Replenisher, surface-treated metallic material, and production method thereof

Abstract

The purpose of the present invention is to provide a replenisher that avoids an increase in the HF concentration in a surface-treatment liquid for metal materials, is capable of supplying zirconium ions at high concentration by using the metal material surface-treatment liquid, and has excellent long-term storage stability, in order to continuously chemically convert and/or electrolytically treat a metal material. This replenisher contains prescribed amounts of: a zirconium compound not containing fluorine and including at least one type selected from a group comprising zirconium basic carbonate, zirconium carbonate, zirconium hydroxide, and ammonium zirconium carbonate; a fluorine-containing matter including at least one type selected from a group comprising hydrofluoric acid, a hydrofluoric acid salt, fluorozirconic acid, and a fluorozirconic acid salt; and an acid component including at least one type selected from a group comprising nitric acid, hydrochloric acid, sulfuric acid, and acetic acid.

1 . A replenisher used to replenish metallic material surface treating solution with zirconium ion, the metallic material surface treating solution containing zirconium ion and fluorine ion and being used to form a chemical conversion coating containing zirconium on/over a metallic material through chemical conversion treatment and/or electrolysis treatment, the replenisher comprising:
 a fluorine-free zirconium compound (A) containing at least one selected from a group consisting of zirconium basic carbonate, zirconium carbonate, zirconium hydroxide and ammonium zirconium carbonate; a fluorine-containing compound (B) containing at least one selected from the group consisting of hydrofluoric acid, a salt of hydrofluoric acid, hexafluorozirconic acid and a salt of hexafluorozirconic acid; and an acid component (C) containing at least one selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid and acetic acid,   wherein following relationships (I) to (III) are satisfied:   (I) a ratio (M AC /M F ) of a total molar quantity (M AC ) of anions derived from the acid component (C) with respect to a total molar quantity (M F ) of fluorine ion derived from the fluorine-containing compound (B) is 0.35 or more and less than 2.00;   (II) a total concentration (g/L) of zirconium ion derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) is 25 or higher; and   (III) a ratio (M F /F Zr ) of a total molar quantity (M F ) of fluorine ion derived from the fluorine-containing compound (B) with respect to a total molar quantity (M Zr ) of zirconium ion derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) is 2.00 or more and less than 6.00.   
     
     
         2 . The replenisher according to  claim 1 , wherein the ratio (M AC /M F ) exceeds 0.50 and is less than 2.00. 
     
     
         3 . The replenisher according to  claim 1 , wherein the ratio (M AC /M F ) exceeds 0.50 and is 1.60 or less. 
     
     
         4 . A method for producing a surface-treated metallic material comprising:
 continuously performing chemical conversion treatment and/or electrolysis treatment on/over a metallic material in metallic material surface treating solution containing zirconium ion and fluorine ion to form a chemical conversion coating containing zirconium on/over the metallic material; and   replenishing the metallic material surface treating solution with zirconium ion by adding the replenisher according to  claim 1  to the metallic material surface treating solution.   
     
     
         5 . A surface-treated metallic material obtained by the method for producing a surface-treated metallic material according to  claim 4 .