CN1966768A - Phosphorization liquid for forming amorphous film coating on iron and zinc surface - Google Patents

Phosphorization liquid for forming amorphous film coating on iron and zinc surface Download PDF

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CN1966768A
CN1966768A CN 200510115266 CN200510115266A CN1966768A CN 1966768 A CN1966768 A CN 1966768A CN 200510115266 CN200510115266 CN 200510115266 CN 200510115266 A CN200510115266 A CN 200510115266A CN 1966768 A CN1966768 A CN 1966768A
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crystalline state
concentration
zinc surface
acid
phosphatization liquid
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CN100494493C (en
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薛振镛
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Abstract

Phosphorization solution for coating amorphous film on the surface of Fe and Zn comprises: first generation phosphate 0.002-0.1mol/L containing one or more of Zn2+, Fe2+, Ca2+, Al2+, amorphous phosphorization catalyst 0.001-0.05mol/L containing one or more of ethanedioic acid, citric acid, tartaric acid, cyclohexanhexol hexa-phosphonic acid, hydroxyethyl di-phosphonic acid and EDTA or the derivants, oxidizing agent 0.001- 0.05mol/L containing one or more of chlorate, nitrate, superoxide, neutralizer containing one or more of sodium hydrate, sodium carbonate and ammonia water for adjusting the free acidity of the solution to 0.0+-1.5. The organic acid or derivants has complexation or chelate ability with metal ions. The film has the advantages of low porosity, good adhesive power with steel and zinc material, and low cost.

Description

Iron and zinc surface obtain the phosphatization liquid of non-crystalline state rete
Technical field: the present invention relates to a kind of phosphatization liquid, particularly a kind of phosphatization liquid that can obtain the non-crystalline state rete at iron and steel, zinc and zinc base alloy (comprising zinc coating) product surface.
Background technology: in background technology, divide, can be divided into crystalline state and non-crystalline state by the structure of phosphatize phosphate coat.Can better suppress underfilm corrosion, sticking power characteristics preferably though the crystalline state phosphatize phosphate coat has, have that phosphatization intergranule hole is more, must show to mediate before the phosphatization and generally need carry out the passivation sealing of hole after reason and the phosphatization and handle and make production more numerous and diverse and defectives such as the sticking power between the pot galvanize product surface coating are unreliable; And the non-crystalline state phosphatize phosphate coat, though have that porosity is lower, needn't show to mediate before the phosphatization and need not carry out sealing treatment after reason and the phosphatization and make the easy characteristics of producing, and normally adopt to add molybdate or tungstate film forming, exist on the steel product phosphatize phosphate coat ADHESION OF PAINTS power is lower than the crystalline state phosphatize phosphate coat, on the pot galvanize goods ADHESION OF PAINTS is subjected to a certain degree limit and because the cost defective such as rise significantly along with the rising significantly of molybdenum, tungsten compound price in recent years.For overcoming these defectives, the phosphatization liquid of iron and zinc surface acquisition non-crystalline state rete is developed.
Summary of the invention: technical problem to be solved by this invention is to provide a kind of iron and zinc surface to obtain the phosphatization liquid of non-crystalline state rete, it can obtain the lower phosphatize phosphate coat of porosity (being lower than crystalline state phosphatize phosphate coat and the common non-crystalline state phosphatize phosphate coat that contains molybdenum, tungsten compound) effectively, to steel and zinc (comprising pot galvanize) goods ADHESION OF PAINTS power better (being better than the common non-crystalline state phosphatize phosphate coat that contains molybdenum, tungsten compound), cost lower (be about crystalline state phosphatize phosphate coat cost 55%, the common non-crystalline state phosphatize phosphate coat cost that contains molybdenum, tungsten compound 42%), produce easy.
The technical scheme that the present invention solves its technical problem employing is that it comprises following component:
By a kind of and above Zn 2+, Fe 2+, Mn 2+, Ca 2+, Mg 2+, Ni 2+, Al 2+The concentration that metal ion constitutes is the primary phosphate of 0.002~0.1mol/l,
The concentration that is made of the organic acid or derivatives thereof of the hydroxyethyl di 2 ethylhexyl phosphonic acid in a kind of and above oxalic acid, propanedioic acid, maleic acid, citric acid, tartrate, bios six phosphoric acid, the phosphonate derivative, ethylenediamine tetraacetic phosphonic acids, EDTA is the non-crystalline state phosphorization filming catalyzer of 0.001~0.05mol/l, this organic acid or derivatives thereof and above-mentioned metal ion have complexing or sequestering power
The concentration that is made of a kind of and above oxymuriate, nitrate, nitrite, superoxide is the oxygenant of 0.001~0.05mol/l,
By being used for of constituting of a kind of and above sodium hydroxide, yellow soda ash, sodium-acetate, ammoniacal liquor, volatile salt the free acidity of solution transferred to 0.0 ± 1.5 neutralizing agent.
The concentration of described primary phosphate is 0.003mol/l; 0.05mol/l; 0.09mol/l.
Described non-crystalline state phosphorization filming catalyst concn is 0.002mol/l; 0.025mol/l; 0.04mol/l.
The concentration of described oxygenant is 0.002mol/l; 0.025mol/l; 0.04mol/l.
Described neutralizing agent free acidity is-1.4; 0; 1.4.
The present invention compares the beneficial effect that is produced with background technology:
1, because the present invention has adopted phosphoric acid salt, non-crystalline state phosphorization filming catalyzer, oxygenant, neutralizing agent to form phosphatization liquid as component in proportion, so it can obtain the lower phosphatize phosphate coat of porosity (being lower than crystalline state phosphatize phosphate coat and the common non-crystalline state phosphatize phosphate coat that contains molybdenum, tungsten compound) effectively, to steel and zinc (comprising pot galvanize) goods ADHESION OF PAINTS power better (being better than the common non-crystalline state phosphatize phosphate coat that contains molybdenum, tungsten compound).
2, because the present invention uses that price is not higher, the molybdenum of scarcity of resources or tungsten compound, thus cost lower (be about crystalline state phosphatize phosphate coat cost 55%, the common non-crystalline state phosphatize phosphate coat cost that contains molybdenum, tungsten compound 42%).
3, owing to need not show before the phosphatization of the present invention to transfer, do not need the passivation sealing of hole after the phosphatization, so produce easy.
Embodiment:
Embodiment 1: get generation zinc phosphate 0.05mol/l, primary iron phosphate 0.001mol/l; Oxalic acid 0.01mol/l, citric acid 0.01mol/l, hydroxyethyl di 2 ethylhexyl phosphonic acid 0.003mol/l, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.003mol/l; Potcrate 0.03mol/l is as solute, the surplus water intaking is as solvent, mixing and stirring, as neutralizing agent its free acidity is transferred to 1.0 points (1 point=0.01N) with sodium hydroxide, under room temperature (20 ° ± 10 ℃), steel work or the zinc products of surface through degreasing, washing and rust cleaning immersed in the above phosphatization liquid, through 3~8min, or, can form the non-crystalline state phosphatize phosphate coat at product surface with above solution spraying 2~5min.
Embodiment 2: get generation zinc phosphate 0.04mol/l, primary iron phosphate 0.002mol/l, primary calcium phosphate 0.003mol/l; Citric acid 0.02mol/l, ethylenediamine tetraacetic phosphonic acids 0.005mol/l; Potcrate 0.025mol/l, SODIUMNITRATE 0.01mol/l is as solute, the surplus water intaking is as solvent, mixing and stirring, (1 point=0.01N) is under room temperature (20 ° ± 10 ℃) as neutralizing agent its free acidity to be transferred to 0.0 point with yellow soda ash, steel work or the zinc products of surface through degreasing, washing and rust cleaning immersed in the above phosphatization liquid, through 3~8min, or, can form the non-crystalline state phosphatize phosphate coat at product surface with above solution spraying 2~5min.
Embodiment 3: get generation zinc phosphate 0.03mol/l, primary iron phosphate 0.001mol/l, generation nickelous phosphate 0.001mol/l; Oxalic acid 0.01mol/l, citric acid 0.01mol/l, nucite six phosphoric acid 0.003mol/l, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.003mol/l; SODIUMNITRATE 0.01mol/l, Sodium Nitrite 0.005mol/l are as solute, the surplus water intaking is as solvent, mixing and stirring, as neutralizing agent its free acidity is transferred to-0.5 point (1 point=0.01N) with yellow soda ash, under room temperature (20 ° ± 10 ℃), steel work or the zinc products of surface through degreasing, washing and rust cleaning immersed in the above phosphatization liquid, through 3~8min, or, can form the non-crystalline state phosphatize phosphate coat at product surface with above solution spraying 2~5min.
Embodiment 4: get generation zinc phosphate 0.002mol/l, generation manganous phosphate 0.04mol/l, tartrate 0.01mol/l; Propanedioic acid 0.005mol/l, hydroxyethyl bisphosphate 0.005mol/l; SODIUMNITRATE 0.02mol/l, Potcrate 0.02mol/l are as solute, the surplus water intaking is as solvent, mixing and stirring, as neutralizing agent its free acidity is transferred to 0.5 point (1 point=0.01N) with volatile salt, under room temperature (20 ° ± 10 ℃), steel work or the zinc products of surface through degreasing, washing and rust cleaning immersed in the above phosphatization liquid, through 3~8min, or, can form the non-crystalline state phosphatize phosphate coat at product surface with above solution spraying 2~5min.

Claims (10)

1, a kind of iron and zinc surface obtain the phosphatization liquid of non-crystalline state rete, it is characterized in that it comprises following component:
By a kind of and above Zn 2+, Fe 2+, Mn 2+, Ca 2+, Mg 2+, Ni 2+, Al 2+The concentration that metal ion constitutes is the primary phosphate of 0.002~0.1mol/l,
The concentration that is made of the organic acid or derivatives thereof of the hydroxyethyl di 2 ethylhexyl phosphonic acid in a kind of and above oxalic acid, propanedioic acid, maleic acid, citric acid, tartrate, bios six phosphoric acid, the phosphonate derivative, ethylenediamine tetraacetic phosphonic acids, EDTA is the non-crystalline state phosphorization filming catalyzer of 0.001~0.05mol/l, this organic acid or derivatives thereof and above-mentioned metal ion have complexing or sequestering power
The concentration that is made of a kind of and above oxymuriate, nitrate, nitrite, superoxide is the oxygenant of 0.001~0.05mol/l,
By being used for of constituting of a kind of and above sodium hydroxide, yellow soda ash, sodium-acetate, ammoniacal liquor, volatile salt the free acidity of solution transferred to 0.0 ± 1.5 neutralizing agent.
2, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described primary phosphate is 0.003mol/l.
3, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described primary phosphate is 0.05mol/l.
4, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described primary phosphate is 0.09mol/l.
5, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, it is characterized in that described non-crystalline state phosphorization filming catalyst concentration is 0.002mol/l.
6, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, it is characterized in that described non-crystalline state phosphorization filming catalyst concentration is 0.025mol/l.
7, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, it is characterized in that described non-crystalline state phosphorization filming catalyst concentration is 0.04mol/l.
8, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described oxygenant is 0.002mol/l.
9, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described oxygenant is 0.025mol/l.
10, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described oxygenant is 0.04mol/l.
CNB2005101152661A 2005-11-15 2005-11-15 Phosphorization liquid for forming amorphous film coating on iron and zinc surface Expired - Fee Related CN100494493C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101671824B (en) * 2009-09-30 2011-02-02 重庆理工大学 Magnesium alloy surface zinc-calcium series phosphating solution and conversion treatment process thereof
CN104651825A (en) * 2015-03-13 2015-05-27 黎建军 Method for surface treatment of petroleum machine parts
CN111167689A (en) * 2020-01-03 2020-05-19 山东尚核电力科技有限公司 Application method of steel pipe inside and outside plastic dipping production system

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101671824B (en) * 2009-09-30 2011-02-02 重庆理工大学 Magnesium alloy surface zinc-calcium series phosphating solution and conversion treatment process thereof
CN104651825A (en) * 2015-03-13 2015-05-27 黎建军 Method for surface treatment of petroleum machine parts
CN104651825B (en) * 2015-03-13 2017-12-26 中国计量大学 Petroleum machinery piece surface processing method
CN111167689A (en) * 2020-01-03 2020-05-19 山东尚核电力科技有限公司 Application method of steel pipe inside and outside plastic dipping production system
CN111167689B (en) * 2020-01-03 2020-10-27 山东尚核电力科技有限公司 Application method of steel pipe inside and outside plastic dipping production system

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