CN102392240A - Zinc alloy blackening liquid - Google Patents

Abstract

The invention relates to a zinc alloy blackening liquid which comprises the following components in percentage by mass: 0.1 to 15 percent of acid, 0.01 to 5 percent of acid salt, 0.1 to 10 percent of hydrogen peroxide, 0.01 to 2 percent of hydrogen peroxide stabilizer, 0.1 to 10 percent of copper sulfate and the balance of water. The preparation method comprises the following steps: mixing water with the amount of 60-80% of the formula amount, acid salt, hydrogen peroxide stabilizer and copper sulfate in sequence, finally adding the balance of water in the formula amount, and stirring for more than 5 minutes to obtain the zinc alloy blackening liquid. The using method of the zinc alloy blackening liquid comprises the following process flows: zinc alloy → degreasing → washing → activation → washing → blackening → washing → sealing → washing → drying. By the invention, the zinc alloy can achieve the effect of blackish film layer of the galvanized part without galvanizing; the blackening liquid is non-toxic and pollution-free, and the wastewater is easy to treat; the use and operation are simple.

Description

A kind of zinc alloy blackening liquid

technical field

The invention relates to the field of metal surface treatment, in particular, the invention relates to a zinc alloy blackening liquid, a preparation method and a use method thereof.

Background technique

Zinc and zinc alloys are widely used in ships, furniture, lamps, automobiles and other fields. In order to beautify the appearance of zinc alloy devices and meet the requirements of light absorption on the surface of some special devices, the surface of zinc alloys needs to be treated to black.

In the current traditional industrial production, most of the formulas used for the blackening of the surface of zinc and zinc alloys contain toxic ingredients such as trivalent chromium, hexavalent chromium, selenium salts, rare metal salts or cyanides, which seriously threaten operators. health and cause serious pollution to the environment.

CN 101283117A provides a treatment solution for forming a black trivalent chromium chemical conversion film with a uniform and stable black, glossy appearance and corrosion resistance, regardless of the type of acidic, neutral or alkaline galvanizing bath and the presence or absence of nickel eutectic, and A method for forming a black trivalent chromium chemical conversion coating. The invention provides a treatment solution for forming a black hexavalent chromium-free chemical conversion coating on zinc or zinc alloys, which contains: trivalent chromium ions; a chelating agent capable of forming a water-soluble complex with trivalent chromium; At least one metal ion selected from cobalt ions, nickel ions, and iron ions; and formic acid or its salt as a hydrogen ion concentration buffer.

CN 102149848 A provides a chrome-free surface treatment method for imparting good blackness and antirust performance to the surface of a metal part having a zinc or zinc alloy surface, and an aqueous solution for chemical conversion treatment that can be used in the treatment method. The aqueous solution does not contain trivalent and hexavalent chromium ions. In 1 liter of the aqueous solution, it contains 5-20 g of phosphate ions, 0.1-3 g of divalent iron ions, 1-10 g of divalent manganese ions, and 1-3 g of Nitrate ion, pH 1-3. Metal parts are immersed in this aqueous solution to form a black coating film of Fe ₃ O ₄ , followed by a chemical conversion coating film of cerium oxide, and then a silicon coating film.

In order to meet the national sewage discharge standard, surface treatment enterprises must increase investment in the treatment of sewage discharge, which greatly increases the production cost; most of the formulas will produce hanging ash or sediment during the blackening process, which increases the treatment of cleaning and blackening liquid difficulty.

Contents of the invention

To address the deficiencies in the prior art, one of the objectives of the present invention is to provide a zinc alloy blackening solution.

The zinc alloy blackening solution is suitable for protective and decorative processing of zinc alloys. The formula does not contain toxic selenium salts and rare metal salts, which achieves the purpose of environmental protection. Processing costs.

Described zinc alloy blackening liquid, its composition comprises by mass percentage:

The hydrogen peroxide can make the obtained black film layer more firmly combined and not easy to fall off.

Preferably, the acid can be an organic acid or/and an inorganic acid, more preferably the acid is one or a combination of at least two of hydrochloric acid, sulfuric acid, oxalic acid, acetic acid, carbonic acid, citric acid, phosphoric acid, nitric acid, The typical but non-exhaustive examples of said combination are: the combination of hydrochloric acid and oxalic acid, the combination of sulfuric acid, oxalic acid and acetic acid, the combination of acetic acid, carbonic acid, citric acid and phosphoric acid, the combination of carbonic acid and nitric acid, etc., especially preferably hydrochloric acid or/and lemon acid.

As a preferred version, the composition of the zinc alloy blackening solution comprises by mass percentage:

Further preferably, the composition of the zinc alloy blackening solution comprises by mass percentage:

Particularly preferably, described zinc alloy blackening liquid, its composition comprises by mass percentage:

Preferably, the acid salt is bisulfate or/and bisulfite, more preferably bisulfate, particularly preferably sodium bisulfate.

Preferably, the hydrogen peroxide stabilizer is sodium silicate, ethylenediaminetetraacetic acid sodium salt (EDTA), sodium stannate, sodium pyrophosphate, 8-hydroxyquinoline, organic phosphite, Changzhou Hansi Chemical Co., Ltd. One or at least two combinations of the highly efficient hydrogen peroxide stabilizer Hansi OS produced, the typical but non-exhaustive examples of the combination are: the combination of sodium silicate, ethylenediaminetetraacetic acid sodium salt (EDTA), sodium stannate , sodium pyrophosphate, the combination of 8-hydroxyquinoline, organic phosphite, the combination of high-efficiency hydrogen peroxide stabilizer Hansi OS produced by Changzhou Hansi Chemical Co., Ltd., etc., further preferably sodium silicate or/and Changzhou Hansi Chemical The high-efficiency hydrogen peroxide stabilizer Hansi OS produced by Changzhou Hansi Chemical Co., Ltd. is particularly preferred.

The zinc alloy blackening liquid of the present invention can be used alone or in combination with other components.

Those skilled in the art can add other components, such as corrosion inhibitors, etc. to the zinc alloy blackening solution of the present invention according to their professional technical knowledge.

Another object of the present invention is to provide a method for preparing the zinc alloy blackening solution.

The preparation method of the zinc alloy blackening liquid is as follows: 50% to 90% of the formula amount of water, and the formula amount of acid, acid salt, hydrogen peroxide, hydrogen peroxide stabilizer, and copper sulfate are mixed in sequence, and finally the remaining amount of the formula is added. water, and stirred for more than 5 minutes to obtain the zinc alloy blackening liquid.

Preferably, the preparation method of the zinc alloy blackening solution is: mixing 50% to 90% of the water in the formula, and hydrochloric acid, acid salt, citric acid, hydrogen peroxide, hydrogen peroxide stabilizer, and copper sulfate in the formula in order, and finally Add the remaining amount of water in the formula and stir for more than 5 minutes to obtain the zinc alloy blackening liquid.

Preferably, the water is added twice, and the amount of water added for the first time is 60% to 80% of the formula amount, that is, if the finally prepared zinc alloy blackening solution contains 70g of water, then when preparing, the first Add 70g×60%～70g×80% at one time, i.e. 42～56g of water, more preferably, the amount of water added for the first time is 65%～75% of the formula amount, especially preferably the amount of water added for the first time is 100% of the formula amount 70%.

Preferably, the stirring time is more than 10 minutes, such as 11 minutes, 12 minutes, 15 minutes, 30 minutes, 2 hours, 12 hours, etc., especially preferably stirring for 10 minutes.

Preferably, a liquid mixer is used for the stirring.

Another object of the present invention is to provide a method for using the zinc alloy blackening solution.

The method for using the zinc alloy blackening liquid includes the following technological process: zinc alloy→oil removal→water washing→activation→water washing→blackening→water washing→sealing→water washing→drying.

Preferably, the activation uses a conventional activated acid salt, which can be obtained from the market or prepared by those skilled in the art according to their professional knowledge/new technology; the amount of the activated acid salt is 10-200 g/L, preferably 30 ~150g/L, especially preferably 50~100g/L.

The dilution of the activated acid salt is preferably diluted with water.

Preferably, the amount of the zinc alloy blackening solution is 10-100mL/L, that is, the blackening solution is diluted for use, the amount is the concentration after dilution, and the concentration of the zinc alloy blackening solution is to dilute the zinc alloy blackening solution For example, add 990mL water in 10mL zinc alloy blackening liquid, then the concentration of zinc alloy blackening liquid is 10mL/L, more preferably 20～70mL/L, particularly preferably 25-50ml/L.

Preferably, the solvent used for diluting the zinc alloy blackening solution is water or/and a water-miscible liquid, such as alcohols, particularly preferably water.

Preferably, the use temperature of the zinc alloy blackening solution is 15-60°C, more preferably 20-50°C, particularly preferably 20-40°C.

Preferably, the blackening treatment time is 0.1-8 minutes, more preferably 0.3-5 minutes, particularly preferably 0.5-3 minutes.

Preferably, the conventional blocking solution for blocking can be commercially available or prepared by those skilled in the art according to their professional knowledge/new technology; the blocking solution is used as the original solution, that is, no concentration or dilution is required; the The blocking time is preferably 0.1 to 5 minutes, more preferably 0.3 to 2 minutes, particularly preferably 0.5 to 1 minute.

Preferably, the drying temperature does not exceed 100°C, more preferably does not exceed 90°C, and particularly preferably does not exceed 80°C.

Preferably, the blackening solution is suitable for direct blackening of zinc alloys without electrogalvanizing.

The beneficial effects of the present invention are as follows:

(1) Zinc alloys can achieve the same black film effect as galvanized parts without galvanizing;

(2) described blackening liquid is nontoxic, non-polluting, and waste water is easy to handle;

(3) Easy to use and operate.

Detailed ways

In order to facilitate understanding of the present invention, the present invention enumerates the following examples. It should be clear to those skilled in the art that the embodiments are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.

Example 1

Add 47.9g of water, 0.05g of sulfuric acid, 0.01g of sodium bisulfate, 10g of oxalic acid, 0.1g of hydrogen peroxide, 0.01g of sodium silicate, and 10g of copper sulfate to a liquid mixer and mix them, then add 31.9g of water and stir for 5 minutes to obtain zinc Alloy blackening fluid.

Degrease the zinc alloy to be treated, wash it with water, activate it with a 10g/L aqueous solution of DC-A activated salt produced by Guangzhou Dazhi Chemical Technology Co., Ltd., wash it with water, and dilute the blackening solution with water to a 10mL/L solution. Blackened at 15°C for 8 minutes, then washed with water, sealed with sealing solution produced by Shenzhen Jiameide Surface Technology Co., Ltd. for 0.1 minute, washed with water, and dried at 80°C to obtain a black zinc alloy with beautiful appearance.

Example 2

Add 41.42g of water, 5g of hydrochloric acid, 0.01g of sodium bisulfite, 0.05g of citric acid, 10g of hydrogen peroxide, 2g of the high-efficiency hydrogen peroxide stabilizer Hansi OS produced by Changzhou Hansi Chemical Co., Ltd., and 0.1g of copper sulfate to the liquid mixer and mix , Then add 41.42g of water and stir for 10 minutes to obtain a zinc alloy blackening solution.

The zinc alloy to be treated is degreased, washed with water, activated with an aqueous solution of 200g/L of KQ-13 type activated salt produced by Guangzhou Kechuang Surface Technology Co., Ltd., washed with water, and diluted with water to a 100mL/L solution. Blackened at 60°C for 0.1 minute, then washed with water, sealed with CX800 sealing solution produced by Shenzhen Changxian Technology Industrial Co., Ltd. for 5 minutes, washed with water, and dried at 100°C to obtain a black zinc alloy with beautiful appearance.

Example 3

Add 76.2g of water, 1g of hydrochloric acid, 0.05g of potassium bisulfite, 5g of citric acid, 8g of hydrogen peroxide, 0.8g of the high-efficiency hydrogen peroxide stabilizer Hansi OS produced by Changzhou Hansi Chemicals Co., Ltd., and 0.5g of copper sulfate into the liquid mixer and mix , Then add 8.45g of water and stir for 11 minutes to obtain a zinc alloy blackening solution.

Degrease the zinc alloy to be treated, wash it with water, activate it with an aqueous solution of 50 g/L of KQ-13 activated salt produced by Guangzhou Kechuang Surface Technology Co., Ltd., wash it with water, and dilute the blackening solution with ethanol to a solution of 50 mL/L. Blackened at 30°C for 5 minutes, then washed with water, sealed with CX800 sealing solution produced by Shenzhen Changxian Technology Industrial Co., Ltd. for 1 minute, washed with water, and dried at 90°C to obtain a black zinc alloy with beautiful appearance.

The applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow process can be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. zinc alloy hair blackening liquid, its composition comprises by mass percentage:

2. zinc alloy hair blackening liquid as claimed in claim 1; It is characterized in that; Said acid can be for organic acid or/and mineral acid; Further preferred said acid is a kind or at least 2 kinds combination in hydrochloric acid, sulfuric acid, oxalic acid, acetic acid, carbonic acid, Hydrocerol A, phosphoric acid, the nitric acid, is preferably hydrochloric acid especially or/and Hydrocerol A;

3. according to claim 1 or claim 2 zinc alloy hair blackening liquid is characterized in that, said zinc alloy hair blackening liquid, and its composition comprises by mass percentage:

4. like each described zinc alloy hair blackening liquid of claim 1-3, it is characterized in that, said zinc alloy hair blackening liquid, its composition comprises by mass percentage:

5. like each described zinc alloy hair blackening liquid of claim 1-4, it is characterized in that, said zinc alloy hair blackening liquid, its composition comprises by mass percentage:

6. like each described zinc alloy hair blackening liquid of claim 1-5; It is characterized in that; Said hydrogen peroxide stabilizer is a kind or at least 2 kinds combination among the efficient hydrogen peroxide stabilizer Hansi OS that produces of water glass, ethylene dinitrilotetra-acetic acid sodium salt (EDTA), sodium stannate, trisodium phosphate, oxine, organophosphite, Hansi Chemical Article Co., Ltd., Changzhou; Further be preferably water glass or/and the efficient hydrogen peroxide stabilizer Hansi OS that Hansi Chemical Article Co., Ltd., Changzhou produces is preferably the efficient hydrogen peroxide stabilizer Hansi OS that Hansi Chemical Article Co., Ltd., Changzhou produces especially;

Preferably, said hydrochlorate be hydrosulfate or/and hydrosulphite further is preferably hydrosulfate, be preferably sodium pyrosulfate especially.

7. preparation method like each described zinc alloy hair blackening liquid of claim 1-6; It is characterized in that; Said method is: with the water of formula ratio 50%～90%, the acid, hydrochlorate, ydrogen peroxide 50, hydrogen peroxide stabilizer, the copper sulfate that reach formula ratio mix successively, add the water of formula ratio surplus at last; Stir more than 5 minutes, promptly get the zinc alloy hair blackening liquid.。

8. method as claimed in claim 7; It is characterized in that; The preparation method of said zinc alloy hair blackening liquid is preferably: with the water of formula ratio 50%～90%, the hydrochloric acid, hydrochlorate, Hydrocerol A, ydrogen peroxide 50, hydrogen peroxide stabilizer, the copper sulfate that reach formula ratio mix successively, add the water of formula ratio surplus at last; Stir more than 5 minutes, promptly get the zinc alloy hair blackening liquid;

Preferably, twice adding of said moisture, the water yield that adds for the first time is 60%～80% of a formula ratio, and further preferred, the water yield that adds for the first time is 65%～75% of a formula ratio, and the preferred especially water yield that adds for the first time is 70% of a formula ratio;

Preferably, said churning time is more than 10 minutes, is preferably especially to stir 10 minutes;

Preferably, liquid stirrers is adopted in said stirring.

9. method of use like each described zinc alloy hair blackening liquid of claim 1-6; It is characterized in that the method for use of said zinc alloy hair blackening liquid comprises following technical process: zinc alloy → oil removing → washing → activation → washing → blackout → washing → sealing → washing → oven dry.

10. method as claimed in claim 9 is characterized in that, conventional activation hydrochlorate is adopted in said activation, and said activation hydrochlorate consumption is 10～200g/L, is preferably 30～150g/L, is preferably 50～100g/L especially;

Preferably, the water dilution is adopted in said activation hydrochlorate dilution.

Preferably, said hair blackening liquid consumption is 10～100mL/L, is about to the hair blackening liquid dilution and uses, and said consumption further is preferably 20～70mL/L for dilution back concentration, is preferably 25-50ml/L especially;

Preferably, it is water or/and the liquid that dissolves each other with water that solvent is adopted in the dilution of said hair blackening liquid, and for example alcohols is preferably water especially;

Preferably, said hair blackening liquid use temperature is 15～60 ℃, further is preferably 20～50 ℃, is preferably 20～40 ℃ especially;

Preferably, the said blackout treatment time is 0.1～8 minute, further is preferably 0.3～5 minute, is preferably 0.5～3 minute especially;

Preferably, conventional confining liquid is used in said sealing, and said confining liquid is that stoste is used, and be preferably 0.1～5 minute said off-period, further is preferably 0.3～2 minute, is preferably 0.5～1 minute especially;

Preferably, said bake out temperature is no more than 100 ℃, further preferably is no more than 90 ℃, especially preferably is no more than 80 ℃;

Preferably, it is black that said hair blackening liquid is applicable to that zinc alloy directly dyes, and need not electro-galvanizing processing.