CN110230049A - A kind of novel non-chrome sealer - Google Patents

Abstract

The present invention is a kind of passivation chrome-free sealing agent for after steel surface phosphatization or zirconium treatment, without chromium or other couples of people or the harmful substance of environment.This product is aqueous solution, composition characteristic are as follows: mass fraction: fluosilicate 5%~10%；Sodium nitrate 6%~15%；Fluozirconate 15%~30%；Fluotitanate 1%~3%；Corrosion inhibiter 0.1%~1%；Surfactant 0.5%~2%；Antioxidant 0.1%~0.5%；The alkaline regulator 0.1%~0.5% of wetting agent 0.1%~0.5%；Silane coupling agent 0.1%~0.8%；Remaining is deionized water.Good passivation effect of the present invention can greatly improve rust resistance and corrosion resistance ability, can substitute sealer containing chromium；Using simple, to equipment without particular/special requirement.

Description

A kind of novel non-chrome sealer

Technical field

The present invention relates to a kind of sealer more particularly to it is a kind of be passivated suitable for steel iron phosphatising or zirconium rear enclosed it is novel Chrome-free sealing agent.The present invention is a kind of novel environment friendly sealer without heavy metal ion such as chromium.

Background technique

Since nineteen ninety-six, China is always the first in the world big steel producing country.More than 10 years, Chinese crude steel yield from 108,910,000 tons of rapid growths in 1997 increase 458,930,000 tons, i.e. crude steel yield is 1997 to 567,840,000 tons of 2009 It is increased more than 4 times on the basis of year, average annual growth rate reaches 16%.However steel is the metal easily corroded.The whole world is every Just there is within 90 seconds 1 ton of steel corrosion at iron rust, and the energy needed for refining 1 ton of steel is then for one family with 3 months.So along with The corrosion resistant surfaces processing technique of the development of steel and iron industry, steel is more important.

Currently, steel surface phosphatization and zirconium treatment are common anti-corrosion means.By steel substrate and contain phosphate Conversion fluid react, steel surface formed phosphating coat.However phosphating coat itself is porous, corrosion resistance is limited, so also Further closing Passivation Treatment must be done to it.

Henkel KGaA company in 2005 is proposed a nanometer vitrification technical products NT-1, it is new one based on fluorine zirconic acid For zirconium technology, seminar, Dalian Polytechnic University also has developed such technology, sees ZL200710010965.9.Its advantages are very Significantly, it can solve environmental pollution first, without containing chromium, nickel and other toxic heavy metals, phosphate free conversion film and volatilization Property organic component, no sediment and waste water handling problem, second is that can energy conservation, it is that room temperature uses, and the good phosphating solution of performance must It must be high temperature, third is that not changing original production technology, additionally it is possible to the saving processing time (phosphatization is impregnated needs ten minutes or more, And technology 1-3 minutes), streamlining management technique (needs table tune, and nanometer zirconium technology does not need the technique) before phosphatization, Fourth is that nanotechnology, thus unit mass product treatment area is big, usual zirconium liquid is capable of handling 150-300 square metres of workpiece, Sometimes thousands of square metres are even capable of handling, and phosphatization is only capable of 10-30 square metres of workpiece of processing, thus processed in units can be reduced The cost of area.But due to the difference of the superficial layer of domestic steel and iron parts processing, there is part iron part zirconium liquid to handle aftereffect Fruit be not it is ideal, often have a red rust appearance, for example, this steel without silicon plate etc., how to avoid these red rusts from occurring and not significant The adhesive force of coating is influenced, and then influences the anti-corrosion effect of coating, is a very crucial problem for these plates. The study found that applying specific this problem of sealer very good solution after zirconium.

Common sealer is chromic acid product salt.Chromic acid product salt has film forming, can form one layer of cause in metal surface Close water and oxidation film, and there are also the functions of self-regeneration.Its is low in cost, simple process, and sealing effect is good.But six Valence chromium has strong toxicity, is one of the carcinogenic substance having confirmed that.In recent years some are studies have shown that chromium is general first with Cr VI Form penetrate into people and animals' cell, be then reduced to trivalent chromium in the cell and constitute " ultimate carcinogen ", and then cause the prominent of cell Change and canceration.Zoopery also indicates that trivalent chromium can pass through placenta and play inhibiting effect and teratogenesis with the growth of fetus.Chromium is also It is a kind of sensibiligen, the irritation and corrosivity that the compound of Cr VI has, strong oxidation are often started with local lesion, It gradually develops to incurable.Trivalent chromium is greater than 5.0 water in pH since the solubility of hydrolysis and Cr (OH) 3 is small Harmful concentration is not up in body.Cr VI exists in the form of CrO42-, is not limited by ambient condition, can be in water Reach very high concentration.Therefore, not trivalent chromium toxicity is little, but because its existing form will not reach under normal circumstances It is horizontal to very high adverse concentration.No matter trivalent chromium or Cr VI, potential danger is fairly obvious, thus country to chromium Stringent limitation is carried out in discharge, some countries have been proposed Chrome-free in waste water and discharge.

Several chromium-free deactivation products have been proposed at present, such as a kind of environment-friendly type multifunctional steel surface processing agent, application Number CN200710195860.5, it is impossible to be used in zirconium treatment.For another example, iron and steel parts normal-temperature film passivating agent for processing before electro-coating and its Preparation method, application number CN200910187640.7, it is impossible to be used in zirconium treatment.In general, it has been suggested that several Chrome-frees Passivation product still exist is only used for phosphating solution passivation aspect, in novel zirconiumization especially cold-reduced sheet without silicon plate, heat Plate, ironcasting etc. are rolled with after zirconium treatment, is mostly easily got rusty, and after spray painting the disadvantages of anti-corrosion ability reduction, need new energy and zirconium Change the matched new passivation agent of liquid.In terms of Coating Pretreatment, due to zirconium liquid not phosphate-containing and heavy metal, normal-temperature operation, The advantages that without slag, belongs to energy saving environmental protection product, but in extension process, and the performance etc. of auxiliary products is also very important factor. The present invention is handled in iron workpiece aiming at zirconium liquid, the iron workpiece especially easily to get rusty, and the mating production specially invented Product.

Summary of the invention

To solve problems of the prior art, the present invention provides a kind of for new after steel iron phosphatising or zirconium treatment Type chrome-free sealing agent.The present invention is water solubility, is free of chromium and other heavy metal ion, without the harmful substances such as formaldehyde, benzene, safety Environmental protection.Seal treatment is carried out to the workpiece after phosphatization or zirconium with it, rust resistance and corrosion resistance ability is strong, and to phosphatization or zirconium film There is no destruction, does not influence subsequent plastic-spraying, dusts, the techniques such as coating.Free from extraneous odour of the present invention, it is at low cost, using simple.Envelope Effect is closed to approach or better than sealer containing chromium.

The present invention adopts the following technical scheme:

A kind of novel non-chrome sealer, composed of the following components by weight percentage:

Fluosilicate 5%~10%；

Sodium nitrate 6%~15%；

Fluozirconate 15%~30%；

Fluotitanate 1%~3%；

Corrosion inhibiter 0.1%~1%；

Surfactant 0.5%~2%；

Antioxidant 0.1%~0.5%；

Wetting agent 0.1%~0.5%

Alkaline regulator 0.1%~0.5%；

Silane coupling agent 0.1%~0.8%；

Deionized water surplus；

The fluosilicate is prodan, 1~2 kind in potassium fluosilicate；The fluozirconate is potassium fluorozirconate, fluorine zirconium 1~2 kind in sour ammonium, the fluotitanate is titanium sodium fluoride, 1~2 kind in potassium fluotitanate；

PH adjusting agent is used to adjust above-mentioned composition pH value as 7.0~9.0；

The corrosion inhibiter is benzotriazole, Alpha-hydroxy benzotriazole, methenamine, a kind in thiocarbamide；

The surfactant is cetyl octyldimethyl ammonium bromide, hexadecyldimethyl benzyl ammonium decyl ammonium bromide, ten Dialkyl benzene amine hydrochlorate, dodecyl benzyl dimethyl ammonium chloride, a kind in dodecylbenzyl pyridinium chloride；

The antioxidant is hydroquinone, resorcinol, a kind in catechol；

The wetting agent is organosilicon wetting agent；Organosilicon wetting agent used in the embodiment of the present invention is this Lip river of Guangzhou Si Luoke (R) wetter8030 of Ke Chemical Co., Ltd. production；

The coalescing agent is decylene glycol ester；Coalescing agent used in the embodiment of the present invention is the ten of BASF AG's production Diol ester.

The pH adjusting agent is citric acid, oxalic acid, sodium carbonate, a kind in sodium bicarbonate.

The silane coupling agent has A151 (vinyltriethoxysilane), A171 (vinyltrimethoxysilane) .A172 (vinyl three (beta-methoxy ethyoxyl) silane) etc..

Deionized water is first heated to 30 DEG C~45 DEG C by the present invention, and fluosilicate is added alternatively, stirring simultaneously, until complete Dissolution, then adds fluozirconate or fluotitanate, sodium nitrate, corrosion inhibiter, surfactant, antioxidant, wetting agent, Alkaline regulator and coalescing agent adjust solution ph to 7.0~9.0, keep the temperature 30min or more, be slowly cooled to room temperature naturally.

For the present invention using fluosilicate as main film forming substance, the two can be deposited in phosphating coat or zirconium film surface, and other Auxiliary agent cooperation inhibits the anodic process and cathodic process of electrochemical metal corrosion, plays the role of protecting metal erosion, especially Can play the role of inhibiting red rust after cold-reduced sheet zirconium, meanwhile, this tunic will not reduce again phosphating coat or the coating of zirconium film it Performance afterwards causes two layers of skin phenomenon, i.e., not will cause zirconium film or phosphating coat is insecure in conjunction with close membrane, avoids and applying Although adhesive force is fine after dress, it is unable to salt-fog resistant test, paint film is easy to fall off, and long-term anti-corrosion ability is bad etc. asks Topic.

The surfactant that the present invention is added, can reduce surface tension, has wetting, emulsification function, also has one Fixed corrosion inhibitive function.Further, since containing a large amount of zirconium titaniferous compounds in sealer provided by the invention, oxygen is formed in close membrane Change zirconium titanium substance, have certain compatibility with the zirconium oxide class in zirconium film, the binding performance of the two is increased, thus one Determine the appearance that pre-treatment film two membranes problem is avoided in degree, therefore the present invention can not only be applied to phosphating solution and play closing work With, and can be used using the substance as zirconium liquid sealer.

The present invention using when can according to sealing effect need by 1: 10~1: 50 be added deionized waters.Steel table processed Face first has to be polished, oil removing, and cleaning carries out phosphatization or zirconiumization pretreatment again, is then passivated processing, adjusts passivating solution PH7.5~9.0, water temperature are room temperature, and steel surface and this product is then made to contact 1min or more, dewatered drying.The present invention Suitable for process means such as dip-coating or sprays.

Specific embodiment

The effect analysis of metal conditioner of the present invention is carried out using following methods:

Metal plating steel plate test specimen plate by 6cm × 4cm containing zinc cleans 5 minutes in quick deoiling agent, at 60 DEG C.So It is rinsed 2 minutes with clear water, is impregnated 2 minutes in novel non-chrome sealer of the invention after 70 DEG C of heated-air dryings afterwards, it is hot after taking-up Air-dry dry, progress nature antirust and adhesive force experiment；Adhesive force experiment needs to be coated with high hydroxy acid polyester priming paint, paint film Thickness: 10 μm, acrylic acid top-coat coating, film thickness: 5 μm.

Natural antirust: the operation of finished product antirust should carry out (35 DEG C of environment temperature < in cleaning, dry environment；It is relatively wet Spend general < 75%), until thering is corrosion point to occur.

Adhesive force experiment (experiment of hundred lattice) is cut on japanning galvanized sheet by cutting machine, and depth of cut is to reach plating It until at zine plate material, after forming the quad mesh of 100 1mm, is removed by cellophane tape, passes through the number of film It is evaluated.

Embodiment 1, a kind of novel non-chrome sealer are composed of the following components by weight percentage:

Sodium metasilicate 22%；

Sodium nitrite 6%；

Potassium fluorozirconate 1%；

Benzotriazole 0.1%；

Dodecyl benzyl dimethyl ammonium chloride 0.5%；

Hydroquinone 0.1%；

Wetter80300.1%

Decylene glycol ester 0.001%

Deionized water surplus；

With lemon acid for adjusting pH value for 7.0, test result is shown in Table 1, table 2.

Embodiment 2, a kind of novel non-chrome sealer are composed of the following components by weight percentage:

Sodium metasilicate 25%；

Sodium nitrite 7.0%；

Potassium fluorozirconate 1.5%；

Benzotriazole 0.7%；

Dodecyl benzyl dimethyl ammonium chloride 0.8%；

Hydroquinone 0.2%；

Wetter80300.1%

Decylene glycol ester 0.004%；

Deionized water surplus；

With lemon acid for adjusting pH value for 7.5, test result is shown in Table 1, table 2.

Embodiment 3, a kind of novel non-chrome sealer are composed of the following components by weight percentage:

Potassium silicate 28%；

Sodium nitrite 8.0%；

Ammonium fluozirconate 2.0%；

Methenamine 0.7%；

Cetyl octyldimethyl ammonium bromide 0.8%；

Catechol 0.2%；

Wetter80300.2%

Decylene glycol ester 0.004%；

Deionized water surplus；

With lemon acid for adjusting pH value for 8.0, test result is shown in Table 1, table 2.

Embodiment 4, a kind of novel non-chrome sealer are composed of the following components by weight percentage:

Potassium silicate 31%；

Sodium nitrite 9.0%；

Ammonium fluozirconate 2.5%；

Methenamine 0.2%；

Cetyl octyldimethyl ammonium bromide 1.0%；

Hydroquinone 0.5%；

Wetter80300.3%；

Decylene glycol ester 0.003%；

Deionized water surplus；

PH value is adjusted as 8.0 with sodium bicarbonate, and test result is shown in Table 1, table 2.

Embodiment 5, a kind of novel non-chrome sealer are composed of the following components by weight percentage:

Potassium metasilicate 35%；

Sodium nitrite 10%；

Potassium fluotitanate 2.5%；

Benzotriazole 1.0%；

Dodecyl benzyl dimethyl ammonium chloride 1.5%；

Resorcinol 0.2%；

Wetter80300.4%

Decylene glycol ester 0.002%；

Deionized water surplus；

PH value is adjusted as 8.5 with sodium bicarbonate, and test result is shown in Table 1, table 2.

Embodiment 6, a kind of novel non-chrome sealer are composed of the following components by weight percentage:

Potassium metasilicate 35%；

Sodium nitrite 15%；

Potassium fluotitanate 3%；

Thiocarbamide 0.7%；

Detergent alkylate amine hydrochlorate 2.0%；

Hydroquinone 0.2%；

Wetter80300.5%:

Decylene glycol ester 0.001%；

Deionized water surplus；

PH value is adjusted as 9.0 with sodium bicarbonate, and test result is shown in Table 1, table 2.

Table 1: phosphating solution carries out Seal treatment (Hangzhou Steel Company material Q235 steel plate, specification 0.6-4.0* after handling cold-rolled steel sheet 250*C):

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
							Natural antirust (winter, day)	3	15	16	18	21	29
Adhesive force	72	90	100	100	100	96

Table 2: Seal treatment (Hangzhou Steel Company material Q235 steel plate, specification 0.6-4.0*250*C) is carried out after zirconium liquid cooling rolled steel plate:

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
							Natural antirust (winter, day)	4	16	16	18	21	30
Adhesive force	78	91	100	100	100	96

In general factory's Coating Pretreatment workshop passivating solution is used as rust prevention during manufacture, and general workpiece passes through phosphatization Or zirconium treatment rear portion division of labor part needs temporarily to place one week or two weeks, it is therefore desirable to naked film due to entire workpiece together coating Antirust time can reach 14 days, at this moment need to use passivating solution.It is closed after 2 to 6 cold-rolled steel sheet phosphatization of embodiment or zirconium Processing is attained by this requirement.This is similar with other Chrome-free closing product effects in the market in terms of phosphatization, but in the market This requirement is not achieved for the effect after zirconium treatment in other closing products, and the present invention is extraordinary solves this hardly possible Topic.

Above-described embodiment is only presently preferred embodiments of the present invention, is not limited the scope of the invention according to this, therefore: it is all according to The equivalence changes that structure of the invention, shape, principle are done, should all be covered by within protection scope of the present invention.

Claims (1)

1. a kind of novel non-chrome sealer, composed of the following components by weight percentage:

Fluosilicate 5%~10%；

Sodium nitrate 6%~15%；

Fluozirconate 15%~30%；

Fluotitanate 1%~3%；

Corrosion inhibiter 0.1%~1%；

Surfactant 0.5%~2%；

Antioxidant 0.1%~0.5%；

Wetting agent 0.1%~0.5%

Alkaline regulator 0.1%~0.5%；

Silane coupling agent 0.1%~0.8%；

Deionized water surplus；

The fluosilicate is prodan, 1~2 kind in potassium fluosilicate；The fluozirconate is potassium fluorozirconate, ammonium fluozirconate In 1~2 kind, the fluotitanate is titanium sodium fluoride, 1~2 kind in potassium fluotitanate；The corrosion inhibiter be benzotriazole, Alpha-hydroxy benzotriazole, methenamine, a kind in thiocarbamide；The surfactant is cetyl octyldimethyl bromination Ammonium, hexadecyldimethyl benzyl ammonium decyl ammonium bromide, detergent alkylate amine hydrochlorate, dodecyl benzyl dimethyl ammonium chloride, 12 1 kind in alkyl benzyl pyridinium chloride；The antioxidant is hydroquinone, resorcinol, a kind in catechol；Institute Stating wetting agent is organosilicon wetting agent；The coalescing agent is decylene glycol ester；Above-mentioned composition pH value is adjusted using pH adjusting agent It is 7.0~9.0, the pH adjusting agent is citric acid, oxalic acid, sodium carbonate, a kind in sodium bicarbonate.