward appearance referring to Fig. 1 b, surface is metal copper layer；
(4) functional layer is prepared using electroplating technology
By the workpiece of Vacuum Deposition technical finesse, followed by electroplating technology processing.Electroplated using electrolysis and combine chemistry Plating, electroplating technology flow：→ flash nickel (0.3 μm) → chemical nickel plating (EN) → Teflon is washed in alkali cleaning → sulfuric acid (10wt.%) Chemical nickel (Ni-PTFE) → drying (90 DEG C, 900s).Electroplating technology processing titanium-based matter workpiece outward appearance be referring to Fig. 1 c, surface Teflon electroless nickel layer.
(5) using the titanium-based matter workpiece of " Vacuum Deposition+plating " composite film coating PROCESS FOR TREATMENT, observation by light microscope, its table Face flawless, stain, collapse the defects of angle, flowing water line, also without fusion line, sand hole, shrink trace, clamping line the defects of.Using change Nickel plating is learned without being powered, and thickness of coating is uniform.Functional layer EN+Ni-PTFE thickness is 7~11 μm, wherein Ni-PTFE thickness 1 ~2 μm.Coating hardness is between 500~550Hv after heat treatment.Adhesion test uses the hundred lattice methods of inspection, and adhesion reaches More than 95%.Resistance to sweat test, places 24h and 48h, at " Vacuum Deposition+plating " composite film coating technique respectively under the conditions of 40 DEG C The titanium-based matter workpiece of reason, surface is without discoloration, corrosion-free particle.
Embodiment 2
(1) pre-treatment
(a) ceramic substrate workpiece to be plated passes through alkalilye degreasing NaOH (10wt%), and temperature is room temperature (25 DEG C), and the time is 30~40s., pure water rinsing, dehydration and the drying of (80~120 DEG C) of hot blast, remove the stains such as rusty stain on workpiece, oil stain；
(b) the ceramic substrate workpiece to be plated by process (a) processing is put into vacuum chamber；
(c) vacuum chamber vacuumizes, and heating, vacuum chamber simultaneously.Heating-up temperature is kept at 420~450 DEG C.Work as vacuum The vacuum of chamber is less than 5 × 10-4After Pa, vacuum chamber temperature is adjusted and stably at 400~420 DEG C；
(d) vacuum chamber is passed through argon gas, runs anode layer ion source under high voltage low current discharge mode, produce argon from Son；Meanwhile open grid bias power supply, bias value is set between -1200~-3000V, treat ceramic platingv matrix workpiece carry out etc. from Daughter aura cleans 30~60min, and wherein grid bias power supply is bipolar pulse grid bias power supply or RF bias power source；
(2) binder course is prepared using vacuum coating technology
It is preferred that the magnetically controlled sputter method deposited metal binder course of vacuum coating technology, the joint thickness is at 0.01~1 μm；Should Binder course is often lamination layer structure, and comprising layer of metal titanium layer, 0.01~0.1 μm of thickness, and layer of metal layers of copper, thickness are big In 0.3 μm.Metal bonding layer thickness is controlled by adjusting sedimentation time.Grid bias power supply is arranged to -20~-200V in deposition process Between, grid bias power supply is preferably bipolar pulse grid bias power supply or radio-frequency power supply；Sputtering target power density is less than 8W/cm2；Plating Vacuum is 0.1~1Pa in membrane process, adjusts vacuum chamber temperature and stably at 400~420 DEG C；
(3) vacuum coating technology prepares binder course and finished, and stops work rest driving, and ceramic substrate workpiece temperature is cooled to 100 Below DEG C；Vacuum chamber is filled with dry air；Blow-on door, plated ceramic substrate workpiece are come out of the stove；
(4) functional layer is prepared using electroplating technology
By the workpiece of Vacuum Deposition technical finesse, followed by electroplating technology processing, using chemical-electrical plating method, galvanizer Skill flow：Pickling (15s) → deionized water rinsing (three times, respectively 20s, 20s, 40s) → pickling (5wt.% sulfuric acid, 20s) The rinsing of → deionized water rinsing (three times, respectively 20s, 20s, 40 seconds) → palladium activation (15s) → deionized water (three times, 20s, 20s, 40s) → chemical nickel plating (EN, 88 DEG C, 400s) → deionized water rinsing (three times, 30s, 30s, 40s) → dry (90 DEG C, 900s)。
(5) the ceramic substrate workpiece of use " Vacuum Deposition+plating " composite film coating PROCESS FOR TREATMENT, observation by light microscope, its Surface flawless, stain, collapse the defects of angle, flowing water line, also without fusion line, sand hole, shrink trace, clamping line the defects of.Chemistry It is uniform to electroplate functional layer thickness, without impressed current.3 ± 0.3 μm of functional layer EN thickness degree.After heat treatment coating hardness between 500~550Hv.Hundred lattice test results show that coating is combined excellent, no demoulding with base material, and adhesion is up to more than 95%.Unleaded time Fluid welding test (260 DEG C, 15s) result show, sample surface coating without bulge, come off, it is functional.
Embodiment 3
(1) bottom is prepared using electroplating technology, uses electrolytic plating method.Mechanical polishing → electrochemical deoiling → acid etch → Direct Electroplating nickel → baking.Wherein electrochemical deoiling uses sodium carbonate (20g/L), sodium phosphate (30g/L), 30~60 DEG C of temperature, when Between 10min.Acid etch oxide layer uses hydrofluoric acid (1：1), room temperature, 30~120s of time.Direct Electroplating nickel uses nickel sulfate (280g/L), boric acid (30~40g/L), 25~35 DEG C of sodium chloride (2~10g/L) temperature, 0.5~1.2A/dm of current density2。 90 DEG C of baking temperature, time 900s.
(2) functional layer is prepared using Vacuum Deposition.
The workpiece handled using electroplating technology, is next handled using vacuum coating technology.Process is as follows：
(a) the aluminum matrix workpiece to be plated by process (1) processing is inserted in vacuum chamber；
(b) vacuum chamber vacuumizes, and heating, vacuum chamber simultaneously.Heating-up temperature is kept at 140~150 DEG C.Work as vacuum The vacuum of chamber is less than 5 × 10-4After Pa, vacuum chamber temperature is adjusted and stably at 130~140 DEG C；
(c) vacuum chamber is passed through argon gas, runs anode layer ion source under high voltage low current discharge mode, produce argon from Son；Meanwhile grid bias power supply is opened, bias value is set between -1200~-3000V, plasma glow is carried out to workpiece to be plated 30~60min is cleaned, wherein grid bias power supply is DC bias power or pulsed bias power supply, preferred pulse grid bias power supply；
(d) the magnetically controlled sputter method deposited metal binder course of preferred vacuum coating technology, the binder course is usually layer of titanium metal, Its thickness is at 0.01~0.3 μm.Grid bias power supply is arranged between -20~-200V in deposition process, and grid bias power supply can be direct current Power supply or the pulse power, preferred pulse grid bias power supply；Sputtering target power density is less than 8W/cm2；Vacuum is in coating process 0.1~1Pa, adjust vacuum chamber temperature and stably at 130~140 DEG C；
(e) the magnetically controlled sputter method deposit functional layers of preferred vacuum coating technology, for black functional layer, are considered as titanium Carbide.Acetylene gas is passed through as reacting gas, is passed through argon gas as working gas, vacuum is set to 0.1 in coating process ~1Pa.Sputtered titanium target power density is less than 8W/cm2；Grid bias power supply is arranged between -20~-200V in deposition process, bias Power supply can be dc source or the pulse power, preferred pulse grid bias power supply；Adjust vacuum chamber temperature and stably 130~ 140℃；Thicknesses of layers is by controlling sedimentation time to control.
(3) vacuum coating technology prepare functional layer finish, stop work rest driving, aluminum matrix workpiece temperature be cooled to 90 DEG C with Under；Vacuum chamber is filled with dry air；Blow-on door, plated aluminum matrix workpiece are come out of the stove；
(4) using the aluminum matrix workpiece of " plating+Vacuum Deposition " composite film coating PROCESS FOR TREATMENT, observation by light microscope, its table Face flawless, stain, collapse the defects of angle, flowing water line, also without fusion line, sand hole, shrink trace, clamping line the defects of.Aluminum matrix Workpiece hardness 135Hv, 9~10 μm of electroless nickel layer thickness, nickel layer hardness is between 740Hv, 1~1.5 μm of Vacuum Deposition functional layer thickness, Vacuum Deposition functional layer hardness 1050Hv.Plating piece surface color is black, wherein L values (characterize blackness, numerical value is smaller, more black) between 35~38.Hundred lattice test results show that coating is combined excellent, no demoulding with base material, and adhesion is up to more than 95%.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

  1. A kind of 1. composite film coating technique, it is characterised in that including：
    Vacuum Deposition depositing Ti/Cu binder courses are used in substrate surface；The vacuum of the vacuum chamber is less than 5 × 10-4Pa, temperature Spend for 400~420 DEG C；
    Functional layer is prepared using electrolysis electronickelling and/or chemical-electrical nickel plating on the binder course, obtains composite film coating.
  2. 2. technique according to claim 1, it is characterised in that the base material is titanium, tungsten, molybdenum, tantalum, ceramics, glass or iron Oxysome.
  3. 3. technique according to claim 1, it is characterised in that it is described electrolysis electronickelling be specially：
    Pre-processed, electronickelling, dried using the one or more in bronsted lowry acids and bases bronsted lowry；The plating is flash；The thickness of the flash Spend for 0.3 μm；The temperature of the flash is 45~55 DEG C；The current density of the flash is 3~5A；The temperature of the drying is 80~100 DEG C, the dry time is 800~1000s.
  4. 4. technique according to claim 1, it is characterised in that the chemical nickel plating is specially：
    Pre-processed using the one or more in bronsted lowry acids and bases bronsted lowry, be 8.5~9 progress chemical nickel platings in 85~90 DEG C, pH value, dry； The plating solution of the chemical nickel plating includes nickel sulfate or adds the nickel sulfate of Teflon.
  5. 5. technique according to claim 1, it is characterised in that the Vacuum Deposition is magnetron sputtering, the magnetron sputtering Vacuum is 0.1~1Pa, and the gas of the magnetron sputtering is argon gas；The bias value of the magnetron sputtering is -20~-200V；Institute The sputtering target power density for stating magnetron sputtering is less than 8W/cm2；The joint thickness is 0.02~1 μm.
  6. 6. technique according to claim 1, it is characterised in that metal Ti thickness degree is 0.02~0.3 μ in the binder course M, Ni metal thickness degree are more than 0.3 μm.
  7. 7. technique according to claim 1, it is characterised in that the surface treatment is specially：
    Base material is by alkalilye degreasing, pure water rinsing, dehydration, 80~120 DEG C of hot-air seasonings.
  8. A kind of 8. composite film coating technique, it is characterised in that including：
    Bottom is prepared using sulfuric acid nickel electrowinning plating in substrate surface；The temperature of the electrolysis plating is 25~35 DEG C；The electricity Current density is 0.5~1.2A/dm2；
    Functional layer is prepared using Vacuum Deposition on the bottom；The Vacuum Deposition is specially：It is less than 5 × 10 in vacuum-4Pa, temperature Spend deposited metal binder course Ti layers in the vacuum chamber for 130~140 DEG C, then on binder course titanium deposition carbide function Layer；Wherein, deposition process vacuum is 0.1~1Pa.
  9. 9. technique according to claim 8, it is characterised in that the base material is aluminium, stainless steel, brass.
  10. 10. technique according to claim 8, it is characterised in that the underlayer thickness is more than 5 μm, and functional layer thickness is 0.5 ~2 μm.
CN201711083492.5A 2017-11-07 2017-11-07 A kind of composite film coating technique Pending CN107779833A (en)

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Publication number Priority date Publication date Assignee Title
CN109560158A (en) * 2018-10-29 2019-04-02 无锡明协科技实业有限公司 A kind of preparation method of Copper base material photovoltaic welding belt
CN110699647A (en) * 2019-10-31 2020-01-17 宇石能源(南通)有限公司 Method for modifying stainless steel bipolar plate of fuel cell
CN111740044A (en) * 2020-07-09 2020-10-02 夏笔文 Composite foil and production process thereof
CN114293188A (en) * 2021-12-30 2022-04-08 中国重汽集团济南动力有限公司 Multi-coating vibration-damping structure cutter pad and preparation method thereof

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CN1940136A (en) * 2005-09-30 2007-04-04 佛山市顺德区汉达精密电子科技有限公司 Magnesium-alloy surface treatment
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CN109560158A (en) * 2018-10-29 2019-04-02 无锡明协科技实业有限公司 A kind of preparation method of Copper base material photovoltaic welding belt
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CN111740044A (en) * 2020-07-09 2020-10-02 夏笔文 Composite foil and production process thereof
CN114293188A (en) * 2021-12-30 2022-04-08 中国重汽集团济南动力有限公司 Multi-coating vibration-damping structure cutter pad and preparation method thereof

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