KR101655426B1 - TRIVALENT CHROMATE COMPOSITION FOR RUST-PROOFING OF Zn-Ni BASED ALLOY AND METHOD FOR PREPARING THE SAME - Google Patents

TRIVALENT CHROMATE COMPOSITION FOR RUST-PROOFING OF Zn-Ni BASED ALLOY AND METHOD FOR PREPARING THE SAME Download PDF

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KR101655426B1
KR101655426B1 KR1020150074822A KR20150074822A KR101655426B1 KR 101655426 B1 KR101655426 B1 KR 101655426B1 KR 1020150074822 A KR1020150074822 A KR 1020150074822A KR 20150074822 A KR20150074822 A KR 20150074822A KR 101655426 B1 KR101655426 B1 KR 101655426B1
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trivalent
acid
trivalent chromate
aqueous solution
chromate composition
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KR1020150074822A
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Korean (ko)
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백승관
이용준
김기웅
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(주)코벤티아코리아
한국화학융합시험연구원
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/185—Refractory metal-containing compounds
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/187—Mixtures of inorganic inhibitors

Abstract

The present invention is a trivalent chromate composition containing no cobalt salt, wherein the trivalent chromate composition is a trivalent chromate salt; Oxidant; Organic acid accelerators; And the balance water; When used for rust-inhibiting treatment of a zinc-nickel alloy, it is possible to form a colored and black chromate film having excellent physical properties such as color clarity and corrosion resistance on the surface of a zinc-nickel alloy, And environmental hazards.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a trivalent chromate composition for rust-inhibiting treatment of zinc-nickel-based alloys, and a trivalent chromate composition for rust-

More particularly, the present invention relates to a colored or black trivalent chromate composition capable of forming an anticorrosive coating on a zinc-nickel-based alloy, and a method of manufacturing the same. More particularly, the present invention relates to a trivalent chromate composition for rust- And a method for producing the same.

Plated steel including conventional zinc-containing plated steel is widely used as a member of home appliances, building materials, automobiles and the like due to the high-functioning function of the plated metal material. However, in the case of the plated steel, there is a phenomenon in which the electrolyte is oxidized by oxygen and moisture present in an atmosphere such as salt contained in the atmosphere, and under high temperature and high humidity environment, and becomes white rust and corroded. Also, under certain circumstances, high temperature and high humidity may cause a blackening phenomenon in which the plated steel is discolored to black.

As a means for preventing the corrosion of the plated steel material and the blackening and peeling of the coating film, surface treatment has been conventionally carried out by various methods of contacting the surface of the plated steel with a treatment liquid containing chromium such as chromic acid chromate or phosphoric acid chromate . Thus, the problem has been solved by forming a so-called reactive chromate film on the surface of the plated steel.

Generally, the plating layer of zinc plating and Au alloy gold plating on iron substrate has corrosion resistance due to the action of sacrificial iron for the base metal, but the corrosion resistance is not sufficient. Therefore, when a chromate film is formed by using an aqueous solution containing hexavalent chromium ions in the upper part of the plating layer, the corrosion resistance can be greatly improved.

However, hexavalent chromium can cause diseases such as respiratory or central nervous system of workers, and may cause a fatal disease called 'non-septic perforation' that melts the mollusk bones in workplaces where there is no proper exhaust system.

In addition, since it causes serious pollution to the ecosystem environmentally, its use is restricted through some regulations (RoHS, REACH) for about 20 years. As a result, a chromate film was formed using trivalent chromium instead of hexavalent chromium. Most of the existing trivalent chromate solutions contain "cobalt (Co)" inorganic salts. However, since cobalt is also designated as a carcinogen in the International Agency for Research on Cancer (IARC), the use of cobalt has become the leading EU regulation.

As a result, a trivalent chromate solution containing no cobalt was developed, but it showed a clear color when colored, but the coating speed was slow and a slight black phenomenon due to the complexing agent contained in the chromate. Further, in the case of black chromate, the blackness is lower than that of the conventional hexavalent chromate.

Therefore, it is required to develop a colored or black trivalent chromate composition capable of forming a chromate film having excellent physical properties such as corrosion resistance and color clarity without using cobalt having high harmfulness.

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-described problems, and it is an object of the present invention to provide a trivalent chromate composition which is excellent in physical properties such as color clarity and corrosion resistance, Which is capable of forming a chromate film of the trivalent chromate composition of the present invention and has low harmfulness to humans and the environment, and a process for producing the same.

According to one aspect of the present invention, there is provided a trivalent chromate composition containing no cobalt salt, wherein the trivalent chromate composition comprises a trivalent chromium salt; Oxidant; Organic acid accelerators; And the balance water; A trivalent chromate composition is provided.

Preferably, the trivalent chromate composition comprises 100 parts by weight of a trivalent chromium salt; 50 to 140 parts by weight of an oxidizing agent; 5 to 40 parts by weight of an organic acid accelerator; And the balance water; . ≪ / RTI >

The trivalent chromate composition may further comprise a complexing agent.

Preferably, the complexing agent may be 50 to 100 parts by weight based on 100 parts by weight of the trivalent chromium compound.

Wherein the complexing agent is selected from the group consisting of glycollic acid, palmitic acid, oxalic acid, tartaric acid, ascorbic acid, citric acid and salts thereof, It may be at least one selected.

The trivalent chromate composition may further comprise a sulfur compound.

The trivalent chromate composition may further comprise an antioxidant.

The antioxidant may be at least one selected from the group consisting of potassium sorbate and calcium sorbate.

The trivalent chromium salt may be at least one selected from chromium chloride (CrCl 3 ), chromium nitrate (Cr (NO 3 ) 3 ) and chromium sulfate (Cr 2 (SO 4 ) 3 ).

The oxidizing agent may be at least one selected from sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ), phosphoric acid (H 3 PO 4 ), hydrochloric acid (HCl) and phosphorous acid (H 3 PO 3 ).

The organic acid promoter may be at least one selected from the group consisting of acetic acid and malonic acid.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing a solution in which water and an oxidizing agent are mixed (step a); Adding a trivalent chromium salt to said solution (step b); And adding an organic acid promoter to the resultant of step b to prepare a colored trivalent chromate composition (step c); ≪ RTI ID = 0.0 > a < / RTI > colored trivalent chromate composition.

After step a, adding a basic aqueous solution (step a '); . ≪ / RTI >

After step c), adding sodium fluoride (step c '); . ≪ / RTI >

According to another aspect of the present invention, there is provided a process for preparing an aqueous solution comprising a trivalent chromium salt (step a); Preparing an aqueous solution containing an oxidizing agent, a complexing agent and an organic acid promoting agent (step b); And mixing the aqueous solution of step a with the aqueous solution of step b to prepare a black trivalent chromate composition (step c); ≪ RTI ID = 0.0 > a < / RTI > black trivalent chromate composition.

Step a is a step of producing an aqueous solution of a trivalent chromium salt (step a-1); Adding a basic aqueous solution to the aqueous solution of the trivalent chromium salt (step a-2); And adding an oxidizing agent to the result of step a-2 (step a-3); . ≪ / RTI >

Step b) comprises mixing water, an oxidizing agent and a complexing agent (step b-1); Adding a sulfur compound and an antioxidant to the result of step b-1 (step b-2); And (b-3) adding an organic acid promoter to the result of step b-2; . ≪ / RTI >

According to another aspect of the present invention, there is provided an anti-corrosive treatment method for forming a corrosion resistant trivalent chromate coating film on a zinc nickel alloy using the trivalent chromate composition.

When a trivalent chromate composition is prepared and used in the rust inhibitive treatment of a zinc nickel alloy, it is possible to form colored and black chromate films excellent in physical properties such as color clarity and corrosion resistance on the surface of a zinc nickel alloy, And to reduce the harmfulness to the environment

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart sequentially showing a production method of a colored trivalent chromate composition of the present invention. FIG.
Fig. 2 is a flowchart sequentially showing a method for producing the black trivalent chromate composition of the present invention.
Fig. 3 shows the appearance of colored hues shown in the specimens of colored film forming examples 1 to 7.
Fig. 4 shows the appearance of the black color shown in the specimens of Examples 8 to 11 of the black coating formation.
Fig. 5 shows the results of comparative analysis of the surface of the specimen of the film forming example 5 and the comparative example 1 after the salt spray test.
Fig. 6 shows the results of comparative analysis of the surfaces of the film forming Example 11 and the Comparative Example 1 after the salt spray test.

The invention is capable of various modifications and may have various embodiments, and particular embodiments are exemplified and will be described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Furthermore, terms including an ordinal number such as first, second, etc. to be used below can be used to describe various elements, but the constituent elements are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.

Also, when an element is referred to as being "formed" or "laminated" on another element, it may be formed or laminated directly on the front surface or one surface of the other element, It will be appreciated that other components may be present in the < / RTI >

The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, the trivalent chromate composition of the present invention will be described.

The present invention is a trivalent chromate composition that does not comprise a cobalt salt, wherein the trivalent chromate composition is a trivalent chromium salt; Oxidant; Organic acid accelerators; And the balance water; .

Wherein the trivalent chromate composition comprises 100 parts by weight of a trivalent chromium salt; 50 to 140 parts by weight of an oxidizing agent; 5 to 40 parts by weight of an organic acid accelerator; And the balance water; . ≪ / RTI >

The trivalent chromate composition may further include a complexing agent.

The complexing agent may be contained in an amount of 50 to 100 parts by weight based on 100 parts by weight of the trivalent chromium compound.

The complexing agent may be an organic acid.

The organic acid darkens the color of the surface of the chromate film, and the more the amount of the organic acid contained in the trivalent chromate composition, the darker the color of the chromate film surface.

The complexing agent may be glycollic acid, palmitic acid, oxalic acid, tartaric acid, ascorbic acid, citric acid, or the like. Preferably, glycolic acid can be used.

The trivalent chromate composition may further comprise a dye.

The dye plays a role of dyeing the surface of the coating so that the surface of the chromate coating becomes black.

The dye may be a sulfur compound, and preferably ammonium thioglycolate may be used.

The trivalent chromate composition may further comprise an antioxidant. The antioxidant may be used to prevent deterioration of the trivalent chromate composition.

The antioxidant may be at least one selected from the group consisting of potassium sorbate and calcium sorbate. Potassium sorbate is preferably used.

The trivalent chromium salt may be chromium chloride (CrCl 3 ), chromium nitrate (Cr (NO 3 ) 3 ), chromium sulfate (Cr 2 (SO 4 ) 3 ) Preferably, chromium chloride and chromium nitrate can be used.

The oxidizing agent may be sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ), phosphoric acid (H 3 PO 4 ), hydrochloric acid (HCl), phosphorous acid (H 3 PO 3 )

The above oxidizing agent may further comprise sodium nitrate (NaNO 3).

When the strong acid such as nitric acid and sulfuric acid is used in the preparation of the trivalent chromate composition, the acidity becomes extremely high, so that sodium nitrate can be used as a buffer for lowering the acidity.

The organic acid promoter may be a monocarboxylic acid, a dicarboxylic acid, or a tricarboxylic acid.

Preferably, it may be acetic acid, malonic acid or the like, more preferably acetic acid.

1 is a flowchart sequentially showing a method of producing a colored trivalent chromate composition in a process for producing a trivalent chromate composition of the present invention.

Hereinafter, a method for producing the colored trivalent chromate composition of the present invention will be described with reference to FIG.

First, a solution prepared by mixing water and an oxidizing agent is prepared (step a).

The temperature of the water may be 40 to 60 占 폚, preferably 45 to 55 占 폚, more preferably 50 占 폚.

The oxidizing agent may be sodium nitrate and nitric acid.

After step a, it may further comprise the step of adding a basic aqueous solution to the result of step a (step a ').

The basic aqueous solution is for controlling the acidity. Since the pH value of the conditions under which the chromate film can be formed is 1 to 2, the pH value is adjusted by adding a basic sodium hydroxide solution.

Next, trivalent chromium salt is added to the result of step a (step b).

The pH of the product of step b may be 1-2. a chromate film can be effectively formed at a pH of 1 to 2.

Finally, an organic acid promoter was added to the resultant product of step b, Chromate  A composition is prepared (step c).

After step c), adding sodium fluoride (step c '); . ≪ / RTI >

The sodium fluoride cleans the surface of the trivalent chromate coating and can control the rate at which the trivalent chromate coating is formed.

Fig. 2 is a flowchart sequentially showing the production method of the black trivalent chromate composition in the process for producing the trivalent chromate composition of the present invention.

Hereinafter, a method for producing the black trivalent chromate composition of the present invention will be described with reference to FIG.

First, an aqueous solution containing a trivalent chromium salt is prepared (step a).

Step a can be carried out sequentially in the following three stages.

First, an aqueous solution of trivalent chromium salt is prepared (step a-1).

The aqueous solution is prepared by adding a trivalent chromium compound to water at 40 to 60 ° C, and the temperature of the water is preferably 45 to 55 ° C, more preferably 50 ° C.

Next, an aqueous solution of the basic compound is added to the aqueous solution of the trivalent chromium salt (step a-2).

The pH value can be adjusted to 1 to 2 using the basic aqueous solution.

Preferably, a sodium hydroxide solution can be used as the basic aqueous solution.

Finally, an oxidizing agent is added to the result of step a-2 (step a-3).

The oxidizing agent may be sodium nitrate.

After step a, Complexing agent  And an organic acid promoting agent (step b).

Step b can be performed in sequence as follows, divided into three steps.

First, water, an oxidizing agent and a complexing agent are mixed (step b-1).

The water is preferably at a temperature of 40 to 80 캜, more preferably at a temperature of about 60 캜.

The oxidizing agent may be sodium nitrate and phosphorous acid, and the complexing agent may be glycolic acid.

Next, a dye and an antioxidant are added to the result of step b-1 (step b-2).

The dye may be ammonium thioglycolate, and the antioxidant may be potassium sorbate.

Finally, an organic acid promoter is added to the result of Step b-2 (Step b-3).

Acetic acid can be used as the organic acid promoter, and the rate can be controlled and the surface can be evened when the trivalent chromate film is formed.

Finally, by mixing the aqueous solution of step a and the aqueous solution of step b, Chromate  A composition is prepared (step c).

In step c, 80 to 100 parts by weight of the aqueous solution of step b may be contained per 100 parts by weight of the aqueous solution of step a.

There is provided a method for forming a trivalent chromate coating film for preventing corrosion of a zinc-nickel alloy using the trivalent chromate composition.

The trivalent chromate film formed on the surface of the zinc nickel alloy can prevent corrosion of the metal and exhibits high color sharpness. In addition, since the trivalent chromate composition does not contain cobalt, the harmfulness to the human body and the environment is low. The trivalent chromate composition can be used for a metal plated with a zinc-nickel alloy such as an automobile internal combustion engine.

Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.

[Example]

Example 1: Preparation of colored trivalent chromate compositions

80 g of sodium nitrate was added to 502 g of water at 50 DEG C and dissolved by stirring for 30 minutes. Then, 80 g of nitric acid was added and stirred for 10 minutes to prepare a solution. A sodium hydroxide solution obtained by dissolving 24 g of sodium hydroxide in 94 g of water was slowly added to the solution to prepare a mixed solution. 200 g of chromium chloride was added to the mixed solution, and the mixture was stirred for 30 minutes, then 20 g of sodium fluoride was added and stirred for 1 hour. Thereafter, the mixture was cooled to a temperature of 30 DEG C or less, 30 g of acetic acid was added, and the mixture was stirred for 1 hour to obtain a colored trivalent chromate composition.

Example 2: Preparation of Black Trivalent Chromate Composition

(1) Preparation of first solution

250 g of chromium nitrate was added to 625 g of water at 50 캜, and the mixture was stirred for 30 minutes to prepare a solution. 25 g of a 20% sodium hydroxide solution was added to the prepared solution, followed by stirring. Thereafter, 100 g of sodium nitrate was added and stirred for 1 hour to prepare a solution containing a chromium compound.

(2) Preparation of the second solution

80 g of sodium nitrate was added to 627 g of water at 60 캜 and stirred for 30 minutes. Then, 160 g of glycolic acid and 30 g of phosphoric acid were added and stirred for 1 hour to prepare a solution. 20 g of nitric acid and 40 g of sulfuric acid were slowly added to the prepared solution and stirred for 30 minutes to prepare a mixed solution. Then, 2 g of ammonium thioglycolate and 1 g of potassium sorbate were added, followed by stirring for 1 hour. Thereafter, the temperature of the solution was cooled to 30 DEG C or lower, 40 g of acetic acid was added, and the mixture was stirred for 1 hour to obtain a mixture.

Finally, 80 ml of the first solution (1) and 70 ml of the second solution (2) were mixed, and 850 ml of water was added thereto to prepare a trivalent chromate composition so as to be 1 liter.

A zinc-nickel alloy plated iron specimen was prepared and the specimen was immersed in the colored chromate composition prepared according to Example 1 while changing the immersion time to form a colored trivalent chromate film on the zinc nickel alloy plated iron specimen. Formation of colored film The immersion time in Examples 1 to 7 was summarized in Table 1 below.

division Coating Formation Example 1 Coating Formation Example 2 Coating Formation Example 3 Coating Formation Example 4 Coating Formation Example 5 Coating Formation Example 6 Coating Formation Example 7 Immersion time 20 seconds 30 seconds 40 seconds 50 seconds 60 seconds 70 seconds 80 seconds

Black film formation Examples 8 to 11

A zinc-nickel alloy plated iron specimen was prepared and the specimen was immersed in the black chromate composition prepared according to Example 2 while changing the immersion time to form a black trivalent chromate film on the zinc nickel alloy plated iron specimen. Black film formation The immersion times in Examples 8 to 11 were summarized in Table 2 below.

division Coating Formation Example 8 Coating Formation Example 9 Coating Formation Example 10 Coating Formation Example 11 Immersion time 20 seconds 30 seconds 40 seconds 50 seconds

Comparative Example 1

Zinc nickel alloy was used as the iron-plated specimen without rust-proofing treatment.

[Test Example]

Test Example  One: Zinc nickel  Alloy specimens were colored 3-valent Chromate  In the composition Immersed  Color analysis over time

Film Formation The color change patterns of the specimens having colored trivalent chromate films formed according to Examples 1 to 7 were observed and shown in Fig.

The color change patterns of FIG. 3 are summarized in Table 3 below.

division Coating Formation Example 1 Coating Formation Example 2 Coating Formation Example 3 Coating Formation Example 4 Coating Formation Example 5 Coating Formation Example 6 Coating Formation Example 7 Immersion time 20 seconds 30 seconds 40 seconds 50 seconds 60 seconds 70 seconds 80 seconds color Brown, blue Yellow, red Yellow, red Red, blue Blue, green Green, red Green, red

As a result, it was confirmed that various colors appeared depending on the time of treatment of the colored trivalent chromate composition prepared according to Example 1. Therefore, when the chromate film is formed on the surface of the zinc nickel alloy by using the chromate composition of Example 1, by adjusting the immersion time in the trivalent chromate composition, a zinc nickel alloy containing a chromate film having a desired color Can be obtained. In particular, the red, red and green colors required by the automobile industry were exhibited in the immersion time range of 40 to 70 seconds.

Test Example  2: Zinc nickel  The alloy is black 3-valent Chromate  In the composition Immersed  Color analysis over time

Film Formation The color change patterns of the black trivalent chromate film-coated specimens were observed in accordance with Examples 8 to 11, and the results are shown in FIG.

The color change patterns of FIG. 4 are summarized in Table 4 below.

division Coating Formation Example 8 Coating Formation Example 9 Coating Formation Example 10 Coating Formation Example 11 Immersion time 20 seconds 30 seconds 40 seconds 50 seconds color Brown Brown Brown Good (black)

As a result, it was confirmed that the black trivalent chromate composition prepared according to Example 2 became black as the treatment time became longer. Therefore, in order to form a black trivalent chromate film on the surface of the zinc nickel alloy, the black trivalent chromate composition prepared according to Example 2 was found to be preferably treated for a sufficient time of about 50 seconds or more.

Test Example 3: Corrosion resistance analysis of colored trivalent chromate film

Coating Formation The corrosion resistance of the specimens of Example 5 and Comparative Example 1 were compared.

For reference, the surface of the test piece before and after the salt spray test of Example 5 was observed and is shown in Fig.

The salt spray test was carried out in a KS D 9502 test under the conditions of 50 g ± 5 g / L of sodium chloride (density (25 ° C.) 1.029 to 1.036), pH 6.5 to 7.2 and an average spray rate of 1.5 ± 0.5 ml per 80 cm 2 It was done by law.

According to Fig. 5, the specimen of film-forming Example 5 showed that the corrosion did not proceed substantially after the spray test. On the contrary, the specimen of Comparative Example 1 was not shown, but most of the surface was highly corroded. Therefore, it can be understood that the corrosion resistance of the zinc alloy plated steel structure can be improved by treating the trivalent chromate composition of the present invention.

Test Example 4: Corrosion resistance analysis of black trivalent chromate film

Coating formation The corrosion resistance of the specimens of Example 11 and Comparative Example 1 were compared.

Specifically, the surface of the test piece before and after the salt spray test was observed and is shown in FIG.

The salt spray test was carried out in a KS D 9502 test under the conditions of 50 g ± 5 g / L of sodium chloride (density (25 ° C.) 1.029 to 1.036), pH 6.5 to 7.2 and an average spray rate of 1.5 ± 0.5 ml per 80 cm 2 It was done by law.

According to Fig. 6, the specimen of film-forming Example 11 showed that almost no corrosion proceeded after the spray test. On the contrary, the specimen of Comparative Example 1 was not shown, but most of the surface was highly corroded. Therefore, it can be understood that the corrosion resistance of the zinc-nickel alloy-plated steel structure can be improved by treating the trivalent chromate composition of the present invention.

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

Claims (12)

A trivalent chromate composition containing no cobalt salt,
The trivalent chromate composition is preferably a trivalent chromate composition,
Trivalent chromium salts;
Oxidant;
Organic acid accelerators;
Complexing agents;
Sulfur compounds; And
Water of the remaining amount,
Wherein the sulfur compound is ammonium thioglycolate. delete The method according to claim 1,
Wherein the complexing agent is selected from the group consisting of glycollic acid, palmitic acid, oxalic acid, tartaric acid, ascorbic acid, citric acid and salts thereof, Wherein the trivalent chromate composition is at least one selected from the group consisting of trivalent chromate compounds. delete The method according to claim 1,
Wherein the trivalent chromium salt is at least one selected from the group consisting of chromium chloride (CrCl 3 ), chromium nitrate (Cr (NO 3 ) 3 ) and chromium sulfate (Cr 2 (SO 4 ) 3 ). The method according to claim 1,
Wherein the organic acid promoting agent is at least one selected from the group consisting of acetic acid and malonic acid. delete delete delete Preparing an aqueous solution comprising a trivalent chromium salt (step a);
Preparing an aqueous solution comprising an oxidizing agent, a complexing agent, a sulfur compound and an organic acid promoting agent (step b); And
Mixing the aqueous solution of step a with the aqueous solution of step b to prepare a black trivalent chromate composition (step c); Lt; / RTI >
Wherein the sulfur compound is ammonium thioglycolate. 11. The method of claim 10,
Step a is
Preparing an aqueous solution of a trivalent chromium salt (step a-1);
Adding a basic aqueous solution to the aqueous solution of the trivalent chromium salt (step a-2); And
Adding an oxidizing agent to the result of step a-2 (step a-3); To
By weight based on the total weight of the black trivalent chromate composition. 12. The method of claim 11,
Step b is
Mixing water, an oxidizing agent and a complexing agent (step b-1);
Adding a sulfur compound and an antioxidant to the result of step b-1 (step b-2); And
Adding an organic acid promoter to the result of step b-2 (step b-3); To
By weight based on the total weight of the black trivalent chromate composition.
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KR102627860B1 (en) 2023-08-24 2024-01-23 (주)엠피피티 Chromate and coating treatment method for electro-galvanized metal with excellent corrosion resistance

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