CN104131305B - Pre-treating fluid for surface corrosion protection of zinc (or aluminium) alloy die castings - Google Patents
Pre-treating fluid for surface corrosion protection of zinc (or aluminium) alloy die castings Download PDFInfo
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- CN104131305B CN104131305B CN201410411551.7A CN201410411551A CN104131305B CN 104131305 B CN104131305 B CN 104131305B CN 201410411551 A CN201410411551 A CN 201410411551A CN 104131305 B CN104131305 B CN 104131305B
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Abstract
The invention discloses a pre-treating fluid for surface corrosion protection of zinc (or aluminium) alloy die castings, which is an aqueous solution composed of a nitric acid, ammonium hydrogen fluoride, sodium fluorosilicate, a boric acid and a rare earth compound, wherein 15-30 g/L of the 65% nitric acid, 50-120 g/L of the ammonium hydrogen fluoride, 1-3 g/L of the sodium fluorosilicate, 1-1.5 g/L of the boric acid, and 0.1-0.3 g/L of the lanthanum-containing or dysprosium-containing rare earth compound are provided. The pre-treating fluid is operated for 15-120 seconds at room temperature. According to the invention, an ultrathin oxidation film and surface dirt and the like formed on the surface of a zinc (or aluminium) alloy die casting can be effectively removed, and a permeable membrane with a microporous structure and good corrosion resistance is generated on the surface of a matrix showing a metallographic structure, so that the binding force, adhesion, corrosion resistance and service life of an electrophoresis coating are greatly increased. The pre-treating fluid disclosed by the invention is reasonable in formula, wide in range of application, rapid in film forming speed, and high in stability.
Description
Technical field
The present invention relates to a kind of anticorrosion permeable membrane treatment fluid, specifically a kind of zinc (or aluminum) alloy pressuring casting surface
Anticorrosion pretreatment liquid before electrophoretic painting.
Background technology
Kirsite or aluminium alloy compression casting make complex-shaped part by one-step molding, with production efficiency height, are easily achieved machine
Tool and automatization, the features such as stock utilization is high, cheap, casting dimension accuracy is high.Due to it is lightweight, have certain strong
Degree and surface brightness, therefore it is widely used in haberdashery and hardware, light industry, household electrical appliances, case and bag accessory, furniture, machinery, electronics, automobile work
All conglomeraties such as industry, toy and artware.
Because zinc or aluminum are amphoteric oxides, chemical stability is poor, strong chemistry occurs with strong acid, highly basic anti-
Should, therefore, zinc (or aluminum) alloy pressuring casting must carry out appropriate surface treatment using front, to improve its corrosion resistance, so as to reach
To protection and the purpose decorated.In many zinc (or aluminum) alloy pressuring casting surface treatment methods, because electrophoretic painting has
Adhesion is strong with adhesive force, anti-corrosion function is optimal, crosslink density（Adherence）High, mechanical performance and chemical resistance are excellent
Different, outward appearance is good, throwing power is high, safety and environmental protection is good, low cost the features such as, therefore its be at present preferably with generally acknowledged surface treatment
Method.However, zinc (or aluminum) alloy pressuring casting not only surface is smooth, and its current potential is relatively born, and surface easily generates oxide-film, it
Have a strong impact on the adhesion and adhesive force of electrophoretic coating and parent metal.Oxide film dissolving is removed, strengthens electrophoretic coating and parent metal
Adhesion and adhesive force it is critical that link.But at present the research report of this respect is little.
Chinese patent application CN201310364134 discloses a kind of for locating before automobile heat zinc coating plate surface cathode electrophoresis
Reason liquid, including organosilan, manganese nitrate, Zinc Oxide, phosphoric acid, nickel nitrate, ferrous phosphate.Chinese patent application
CN201310023256 discloses a kind of acid washing method of Electroplating on Zinc Die Castings pre-treatment, by original hydrofluoric acid containing or sulphuric acid
Highly acid pickle be re-dubbed the faintly acid pickle containing organic acid and surfactant.Chinese patent application
CN201410074364 discloses a kind of aluminum alloy surface treatment fluid, including ammonium fluosilicate and other fluorine compounds without aluminum.
But, above-mentioned treatment fluid or method be present in varying degrees, it is difficult to meet actual demand.Its problem is：Electrophoresis is applied
Layer adhesion it is excessively poor with adhesive force, easy to foaming, peeling with come off, corrosion resistance is short with the service life of coating, coating quality
It is relatively low with qualification rate, so as to limit promoting the use of for zinc (or aluminum) alloy pressuring casting；Narrow application range, cumbersome, workman
High labor intensive, work efficiency is low；Treatment fluid stability is poor, and troublesome maintenance is big with waste, and processing cost is high；Waste gas overflows hurts sb.'s feelings, and gives up
Aqueous waste solution is not disposable, big to harm and environmental pollution.
The content of the invention
The technical problem to be solved is to overcome above-mentioned the deficiencies in the prior art, there is provided a kind of formula is reasonable, work
Skill is simple, and film forming is rapid, is easily controlled, applied widely, overflows without waste gas, integrated cost low zinc (or aluminum) alloy pressuring casting
Surface anticorrosive pretreatment liquid.
The present invention solves the technical scheme of above-mentioned technical problem employing：A kind of zinc (or aluminum) alloy pressuring casting surface anticorrosion
Erosion pretreatment liquid, is characterized in that：Its aqueous solution being made up of nitric acid, ammonium acid fluoride, prodan, boric acid, rare earth compound,
The content of wherein each constituent is：65% nitric acid (HNO3) 15～30g/L, ammonium acid fluoride（NH4HF2）50～120g/L, fluorine
Sodium silicate（Na2SiF6）1～3g/L, boric acid（H3BO3）1～1.5g/L, the 0.1～0.3g/L of rare earth compound containing lanthanum or containing dysprosium.
Currently preferred solution formula is：65% nitric acid (HNO3) 20g/L, ammonium acid fluoride（NH4HF2）80g/L, fluorine silicon
Sour sodium（Na2SiF6）2g/L, boric acid（H3BO3）1.2g/L, the rare earth compound 0.2g/L containing lanthanum or containing dysprosium.
The present invention can remove the oxide-film and surface contaminants on kirsite or aluminum alloy die casting surface etc., be allowed to manifest newly
Fresh metallographic structure, improves the activity of matrix surface, and generates the uneven permeable membrane of micro-rough in matrix surface, applies electrophoresis
Layer increases with the contact surface area of matrix, causes mechanical snap between the two to act on, hence it is evident that to enhance the attachment of electrophoretic coating
Power and adhesion.Against existing technologies, rationally, process is simple, film forming is rapid, is easily controlled, applied widely for inventive formulation,
Overflow without waste gas, integrated cost is low, little to harm and environmental pollution, is a kind of preferable zinc (or aluminum) alloy pressuring casting table
Face anticorrosion pretreatment liquid, is suitable for the surface cathode electrophoresis pre-treatment of zinc (or aluminum) alloy pressuring casting and uses.
Specific embodiment
With reference to embodiment, the present invention will be further described.
A kind of zinc (or aluminum) alloy pressuring casting surface anticorrosive pretreatment liquid, it is by nitric acid, ammonium acid fluoride, hexafluosilicic acid
Sodium, boric acid, the aqueous solution of rare earth compound composition, wherein the content of each constituent is：Nitric acid (the HNO of concentration 65%3) 15～
30g/L, ammonium acid fluoride（NH4HF2）50～120g/L, prodan（Na2SiF6）1～3g/L, boric acid（H3BO3）1～1.5g/L,
0.1～0.3g/L of rare earth compound containing lanthanum or containing dysprosium.
The effect of nitric acid in solution of the present invention is oxide-film, the part hook stricture of vagina for removing kirsite or aluminum alloy die casting surface
Interior remaining alkali liquor, surface contaminants and silicon compound etc., are allowed to manifest fresh metallographic structure, improve the work of matrix surface
Property.Ammonium acid fluoride assists nitric acid to complete above effect with prodan, while generating the anti-of micro-rough injustice in matrix surface
Corrosion penetration film, this film can penetrate inside matrix surface, and the adhesion with matrix is fine, and can prevent oxide-film from producing again.
Boric acid plays complexation and cushioning effect in solution composition consumption process, is conducive to stablizing for working solution.Rare earth compound can be refined
Film layer crystal grain, further enhances the anti-corrosion capability of film layer.
The compound method of solution of the present invention is：The pure water of cumulative volume 1/4 is injected in groove, calculating is sequentially added while stirring
The nitric acid of amount, ammonium acid fluoride, prodan and rare earth compound, are then fully dissolved after the boric acid of amount of calculation with a small amount of hot water again
In adding tank liquor, pure water is finally injected to operating fluid level, stirring stands after 30 minutes and uses for 1 hour.
When the present invention is used, solution is configured by compound method, will do dry blasting（Or husky tumbling）, ultrasound wave cleaning with from
The zinc of water cleaning（Or aluminum）Alloy pressuring casting is put in the anticorrosion permeable membrane treatment fluid, and temperature is room temperature, and the time is 15
～120 seconds.Specifically, first by zinc（Or aluminum）Alloy pressuring casting dry blasting（Or husky tumbling）, remove greasy dirt, the oxidation of piece surface
The defects such as skin, burr, dirt, obtain accurate bright and clean surface.It is subsequently placed in ultrasound wave and cleans, makes blind hole, the groove of workpiece
The dirt such as lint, dust granule, greasy dirt Deng position thoroughly cleaning is clean, obtains thoroughly clean optimum state.Then with certainly
Water thoroughly cleans the remaining weak lye of surface of the work.Finally anticorrosion pretreatment liquid of the present invention is immersed under room temperature state
In, the time is 15～120 seconds（The general working solution concentration high time newly matched somebody with somebody is shorter, and the old working solution concentration low time is slightly long）.
The present invention can remove the oxide-film and surface contaminants on kirsite or aluminum alloy die casting surface etc., be allowed to manifest newly
Fresh metallographic structure, improves the activity of matrix surface, and generates the uneven permeable membrane of micro-rough in matrix surface, applies electrophoresis
Layer increases with the contact surface area of matrix, causes mechanical snap between the two to act on, hence it is evident that to enhance the attachment of electrophoretic coating
Power and adhesion.Electrophoretic coating can produce in the curing process very big internal stress, and the presence of anticorrosion permeable membrane can be effective
The stress concentration in coating is eliminated, coating cracking is prevented.Permeable membrane has extraordinary anti-corrosion capability, substantially prolongs electrophoresis
The service life of coating, gives full play to protection and the decoration function of electrophoretic coating.With reference to GB/T9753-2007《Paint and varnish
AEG-process》, test electrophoretic coating adhesion, as a result for：It is processed by the invention after gained electrophoretic coating test piece for >=
9mm, and prior art test piece is 1mm.With reference to GB/T9286-1998《The cross cut test of paint and varnish paint film》, test electrophoresis
The adhesive force of coating, as a result for：The electrophoretic coating test piece of gained is 0 grade after processed by the invention, and prior art test piece is 5
Level.With reference to GB/T1771-91《Colored paint and blue or green paint-resistance to neutral salt spray performance measurement》, test the antiseptic power of electrophoretic coating（h）With
Its service life, as a result for：The electrophoretic coating test piece of gained is >=1000h after processed by the invention, and prior art test piece is
≤72h。
The present invention can effectively remove very thin oxide-film that dezincify (or aluminum) alloy pressuring casting surface formed and surface contaminants etc.,
And generate with microporosity structure and the extraordinary permeable membrane of corrosion resistance in the matrix surface for manifesting metallographic structure.This film
Adhesion, adhesive force, antiseptic power and its service life to electrophoretic coating etc. have remarkable result, and the qualification rate of electrophoretic coating
Height, without foaming, peeling and the defect that comes off.Treatment fluid stability is high, and film forming is rapid, consumes few, and maintenance is easier to, with without waste, use
Life-span length, cost performance is high, and integrated cost is low, overflows without waste gas, and waste water and waste liquid is disposable, therefore good work environment, to harm
It is little with environmental pollution.
The present invention is applied widely, is not only suitable for zinc alloy diecasting, is also applied for aluminum alloy die casting.The present invention is also fitted
For the electrophoretic painting of various resinous types, plastic-blasting（Powder）, spray painting, the pre-treatment of the coating such as dipping lacquer.And prior art is only suitable for
Kirsite or aluminum alloy die casting one kind therein, it is impossible to which the two is shared, and undesirable to the effect of the hot curing varnishes such as electrophoretic coating.
Anticorrosion permeable membrane can make negative electrode or anodic electrophoresis coating reaches optimum performance state, including modified epoxy, acrylic acid, acrylic acid
The electrophoretic coating of the resinous types such as polyurethane, Polyurethane.In addition, it is suitable for the plastic-blasting of various resinous types（Powder）、
The pre-treatment of the coatings such as spray painting, dipping lacquer.
Embodiment 1：A kind of zinc (or aluminum) alloy pressuring casting surface anticorrosive pretreatment liquid, its be by nitric acid, ammonium acid fluoride,
Prodan, boric acid, the aqueous solution of rare earth compound composition, wherein, the nitric acid (HNO of concentration 65%3) 15g/L, ammonium acid fluoride
（NH4HF2）50g/L, prodan（Na2SiF6）1g/L, boric acid（H3BO3）1g/L, rare earth compound（Including containing lanthanum or containing dysprosium
One kind in compound or two kinds）0.1g/L.Dry blasting will be done（Or husky tumbling）, ultrasound wave cleaning with tap water cleaning zinc
（Or aluminum）Alloy pressuring casting is put in above-mentioned anticorrosion permeable membrane treatment fluid, and temperature is room temperature, and the time is 100～120 seconds, matrix
Surface Creation has the permeable membrane of microporosity structure and corrosion resistance.Treatment fluid overflows without waste gas, to harm and environment
Pollution is little.The electrophoretic coating qualification rate of gained is high, without foaming, peeling and the defect that comes off.It is detected with reference to relevant criterion,
As a result it is：Adhesion (cupping) be 9mm, adhesive force be 0 grade, resistance to neutral salt spray when 1000h is accomplished, part be showed no foaming,
Come off and the bad phenomenon such as get rusty.
Embodiment 2：A kind of zinc (or aluminum) alloy pressuring casting surface anticorrosive pretreatment liquid, is characterized in that：It is by nitric acid,
Ammonium acid fluoride, prodan, boric acid, the aqueous solution of rare earth compound composition, wherein, nitric acid (HNO3, 65%) 30g/L, fluohydric acid gas
Ammonium（NH4HF2）120g/L, prodan（Na2SiF6）3g/L, boric acid（H3BO3）1.5g/L, rare earth compound（Including containing lanthanum or
Containing the one kind in dysprosium compound or two kinds）0.3g/L.Dry blasting will be done（Or husky tumbling）, ultrasound wave cleaning with tap water cleaning
Zinc（Or aluminum）Alloy pressuring casting is put in above-mentioned anticorrosion permeable membrane treatment fluid, and temperature is room temperature, and the time is 15～30 seconds, base
Body Surface Creation has the permeable membrane of microporosity structure and good corrosion resistance.Treatment fluid overflows without waste gas, to harm and
Environmental pollution is little.The electrophoretic coating qualification rate of gained is high, without foaming, peeling and the defect that comes off.It is carried out with reference to relevant criterion
Detection, as a result for：Adhesion (cupping) is 9.3mm, and adhesive force is 0 grade, and, when 1000h is accomplished, part is not for resistance to neutral salt spray
See foaming, come off and the bad phenomenon such as get rusty.
Embodiment 3：A kind of zinc (or aluminum) alloy pressuring casting surface anticorrosive pretreatment liquid, is characterized in that：It is by nitric acid,
Ammonium acid fluoride, prodan, boric acid, the aqueous solution of rare earth compound composition, wherein, nitric acid (HNO3, 65%) 20g/L, fluohydric acid gas
Ammonium（NH4HF2）80g/L, prodan（Na2SiF6）2g/L, boric acid（H3BO3）1.2g/L, rare earth compound（Including containing lanthanum or containing
One kind in dysprosium compound or two kinds）0.2g/L.Dry blasting will be done（Or husky tumbling）, ultrasound wave cleaning with tap water cleaning
Zinc（Or aluminum）Alloy pressuring casting is put in above-mentioned anticorrosion permeable membrane treatment fluid, and temperature is room temperature, and the time is 15～120 seconds, base
Body Surface Creation has the permeable membrane of microporosity structure and good corrosion resistance.Treatment fluid overflows without waste gas, to harm and
Environmental pollution is little.The electrophoretic coating qualification rate of gained is high, without foaming, peeling and the defect that comes off.It is carried out with reference to relevant criterion
Detection, as a result for：Adhesion (cupping) is 9.6mm, and adhesive force is 0 grade, and, when 1000h is accomplished, part is not for resistance to neutral salt spray
See foaming, come off and the bad phenomenon such as get rusty.
Claims (2)
1. a kind of zinc or aluminum alloy die casting surface anticorrosive pretreatment liquid, is characterized in that：It is by nitric acid, ammonium acid fluoride, fluorine
Sodium silicate, boric acid, the aqueous solution of rare earth compound composition, wherein the content of each constituent is：65% nitric acid (HNO3) 15～
30g/L, ammonium acid fluoride（NH4HF2）50～120g/L, prodan（Na2SiF6）1～3g/L, boric acid（H3BO3）1～1.5g/L,
Containing lanthanum or containing the 0.1～0.3g/L of rare earth compound in dysprosium compound.
2. zinc according to claim 1 or aluminum alloy die casting surface anticorrosive pretreatment liquid, is characterized in that：It is described by nitre
Acid, ammonium acid fluoride, prodan, boric acid, the aqueous formulation of rare earth compound composition are：65% nitric acid (HNO3) 20g/L,
Ammonium acid fluoride（NH4HF2）80g/L, prodan（Na2SiF6）2g/L, boric acid（H3BO3）1.2g/L, the rare earth containing lanthanum or containing dysprosium
Compound 0.2g/L.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410411551.7A CN104131305B (en) | 2014-08-20 | 2014-08-20 | Pre-treating fluid for surface corrosion protection of zinc (or aluminium) alloy die castings |
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| CN201410411551.7A CN104131305B (en) | 2014-08-20 | 2014-08-20 | Pre-treating fluid for surface corrosion protection of zinc (or aluminium) alloy die castings |
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| CN104131305B true CN104131305B (en) | 2017-04-19 |
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| US5538600A (en) * | 1994-07-27 | 1996-07-23 | Aluminum Company Of America | Method for desmutting aluminum alloys having a highly-reflective surface |
| CN101665934B (en) * | 2009-09-27 | 2012-04-11 | 大连三达奥克化学股份有限公司 | Film treating agent for treatment before electro-coating of die-cast aluminum alloy workpiece and preparation method thereof |
| CN103103512B (en) * | 2011-11-15 | 2016-07-06 | 广东兴发铝业有限公司 | The rare earth modified titanium zirconium system's chemical passivation liquid processed for aluminium shape surface and using method |
| CN102443794B (en) * | 2011-12-06 | 2013-07-24 | 中国科学院金属研究所 | Aluminum alloy scratch resistant and fingerprint resistant chromium-free chemical conversion solution for ship and preparation method of conversion film |
| CN102808170A (en) * | 2012-08-01 | 2012-12-05 | 天津大学 | Treating fluid for corrosion-resistant rare earth conversion film on surface of aluminum alloy, and application method thereof |
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