CN101665938A - Preparation method of high anti-corrosion zinc coat titanium salt protective film - Google Patents

Preparation method of high anti-corrosion zinc coat titanium salt protective film Download PDF

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CN101665938A
CN101665938A CN200910192900A CN200910192900A CN101665938A CN 101665938 A CN101665938 A CN 101665938A CN 200910192900 A CN200910192900 A CN 200910192900A CN 200910192900 A CN200910192900 A CN 200910192900A CN 101665938 A CN101665938 A CN 101665938A
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titanium salt
corrosion
protective film
passivating solution
high anti
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CN101665938B (en
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许乔瑜
姜瑞
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South China University of Technology SCUT
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Abstract

The invention discloses a preparation method of a high anti-corrosion zinc coat titanium salt protective film. The method includes the following steps: after galvanizing an iron and steel workpiece, adopting an impregnated method with constant temperature to place the workpiece in the passivation solution of titanium salt for 5-20min, and taking out the workpiece, thus forming the high anti-corrosion zinc coat titanium salt protective film, wherein the processing temperature is 20-40 DEG C. Counted by the content of raw materials in the passivation solution of titanium salt, the raw material formula of the passivation solution of titanium salt consists of the following components: 0.6-1.8g/L of film forming agent Ti(SO4)2, 12-28mL/L of additive component phytic acid for improving anti-corrosion performance and 48-72mL/L of film forming oxidation promoter component H2O2. The preparation method forms a layer of protective film being good in adhesive power, neat and compact and equivalentto normal chromate passivation in corrosion resistance on the surface of zinc coat. Showed by electrochemical and salt spray corrosion results, the protective film has favorable protection performance. The method is low in cost, can substitute for the presently widely adopted normal passivation of poisonous hexavalent chromium and is beneficial to environment protection.

Description

A kind of preparation method of high anti-corrosion zinc coat titanium salt protective film
Technical field
The present invention relates to galvanizing, particularly relate to the method that a kind of zinc coating surface forms the titanium salt protective membrane with high anti-corrosion.
Background technology
Galvanizing is one of important preventive means of iron and steel, and galvanized steel is widely used in a plurality of industries such as automobile, electric power, traffic, building, telecommunication.Yet hot galvanized layer easily corrodes under wet environment, influences the outward appearance of product, also can reduce the work-ing life of galvanized workpiece.Present most popular anti-corrosion method is low concentrations of chromium hydrochlorate (about 0.2% dichromate or chromic anhydride) passivation, the advantage of its passivation is: chromate passivation film has solidity to corrosion and smooth densification on the one hand, with the firm binding force of matrix metal, in the corrosive environment, matrix metal is played the effect of insulation blocking; Contain the solubility hexavalent chromium compound on the other hand in the chromate passivation film, can play restraining effect to further corrosion, promptly usually said " self-healing ability " the zinc passivation once more of naked leak.But sexavalent chrome toxicity is very big, serious harm HUMAN HEALTH and environment and used by strict restriction.The domestic and international non-chromium inactivating technique of reporting mainly contains molybdate and rare earth metal salt passivation, silicate passivation, vanadate passivation, titanium salt passivation, organism passivation and tungstate passivation etc. at present, but the corrosion resisting property of these Chrome-free conversion films is compared with chromate conversion coating and is also had a certain distance, though the compound conversion film corrosion resisting property of part near or surpass chromate conversion coating, but the treatment process more complicated, cost is too high.
Titanium salt is the low pollution substance of a kind of low toxicity, carries out the titanium salt conversion processing at metal material surfaces such as copper, aluminium, iron and steel, can obtain to have good corrosion proof conversion film.The titanium salt Passivation Treatment is to improve the corrosion proof a kind of effective means of metal.Titanium salt passivation film structure and chromate passivation film similar are unbodied porous-film, take to seal and the titanium salt of back coating after handling transforms the corrosion resisting property of rete the chromate passivation film with common is suitable.But sealing and back coating are handled, and have increased the operation of Passivation Treatment.
Summary of the invention
The objective of the invention is to propose a kind of method that can form environment-friendly chromium-free protective membrane on the zinc coating surface with high anti-corrosion; To guarantee also that simultaneously technology is simple, it can be widely used industrial.
Additive of the present invention adopts phytic acid, and the additive phytic acid is added in the titanium salt passivating solution, forms new titanium salt passivating solution, realizes that Passivation Treatment and these two kinds of technologies of sealing treatment " unite two into one ", has simplified step, has saved cost.
For reaching above-mentioned purpose, the technical solution used in the present invention is:
A kind of preparation method of high anti-corrosion zinc coat titanium salt protective film after iron and steel parts is zinc-plated, adopts the method for constant temperature dipping to place the titanium salt passivating solution to take out after 5~20 minutes workpiece, and treatment temp is 20~40 ℃, forms high anti-corrosion zinc coat titanium salt protective film; Press the cubage of raw material in the titanium salt passivating solution, described titanium salt passivating solution composition of raw materials is made up of following component: membrane-forming agent Ti (SO 4) 20.6 the additive component phytic acid (C of~1.8g/L, raising corrosion resisting property 6H 18O 24P 6) 12~28mL/L, film forming oxidation promotor component H 2O 248~72mL/L; Titanium salt passivating solution pH value is 0.9~2.0.
Described titanium salt passivating solution collocation method comprises the steps:
(1) with distilled water, film forming oxidation promotor component H 2O 2Dissolving is configured to film Ti (SO 4) 2, it is orange red that solution is;
(2) add in advance with the good phytic acid of dissolved in distilled water (phytinic acid, C 6H 18O 24P 6), solution by orange red become orange-yellow;
(3) press the cubage of raw material in the titanium salt passivating solution, replenish distilled water to membrane-forming agent Ti (SO 4) 2Content is 0.6~1.8g/L, the binder component phytic acid (C that improves corrosion resisting property 6H 18O 24P 6) be 12~28mL/L, film forming oxidation promotor component H 2O 2Content is 48~72mL/L; And to regulate titanium salt passivating solution pH value with sulfuric acid be 0.9~2.0.
Described workpiece places the titanium salt passivating solution to be preferably 10~15 minutes.
Described treatment temp is preferably 25~35 ℃.
With respect to prior art, the invention has the beneficial effects as follows: the present invention has overcome single titanium salt solution and has handled defectives such as formed passive film is inhomogeneous, tiny crack is many, handle even, the smooth densification of protective membrane that forms through this passivating solution, the corrosion resisting property of titanium salt film is largely increased; This invented technology is simple simultaneously, and cost is low, adopts single passivating solution to carry out simple chemical immersion treatment and obtains protective membrane fast.
Description of drawings
Fig. 1 for zinc coating and phytic acid modified version titanium salt passivation film respectively in 5%NaCl salt air corrosion zinc coating begin to occur the histogram of 5% white rust time.
Fig. 2 is zinc coating and the polarization curve of phytic acid modified version titanium salt passivation film in 5%NaCl solution.
Embodiment
For further understanding the present invention, below in conjunction with embodiment the present invention is made specific description, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
The common process of steel plate galvanizing is as follows: thermokalite is bathed oil removing → hot water injection → acid pickling and rust removing → cold water flush → plating assistant agent and is helped plating → oven dry → hot dip process → water-cooled.
Titanium salt passivating solution and treatment process process:
After iron and steel parts is zinc-plated, adopt the method for constant temperature dipping to place the titanium salt passivating solution to take out after 10 minutes workpiece, seasoning, passivation temperature is 25 ℃; The titanium salt passivating solution is formed and is comprised membrane-forming agent component Ti (SO 4) 2, its content is 1.0g/L; Binder component is phytic acid (C 6H 18O 24P 6), its content is 20mL/L; Film forming oxidation promotor component is H 2O 2, content is 60mL/L; Regulating titanium salt passivating solution pH value with sulfuric acid is 1.5.
Titanium salt passivating solution configuration concrete grammar is:
(1) in the 1000mL beaker, with distilled water and the 60mL H of 100mL 2O 2Ti (the SO of dissolving configuration 1.0g 4) 2, it is orange red that solution is.
(2) add water in advance and dissolve good 20mL phytic acid (C 6H 18O 24P 6), solution by orange red become orange-yellow.
(3) replenish distilled water to 1000mL, and with sulphur acid for adjusting pH value to 1.5.
Place electric-heated thermostatic water bath to be heated to 25 ℃ of insulations in the beaker that fills passivating solution.Sample steel plate is put into the passivating solution Passivation Treatment of present embodiment immediately after the common process of galvanizing is handled, take out after 10 minutes, places the air seasoning, forms high anti-corrosion zinc coat titanium salt protective film.
Contrast test
Steel plate galvanized is respectively at the titanium salt passivating solution, and handles in the present embodiment phytic acid modified version titanium salt passivating solution.Its treatment step is identical with embodiment 1 with processing condition.
Estimate the coating corrosion resistance nature with the neutral salt spray corrosion test method, adopt YWX/Q-150 type centrifugal sale mist testing chamber, sample is carried out neutral salt spray test according to GB6458-86.Etchant solution is 5% (weight) NaCl aqueous solution, pH6.5~7.0, and temperature is (35 ± 2) ℃ in the spray box, sinkability is 2mL/ (80cm 2H), sample becomes 25~30 ° of placements with vertical direction; The edge of sample applies sealing to avoid side effect with organic gel; Sample every day continuously spray 8h, to stop 16h be one-period; The used time of 5% white rust occurs with coating surface and estimate the solidity to corrosion of coating, the results are shown in Figure 1.Untreated as can be known from Fig. 1 zinc coating is after the neutral salt spray corrosion, and 5% white rust time occurring for is 3 hours; After passivation in the phytic acid modified version titanium salt passivating solution, 5% white rust time occurring for is 80 hours.Experimental result shows that steel plate galvanized can delay the generation of white rust by a relatively large margin after the passivation in phytic acid modified version titanium salt passivating solution, and corrosion resistance nature obviously improves.
With electrochemical measurement test evaluation coating corrosion resistance nature, sample is coated with envelope with Resins, epoxy, expose the working area of 10mm * 10mm, estimate the electrochemical corrosion performance of sample by Ta Feier polarization, electrochemical impedance measurement.All electrochemical measurements all are to carry out on CHI604B electrochemical workstation (Shanghai occasion instrument company), adopt conventional three-electrode system, and supporting electrode is 10cm 2Platinum electrode, reference electrode are saturated calomel electrode (SCE), and sample to be tested is as working electrode, and test soln is 5% (weight) NaCl aqueous solution, under the condition of room temperature, not degasification, soak 20min, treat that corrosion potential carries out after stable.The scanning speed that polarization curve is measured is 1mV/s.Comparison such as Fig. 2 of the electrochemical tests of coating show that table 1 is corresponding electrochemical polarization parameter.From Fig. 2 and table 1 as can be seen, untreated zinc coating electrochemical impedance in the 5%NaCl aqueous solution is 1.043k Ω cm 2, corrosion electric current density I CorrBe 9.020 μ Acm -2After passivation in the phytic acid modified version titanium salt passivating solution, electrochemical impedance is 77.64k Ω cm in the 5%NaCl aqueous solution 2Corrosion electric current density I CorrBe 0.124 μ Acm -2After experimental result shows that zinc coating carries out the titanium salt Passivation Treatment, polarization resistance R pEnlarge markedly corrosion electric current density I CorrSignificantly reduce.Show that phytic acid modified version titanium salt passive film has good solidity to corrosion.
Table 1 galvanizing, phytic acid modified version titanium salt passive film electrochemical polarization parameter
Figure G200910192900XD00041
The high anti-corrosion zinc coat titanium salt protective film of following embodiment gained all is to handle gained by phytic acid modified version titanium salt passivating solution, and its performance test situation is substantially the same manner as Example 1, not explanation one by one.
Embodiment 2
The steel plate galvanizing, technology is as follows: thermokalite is bathed oil removing → hot water injection → acid pickling and rust removing → cold water flush → plating assistant agent and is helped plating → oven dry → hot dip process → water-cooled.
Titanium salt passivating solution and treatment process process:
After iron and steel parts is zinc-plated, adopt the method for constant temperature dipping to place the titanium salt passivating solution to take out after 5 minutes workpiece, seasoning, passivation temperature is for being 20 ℃; The titanium salt passivating solution is formed and is comprised membrane-forming agent component Ti (SO 4) 2, its content is 0.6g/L; Binder component is phytic acid (C 6H 18O 24P 6), its content is 12mL/L; Film forming oxidation promotor component is H 2O 2, content is 60mL/L; Regulating titanium salt passivating solution pH value with sulfuric acid is 2.0.
Concrete grammar is:
(1) in the 1000mL beaker, with distilled water and the 60mL H of 100mL 2O 2Ti (the SO of dissolving configuration 0.6g 4) 2, it is orange red that solution is.
(2) add water in advance and dissolve good 12mL phytic acid (C 6H 18O 24P 6), solution by orange red become orange-yellow.
(3) replenish distilled water to 1000mL, and with sulphur acid for adjusting pH value to 2.0.
Place electric-heated thermostatic water bath to be heated to 20 ℃ of insulations in the beaker that fills passivating solution.Sample is put into the passivating solution Passivation Treatment immediately after pot galvanize and water-cooled, take out after 5 minutes, places the air seasoning, forms high anti-corrosion zinc coat titanium salt protective film.
Embodiment 3
The steel plate galvanizing, technology is as follows: thermokalite is bathed oil removing → hot water injection → acid pickling and rust removing → cold water flush → plating assistant agent and is helped plating → oven dry → hot dip process → water-cooled.
Titanium salt passivating solution and treatment process process:
After iron and steel parts is zinc-plated, adopt the method for constant temperature dipping to place the titanium salt passivating solution to take out after 20 minutes workpiece, seasoning, passivation temperature is for being 30 ℃; The titanium salt passivating solution is formed and is comprised membrane-forming agent component Ti (SO 4) 2, its content is 1.4g/L; Binder component is phytic acid (C 6H 18O 24P 6), its content is 20mL/L; Film forming oxidation promotor component is H 2O 2, content is 72mL/L; Regulating titanium salt passivating solution pH value with sulfuric acid is 0.9.
Concrete grammar is:
(1) in the 1000mL beaker, with distilled water and the 72mL H of 100mL 2O 2Ti (the SO of dissolving configuration 1.4g 4) 2, it is orange red that solution is.
(2) add water in advance and dissolve good 20mL phytic acid (C 6H 18O 24P 6), solution by orange red become orange-yellow.
(3) replenish distilled water to 1000mL, and with sulphur acid for adjusting pH value to 0.9.
Place electric-heated thermostatic water bath to be heated to 30 ℃ of insulations in the beaker that fills passivating solution.Sample is put into the passivating solution Passivation Treatment immediately after pot galvanize and water-cooled, take out after 20 minutes, places the air seasoning, forms high anti-corrosion zinc coat titanium salt protective film.
Embodiment 4
The steel plate galvanizing, technology is as follows: thermokalite is bathed oil removing → hot water injection → acid pickling and rust removing → cold water flush → plating assistant agent and is helped plating → oven dry → hot dip process → water-cooled.
Titanium salt passivating solution and treatment process process:
After iron and steel parts is zinc-plated, adopt the method for constant temperature dipping to place the titanium salt passivating solution to take out after 10 minutes workpiece, seasoning, passivation temperature is for being 35 ℃; The titanium salt passivating solution is formed and is comprised membrane-forming agent component Ti (SO 4) 2, its content is 1.8g/L; Binder component is phytic acid (C 6H 18O 24P 6), its content is 28mL/L; Film forming oxidation promotor component is H 2O 2, content is 60mL/L; Regulating titanium salt passivating solution pH value with sulfuric acid is 1.5.
Concrete grammar is:
(1) in the 1000mL beaker, with distilled water and the 60mL H of 100mL 2O 2Ti (the SO of dissolving configuration 1.8g 4) 2, it is orange red that solution is.
(2) add water in advance and dissolve good 28mL phytic acid (C 6H 18O 24P 6), solution by orange red become orange-yellow.
(3) replenish distilled water to 1000mL, and with sulphur acid for adjusting pH value to 1.5.
Place electric-heated thermostatic water bath to be heated to 35 ℃ of insulations in the beaker that fills passivating solution.Sample is put into the passivating solution Passivation Treatment immediately after pot galvanize and water-cooled, take out after 10 minutes, places the air seasoning, forms high anti-corrosion zinc coat titanium salt protective film.
Embodiment 5
The steel plate galvanizing, technology is as follows: thermokalite is bathed oil removing → hot water injection → acid pickling and rust removing → cold water flush → plating assistant agent and is helped plating → oven dry → hot dip process → water-cooled.
Titanium salt passivating solution and treatment process process:
After iron and steel parts is zinc-plated, adopt the method for constant temperature dipping to place the titanium salt passivating solution to take out after 15 minutes workpiece, seasoning, passivation temperature is for being 40 ℃; The titanium salt passivating solution is formed and is comprised membrane-forming agent component Ti (SO 4) 2, its content is 1.0g/L; Binder component is phytic acid (C 6H 18O 24P 6), its content is 20mL/L; Film forming oxidation promotor component is H 2O 2, content is 48mL/L; Regulating titanium salt passivating solution pH value with sulfuric acid is 1.2.
Concrete grammar is:
(1) in the 1000mL beaker, with distilled water and the 48mL H of 100mL 2O 2Ti (the SO of dissolving configuration 1.0g 4) 2, it is orange red that solution is.
(2) add water in advance and dissolve good 20mL phytic acid (C 6H 18O 24P 6), solution by orange red become orange-yellow.
(3) replenish distilled water to 1000mL, and with sulphur acid for adjusting pH value to 1.2.
Place electric-heated thermostatic water bath to be heated to 40 ℃ of insulations in the beaker that fills passivating solution.Sample is put into the passivating solution Passivation Treatment immediately after pot galvanize and water-cooled, take out after 15 minutes, places the air seasoning, forms high anti-corrosion zinc coat titanium salt protective film.

Claims (4)

1, a kind of preparation method of high anti-corrosion zinc coat titanium salt protective film, it is characterized in that: after iron and steel parts is zinc-plated, adopt the method for constant temperature dipping to place the titanium salt passivating solution to take out after 5~20 minutes workpiece, treatment temp is 20~40 ℃, forms high anti-corrosion zinc coat titanium salt protective film; Press the cubage of raw material in the titanium salt passivating solution, described titanium salt passivating solution composition of raw materials is made up of following component: membrane-forming agent Ti (SO 4) 20.6 the additive component phytic acid (C of~1.8g/L, raising corrosion resisting property 6H 18O 24P 6) 12~28mL/L, film forming oxidation promotor component H 2O 248~72mL/L; Titanium salt passivating solution pH value is 0.9~2.0.
2, the preparation method of high anti-corrosion zinc coat titanium salt protective film according to claim 1 is characterized in that: described titanium salt passivating solution collocation method comprises the steps:
(1) with distilled water, film forming oxidation promotor component H 2O 2Dissolving is configured to film Ti (SO 4) 2, it is orange red that solution is;
(2) add in advance with the good phytic acid of dissolved in distilled water (phytinic acid, C 6H 18O 24P 6), solution by orange red become orange-yellow;
(3) press the cubage of raw material in the titanium salt passivating solution, replenish distilled water to membrane-forming agent Ti (SO 4) 2Content is 0.6~1.8g/L, the binder component phytic acid (C that improves corrosion resisting property 6H 18O 24P 6) be 12~28mL/L, film forming oxidation promotor component H 2O 2Content is 48~72mL/L; And to regulate titanium salt passivating solution pH value with sulfuric acid be 0.9~2.0.
3, the preparation method of high anti-corrosion zinc coat titanium salt protective film according to claim 1 is characterized in that: described workpiece placed the titanium salt passivating solution 10~15 minutes.
4, the preparation method of high anti-corrosion zinc coat titanium salt protective film according to claim 1 is characterized in that: described treatment temp is 25~35 ℃.
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Cited By (4)

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CN102251203B (en) * 2010-05-18 2014-03-12 海洋王照明科技股份有限公司 Technology of hot dip aluminium-plating and application thereof
CN106623429A (en) * 2016-10-21 2017-05-10 过冬 Rolling forming method for low-oxygen-content aero titanium alloy precision thin sheet
CN107090576A (en) * 2017-05-22 2017-08-25 厦门建霖健康家居股份有限公司 A kind of kirsite chromium-free passivation liquid
CN110760825A (en) * 2019-11-27 2020-02-07 江苏大亿智能科技有限公司 Surface coating anticorrosive material and preparation method thereof

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