CN109055880A - Zinc-plated rear electrophoresis technique - Google Patents
Zinc-plated rear electrophoresis technique Download PDFInfo
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- CN109055880A CN109055880A CN201811133634.9A CN201811133634A CN109055880A CN 109055880 A CN109055880 A CN 109055880A CN 201811133634 A CN201811133634 A CN 201811133634A CN 109055880 A CN109055880 A CN 109055880A
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- 238000001962 electrophoresis Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 66
- 239000000956 alloy Substances 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 230000004913 activation Effects 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 238000012545 processing Methods 0.000 claims abstract description 24
- 238000002203 pretreatment Methods 0.000 claims abstract description 14
- 238000010828 elution Methods 0.000 claims abstract description 10
- 238000012805 post-processing Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Natural products OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 53
- 239000002245 particle Substances 0.000 claims description 48
- 239000007787 solid Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000012190 activator Substances 0.000 claims description 22
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 19
- BIXHRBFZLLFBFL-UHFFFAOYSA-N germanium nitride Chemical group N#[Ge]N([Ge]#N)[Ge]#N BIXHRBFZLLFBFL-UHFFFAOYSA-N 0.000 claims description 19
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000001667 (E)-4-furan-2-ylbut-3-en-2-one Substances 0.000 claims description 9
- GBKGJMYPQZODMI-SNAWJCMRSA-N (e)-4-(furan-2-yl)but-3-en-2-one Chemical compound CC(=O)\C=C\C1=CC=CO1 GBKGJMYPQZODMI-SNAWJCMRSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 2
- -1 furfuryl alcohol phenolic aldehyde Chemical class 0.000 claims 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000001681 protective effect Effects 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 3
- 230000002421 anti-septic effect Effects 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000007664 blowing Methods 0.000 description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 239000005011 phenolic resin Substances 0.000 description 8
- 229920001568 phenolic resin Polymers 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention belongs to field of metal surface treatment technology, and in particular to zinc-plated rear electrophoresis technique includes the following steps: pre-treatment: successively carrying out oil removing, hot water wash, derusting, cold washing process to alloy workpiece, then successively carry out physically activated, chemical activation processing；Film: first carrying out zinc-plated processing to the alloy workpiece after activation, then phosphorating treatment, then immerses progress anodic electrophoresis in electrolyte and handle to obtain tool film workpiece；Post-processing: tool film workpiece is rinsed through clear water, cold water elution, dries to obtain alloy workpiece finished product; alloy workpiece is after forming electrophoretic coating; workpiece is cathode; anodic solution does not occur; and then safeguard that workpiece surface and phosphating coat are not destroyed, alloy components surface is first zinc-plated, phosphatization carries out electrophoretic coating again has protective effect to metal, and paint valence height used is of fine quality; and high antiseptic property can be obtained, high durable, epipodium guaranteed cost.
Description
Technical field
The invention belongs to field of metal surface treatment technology, and in particular to zinc-plated rear electrophoresis technique.
Background technique
The continuous development of science and technology has driven the continuous development of society and scientific research, from high-end aerospace, industrial and commercial bank of army
Industry embodies the progress of science and technology to the clothing, food, lodging and transportion -- basic necessities of life of the common people invariably.And constantly bringing forth new ideas for the vehicles, it highly shortened that
This distance.Automobile is largely affected as the now main vehicles, material composition and process of surface treatment
Service life.
With the development of the automobile industry, advanced painting dressing automobiles especially car coating technology and equipment is able to fastly in China
Speed application, currently, the level in the coating equipment of China's installation has had great progress, from now on as water paint and powder apply
The use of the environmental protection coating materials such as material, the application techniques level in China will integrally reach world-class levels.
The structural material and exterior trimming parts material of automobile are usually steel alloy or aluminium alloy, and with the hair of automotive light weight technology
Aluminium alloy is opened up more and more using as a kind of inexorable trend.Aluminium alloy is high with specific strength, good thermally conductive and electric conductivity,
Moulding is good, good moldability, without black brittleness, resistance to corrosion is strong, cheap the advantages that and be widely used.Especially to aluminium
After alloy is surface-treated, surface hardness, wearability and corrosion resistance are all greatly improved.But at common metal surface
The surface property promotion managed to alloy is limited.
For the defect of existing aluminum alloy surface processing technique, publication number 106835243A discloses automobile electrophoresis process,
Its requirement that salt spray test is coped with only by conventional electrophoretic technique.But by the requirement of salt spray test, this is only to produce
The basis of product factory, this is the use for being much unable to satisfy surroundings.
Summary of the invention
In view of the above problems, the present invention provides zinc-plated rear electrophoresis technique.
To achieve the goals above, the invention adopts the following technical scheme:
Zinc-plated rear electrophoresis technique, includes the following steps:
(1) pre-treatment: oil removing, hot water wash, derusting, cold washing process are successively carried out to alloy workpiece, then successively carries out object
Reason activation, chemical activation processing；
(2) it is film-made: zinc-plated processing first being carried out to the alloy workpiece after activation, then phosphorating treatment, then immersed in electrolyte
It carries out anodic electrophoresis and handles to obtain tool film workpiece；
(3) it post-processes: tool film workpiece being rinsed through clear water, cold water elution, dries to obtain alloy workpiece finished product.
General alloy components can carry out the pretreatment such as degreasing and rust removal, first before surface treatment (plating etc.) to prevent
Oil, rust etc. cause plating solution failure or effect to reduce, and the present invention is on this basis, needs to be activated alloy surface,
The technique of activation processing has more form, how to activate, and activation degree is how, will cause the effect of sequent surface processing,
Protective layer thickness, compactness extent such as formation, and then influence the using effect and service life of alloy components.The present invention directlys adopt
The physically activated mode combined with chemical activation, to obtain better activation effect.The mode of activation processing is although a variety of more
Sample, generally all simple to carry out activating using acid, still, it is uneven that such form will cause activation degree, and is easy
It causes alloy surface to form loss pit, and then subsequent plating/electrophoresis is caused to have deviation.
Preferably, described physically activated specifically: alloy workpiece is tilted 40-60 °, with superheated steam by workpiece bottom
After being persistently blown 10-30s upwards, in -2-0 DEG C of cold water of immersion, cyclic steam blowing, cold water soak are operated 3-5 times.Using physics
The method of activation can greatly simplify activating process, save labour turnover, and the present invention uses extremely simple physically activated technique,
Steam condensing reflux is avoided using the inclination angle of alloy components, while using (150-200 DEG C) of superheated steam blowing, can to steam
Vapour loss at once after blowing over alloy components surface, reducing condensing droplet falling, (droplets fall back will form part to alloy components surface
Supercooling, it is possible to create localized cracks).The mode of hot and cold alternation is recycled, alloy surface phase constitution form (activating) is changed.
Preferably, the chemical activation is impregnated using activator, the activator includes hydrogen fluoride 25-75g/L, fluorine boron
Sour 50-90g/L, perchloric acid 4-8g/L, sodium citrate 3-5g/L, polytetrafluoroethylgranule granule 40-60g/L.General chemical activation
Agent is activated using common acid, but practicability is not high, and first common acid is difficult erodable section to the insensitive alloy of acid,
Second it will form the different pit of degree (naked eyes are invisible) after acid corrosion, and then influence the protective layer shape of subsequent plating/electrophoresis
At.And the activator of the specific allotment of the present invention, with extremely wide application field (alloy use that can be insensitive to acid), and add
Polytetrafluoroethylgranule granule, can greatly slow down the extent of reaction of the application activator and alloy surface, can artificially control work
Change degree.
Preferably, the zinc coating thickness after zinc-plated described in film is 4-6 μm, phosphorating treatment is the phosphatization at 70-90 DEG C
8-12min.Workpiece after zinc-plated forms first layer protective layer, but the protective layer is only more loose structure, can not be coped with
The variation of environment, and phosphorating treatment can further densify protective layer, form the composite layer of acid and alkali-resistance, but it is easy to happen anode
It dissolves (phosphating coat is destroyed).
Preferably, electrolyte described in film includes, by mass percentage: solid part coating 9-12%, liquid part
Solvent 88-91%.
Further preferably, after the completion of the electrolyte configuration, it is additionally added the compounding particle of germanium nitride particle, cerium oxide particle
The volume ratio of composition, composition and electrolyte is 0.6-1.8:1.In electrophoresis process, due to the effect of electric current, electrolyte meeting
Form new protective film on phosphating coat, and the compounding particulate composition of specific addition, protection can be incorporated under the action of electric current
In film, be conducive to improve film hardness, improve tribological property, corrosion resisting property, the preferably micro- polishing machine of film layer, for hair
The effect of particle is waved, preferably controls germanium nitride particle here, the volume ratio of cerium oxide particle is 1:1.
Further preferably, solid part coating includes furfuryl alcohol phenolic resin, furfural acetone resin, in furfuryl alcohol pollopas
It is one or more, in solid part coating nitrogen content be 10-20%.And the main component resins as electrophoresis electrolyte, this hair
It is bright also specifically to use resinamines, compared to common resin, compared in the resin of high nitrogen content, due to the presence of nitrogen, and
Nitrogen cerium compound is formed with particulate composition is compounded, further enhances the comprehensive performance of protective film.
Preferably, being dried described in post-processing specifically: workpiece is placed in baking oven, keeps 30- at 108-190 DEG C
50min。
Compared with prior art, the present invention has the advantage that
(1) for alloy workpiece after forming electrophoretic coating, workpiece is cathode, anodic solution does not occur, and then safeguard workpiece table
Face and phosphating coat are not destroyed.
(2) alloy components surface is first zinc-plated, phosphatization carries out electrophoretic coating again has protective effect to metal, and paint valence used is high-quality
It is excellent, and high antiseptic property can be obtained, high durable, epipodium guaranteed cost.
(3) present invention use physically activated carry out pre-treatment, be blown using superheated steam, then it is water cooled recycle into
Row to change alloy surface Phase Morphology, and then guarantees the perfect fitting of subsequent plating/electrophoresis.
(4) present invention uses specific chemical activating agent, (can make to sour insensitive alloy with extremely wide application field
With), and it is added to polytetrafluoroethylgranule granule, it can greatly slow down the extent of reaction of activator and alloy surface, able person is control
Activation degree.
(5) in the electrolyte of electrophoresis of the present invention specific addition compounding particulate composition, be conducive to improve film hardness, change
The tribological property of kind film layer, corrosion resisting property, preferably micro- polishing machine.
Specific embodiment
The following is specific embodiments of the present invention, and technical scheme of the present invention will be further described, but the present invention is simultaneously
It is not limited to these embodiments.
Embodiment 1
Pre-treatment: oil removing, hot water wash, derusting, cold washing process are successively carried out to alloy workpiece, first tilts alloy workpiece
It 50 °, after being persistently blown 20s upwards by workpiece bottom with superheated steam, immerses in -1 DEG C of cold water, cyclic steam blowing, cold water leaching
Bubble operation 4 times, then alloy workpiece is impregnated with activator, wherein activator includes hydrogen fluoride 50g/L, fluoboric acid 70g/L, high chlorine
Sour 6g/L, sodium citrate 4g/L, polytetrafluoroethylgranule granule 50g/L carry out physics, chemically composited activation processing；
Film: zinc-plated processing formation is first carried out to the alloy workpiece after activation with a thickness of 5 μm of zinc coat, then at 80 DEG C
Lower phosphatization 10min forms phosphating coat, then immerses the electricity of solid part coating 11% by mass percentage, liquid part solvent 89%
It solves in liquid, to be added into electrolyte be the germanium nitride particle of 1.2:1 with the volume ratio of electrolyte, cerium oxide particle compounds particle
Composition, and control germanium nitride particle, cerium oxide particle volume ratio be 1:1, carry out anodic electrophoresis handle to obtain tool film workpiece,
Middle solid part coating includes one of furfuryl alcohol phenolic resin, furfural acetone resin, furfuryl alcohol pollopas or a variety of, and solid part applies
Nitrogen content is 15% in material；
Post-processing: tool film workpiece is rinsed, cold water elution through clear water, workpiece is placed in baking oven, is kept at 150 DEG C
40min obtains alloy workpiece finished product.
Embodiment 2
Pre-treatment: oil removing, hot water wash, derusting, cold washing process are successively carried out to alloy workpiece, first tilts alloy workpiece
It 40 °, after being persistently blown 10s upwards by workpiece bottom with superheated steam, immerses in -2 DEG C of cold water, cyclic steam blowing, cold water leaching
Bubble operation 3 times, then alloy workpiece is impregnated with activator, wherein activator includes hydrogen fluoride 25g/L, fluoboric acid 50g/L, high chlorine
Sour 4g/L, sodium citrate 3g/L, polytetrafluoroethylgranule granule 40g/L carry out physics, chemically composited activation processing；
Film: zinc-plated processing formation is first carried out to the alloy workpiece after activation with a thickness of 5 μm of zinc coat, then at 80 DEG C
Lower phosphatization 10min forms phosphating coat, then immerses the electricity of solid part coating 11% by mass percentage, liquid part solvent 89%
It solves in liquid, to be added into electrolyte be the germanium nitride particle of 1.2:1 with the volume ratio of electrolyte, cerium oxide particle compounds particle
Composition, and control germanium nitride particle, cerium oxide particle volume ratio be 1:1, carry out anodic electrophoresis handle to obtain tool film workpiece,
Middle solid part coating includes one of furfuryl alcohol phenolic resin, furfural acetone resin, furfuryl alcohol pollopas or a variety of, and solid part applies
Nitrogen content is 15% in material；
Post-processing: tool film workpiece is rinsed, cold water elution through clear water, workpiece is placed in baking oven, is kept at 150 DEG C
40min obtains alloy workpiece finished product.
Embodiment 3
Pre-treatment: oil removing, hot water wash, derusting, cold washing process are successively carried out to alloy workpiece, first tilts alloy workpiece
It 60 °, after being persistently blown 30s upwards by workpiece bottom with superheated steam, immerses in 0 DEG C of cold water, cyclic steam blowing, cold water soak
Operation 5 times, then alloy workpiece is impregnated with activator, wherein activator includes hydrogen fluoride 75g/L, fluoboric acid 90g/L, perchloric acid
8g/L, sodium citrate 5g/L, polytetrafluoroethylgranule granule 60g/L carry out physics, chemically composited activation processing；
Film: zinc-plated processing formation is first carried out to the alloy workpiece after activation with a thickness of 5 μm of zinc coat, then at 80 DEG C
Lower phosphatization 10min forms phosphating coat, then immerses the electricity of solid part coating 11% by mass percentage, liquid part solvent 89%
It solves in liquid, to be added into electrolyte be the germanium nitride particle of 1.2:1 with the volume ratio of electrolyte, cerium oxide particle compounds particle
Composition, and control germanium nitride particle, cerium oxide particle volume ratio be 1:1, carry out anodic electrophoresis handle to obtain tool film workpiece,
Middle solid part coating includes one of furfuryl alcohol phenolic resin, furfural acetone resin, furfuryl alcohol pollopas or a variety of, and solid part applies
Nitrogen content is 15% in material；
Post-processing: tool film workpiece is rinsed, cold water elution through clear water, workpiece is placed in baking oven, is kept at 150 DEG C
40min obtains alloy workpiece finished product.
Embodiment 4
Pre-treatment: oil removing, hot water wash, derusting, cold washing process are successively carried out to alloy workpiece, first tilts alloy workpiece
It 50 °, after being persistently blown 20s upwards by workpiece bottom with superheated steam, immerses in -1 DEG C of cold water, cyclic steam blowing, cold water leaching
Bubble operation 4 times, then alloy workpiece is impregnated with activator, wherein activator includes hydrogen fluoride 50g/L, fluoboric acid 70g/L, high chlorine
Sour 6g/L, sodium citrate 4g/L, polytetrafluoroethylgranule granule 50g/L carry out physics, chemically composited activation processing；
Film: zinc-plated processing formation is first carried out to the alloy workpiece after activation with a thickness of 4 μm of zinc coat, then at 70 DEG C
Lower phosphatization 8min forms phosphating coat, then immerses the electrolysis of solid part coating 9%, liquid part solvent 91% by mass percentage
In liquid, to be added into electrolyte be the germanium nitride particle of 0.6:1 with the volume ratio of electrolyte, cerium oxide particle compounds particle group
Close object, and control germanium nitride particle, cerium oxide particle volume ratio be 1:1, carry out anodic electrophoresis handle to obtain tool film workpiece, wherein
Solid part coating includes one of furfuryl alcohol phenolic resin, furfural acetone resin, furfuryl alcohol pollopas or a variety of, solid part coating
Middle nitrogen content is 10%；
Post-processing: tool film workpiece is rinsed, cold water elution through clear water, workpiece is placed in baking oven, is kept at 150 DEG C
40min obtains alloy workpiece finished product.
Embodiment 5
Pre-treatment: oil removing, hot water wash, derusting, cold washing process are successively carried out to alloy workpiece, first tilts alloy workpiece
It 50 °, after being persistently blown 20s upwards by workpiece bottom with superheated steam, immerses in -1 DEG C of cold water, cyclic steam blowing, cold water leaching
Bubble operation 4 times, then alloy workpiece is impregnated with activator, wherein activator includes hydrogen fluoride 50g/L, fluoboric acid 70g/L, high chlorine
Sour 6g/L, sodium citrate 4g/L, polytetrafluoroethylgranule granule 50g/L carry out physics, chemically composited activation processing；
Film: zinc-plated processing formation is first carried out to the alloy workpiece after activation with a thickness of 6 μm of zinc coat, then at 90 DEG C
Lower phosphatization 12min forms phosphating coat, then immerses the electricity of solid part coating 12% by mass percentage, liquid part solvent 88%
It solves in liquid, to be added into electrolyte be the germanium nitride particle of 1.8:1 with the volume ratio of electrolyte, cerium oxide particle compounds particle
Composition, and control germanium nitride particle, cerium oxide particle volume ratio be 1:1, carry out anodic electrophoresis handle to obtain tool film workpiece,
Middle solid part coating includes one of furfuryl alcohol phenolic resin, furfural acetone resin, furfuryl alcohol pollopas or a variety of, and solid part applies
Nitrogen content is 20% in material；
Post-processing: tool film workpiece is rinsed, cold water elution through clear water, workpiece is placed in baking oven, is kept at 150 DEG C
40min obtains alloy workpiece finished product.
Embodiment 6
Pre-treatment: oil removing, hot water wash, derusting, cold washing process are successively carried out to alloy workpiece, first tilts alloy workpiece
It 50 °, after being persistently blown 20s upwards by workpiece bottom with superheated steam, immerses in -1 DEG C of cold water, cyclic steam blowing, cold water leaching
Bubble operation 4 times, then alloy workpiece is impregnated with activator, wherein activator includes hydrogen fluoride 50g/L, fluoboric acid 70g/L, high chlorine
Sour 6g/L, sodium citrate 4g/L, polytetrafluoroethylgranule granule 50g/L carry out physics, chemically composited activation processing；
Film: zinc-plated processing formation is first carried out to the alloy workpiece after activation with a thickness of 5 μm of zinc coat, then at 80 DEG C
Lower phosphatization 10min forms phosphating coat, then immerses the electricity of solid part coating 11% by mass percentage, liquid part solvent 89%
It solves in liquid, to be added into electrolyte be the germanium nitride particle of 1.2:1 with the volume ratio of electrolyte, cerium oxide particle compounds particle
Composition, and control germanium nitride particle, cerium oxide particle volume ratio be 1:1, carry out anodic electrophoresis handle to obtain tool film workpiece,
Middle solid part coating includes one of furfuryl alcohol phenolic resin, furfural acetone resin, furfuryl alcohol pollopas or a variety of, and solid part applies
Nitrogen content is 15% in material；
Post-processing: tool film workpiece is rinsed, cold water elution through clear water, workpiece is placed in baking oven, is kept at 108 DEG C
30min obtains alloy workpiece finished product.
Embodiment 7
Pre-treatment: oil removing, hot water wash, derusting, cold washing process are successively carried out to alloy workpiece, first tilts alloy workpiece
It 50 °, after being persistently blown 20s upwards by workpiece bottom with superheated steam, immerses in -1 DEG C of cold water, cyclic steam blowing, cold water leaching
Bubble operation 4 times, then alloy workpiece is impregnated with activator, wherein activator includes hydrogen fluoride 50g/L, fluoboric acid 70g/L, high chlorine
Sour 6g/L, sodium citrate 4g/L, polytetrafluoroethylgranule granule 50g/L carry out physics, chemically composited activation processing；
Film: zinc-plated processing formation is first carried out to the alloy workpiece after activation with a thickness of 5 μm of zinc coat, then at 80 DEG C
Lower phosphatization 10min forms phosphating coat, then immerses the electricity of solid part coating 11% by mass percentage, liquid part solvent 89%
It solves in liquid, to be added into electrolyte be the germanium nitride particle of 1.2:1 with the volume ratio of electrolyte, cerium oxide particle compounds particle
Composition, and control germanium nitride particle, cerium oxide particle volume ratio be 1:1, carry out anodic electrophoresis handle to obtain tool film workpiece,
Middle solid part coating includes one of furfuryl alcohol phenolic resin, furfural acetone resin, furfuryl alcohol pollopas or a variety of, and solid part applies
Nitrogen content is 15% in material；
Post-processing: tool film workpiece is rinsed, cold water elution through clear water, workpiece is placed in baking oven, is kept at 190 DEG C
50min obtains alloy workpiece finished product.
Embodiment 8
The difference from embodiment 1 is that only being carried out in 8 pre-treatment of embodiment physically activated.
Embodiment 9
The difference from embodiment 1 is that only carrying out chemical activation in 9 pre-treatment of embodiment.
Embodiment 10
The difference from embodiment 1 is that embodiment 10 is physically activated only primary with steam, cold water treatment.
Embodiment 11
The difference from embodiment 1 is that germanium nitride particle is only added in the electrolyte of embodiment 11.
Embodiment 12
The difference from embodiment 1 is that cerium oxide particle is only added in the electrolyte of embodiment 12.
Embodiment 13
The difference from embodiment 1 is that nitrogen content is 9% in 13 solid part coating of embodiment.
Comparative example 1
The difference from embodiment 1 is that without being activated when 1 pre-treatment of comparative example.
Comparative example 2
The difference from embodiment 1 is that the compounding of germanium nitride particle, cerium oxide particle is not added in 2 electrolyte of comparative example
Particulate composition.
Comparative example 3
The difference from embodiment 1 is that being free of polytetrafluoroethylgranule granule in 3 activator of comparative example.
The workpiece protective film of embodiment 1-13 and comparative example 1-3 are tested, its hardness, film thickness, film outward appearance are tested, is tied
Fruit is as shown in table 1:
Table 1: the performance of workpiece protective film in embodiment 1-13 and comparative example 1-3
It is skilled to this field although present invention has been described in detail and some specific embodiments have been cited
For technical staff, as long as it is obvious for can making various changes or correct without departing from the spirit and scope of the present invention.
Claims (8)
1. zinc-plated rear electrophoresis technique, which is characterized in that the technique includes the following steps:
(1) pre-treatment: successively carrying out oil removing, hot water wash, derusting, cold washing process to alloy workpiece, then successively carries out physics and live
Change, chemical activation processing；
(2) it is film-made: zinc-plated processing first being carried out to the alloy workpiece after activation, then phosphorating treatment, then immerse in electrolyte and carry out
Anodic electrophoresis handles to obtain tool film workpiece；
(3) it post-processes: tool film workpiece being rinsed through clear water, cold water elution, dries to obtain alloy workpiece finished product.
2. zinc-plated rear electrophoresis technique according to claim 1, which is characterized in that described physically activated specifically: by alloy
Workpiece tilts 40-60 °, after being persistently blown 10-30s upwards by workpiece bottom with superheated steam, in -2-0 DEG C of cold water of immersion, and circulation
Steam blast, cold water soak operate 3-5 times.
3. zinc-plated rear electrophoresis technique according to claim 1, which is characterized in that the chemical activation is soaked using activator
Bubble, the activator include hydrogen fluoride 25-75g/L, fluoboric acid 50-90g/L, perchloric acid 4-8g/L, sodium citrate 3-5g/L, gather
Tetrafluoroethene particle 40-60g/L.
4. zinc-plated rear electrophoresis technique according to claim 1, which is characterized in that the zinc coating thickness after zinc-plated described in film
It is 4-6 μm, phosphorating treatment is the phosphatization 8-12min at 70-90 DEG C.
5. zinc-plated rear electrophoresis technique according to claim 1, which is characterized in that electrolyte described in film includes, by matter
Measure percentages: solid part coating 9-12%, liquid part solvent 88-91%.
6. zinc-plated rear electrophoresis technique according to claim 5, which is characterized in that after the completion of electrolyte configuration, also plus
Enter the compounding particulate composition of germanium nitride particle, cerium oxide particle, the volume ratio of composition and electrolyte is 0.6-1.8:1.
7. zinc-plated rear electrophoresis technique according to claim 5, which is characterized in that solid part coating includes furfuryl alcohol phenolic aldehyde
One of resin, furfural acetone resin, furfuryl alcohol pollopas are a variety of, and nitrogen content is 10-20% in solid part coating.
8. zinc-plated rear electrophoresis technique according to claim 1, which is characterized in that dried described in post-processing specifically: will
Workpiece is placed in baking oven, keeps 30-50min at 108-190 DEG C.
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