CN103255405A - Rare earth chromate-free passivation liquid for coating treatment of material and application of rare earth chromate-free passivation liquid - Google Patents
Rare earth chromate-free passivation liquid for coating treatment of material and application of rare earth chromate-free passivation liquid Download PDFInfo
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Abstract
The invention discloses a rare earth chromate-free passivation liquid for coating treatment of a material and an application of the rare earth chromate-free passivation liquid. The passivation liquid comprises the following components: boric acid, hydrogen peroxide, tervalent cerate, phytic acid and water, wherein a molar ratio of the boric acid, to H2O2 to Ce<3+> to the phytic acid to water in the passivation liquid is (1-50):(24.5-245):(1.66-83.2):(0.62-62):(1722-17220). The passivation liquid is used for surface treatment of a galvanized metal plate. According to the galvanized salt mist resisting passivation liquid used for surface treatment of the galvanized metal plate, the galvanized metal plate has the salt mist resistance, and the corrosive resistance is further remarkably improved. The experiments show that the anti-corrosion time of the treated galvanized metal plate to a lead acetate solution is raised from average 31 seconds before passivation to 35-360 seconds, and the salt mist resisting time of the treated galvanized metal plate is raised from average 6 hours before passivation to 6-180 hours.
Description
Technical field
The present invention relates to a kind of rare earth chromium-free passivation liquid and application thereof for the processing of material coating, relate in particular to a kind of environmental protection rare earth/H
2O
2/ phytic acid composite passivation solution and application thereof.
Background technology
Zinc-plated is the erosion-resisting effective ways of using always of raising metallic substance, but in a humid environment, and exposed zinc coating is easy to be corroded and forms the white rust of loose shape.Because the chemical property of zinc is more active, under airtight or improper ventilation and the condition that there was dampness in the air, subject to corrosion, also can carry out metal passivation at the galvanized workpiece outside surface usually and handle, with further raising its work-ing life.Characteristics such as tradition hexavalent chromate passivating solution is because of stable performance, and is with low cost, easy to use, and etch resistant properties is good, and passivation technology is simple and being used widely.But sexavalent chrome toxicity very high and can cause carcinogenic, very big to the harm of human body and environment, in recent years along with the raising of environmental consciousness, all chromic uses of strict restriction of countries in the world.At present, continue to increase the research and development to the chromium-free deactivation new technology both at home and abroad, chromium-free deactivation mainly includes the composite passivated of machine passivation and inorganic passivation and organic-inorganic, usually single organism passivation has stronger solidity to corrosion, but sticking power and thermotolerance are relatively poor, inorganics is then relative with it, and erosion resistance is slightly poor, and sticking power and thermotolerance are better.The organism passivation adds inorganics in the chromium-free deactivation, can play synergistic slow corrosion and performance complement effect when perhaps adding organism in the inorganics passivation, thereby improves the performances such as erosion resistance of passive film.It is inexorable trend that novel non-chromium inactivating technique replaces traditional sexavalent chrome passivation.
The present situation that the salt air corrosion of coastland, Guangdong Province is serious is although the steel metal frame surface of finished product has plated layer of metal zinc.Outer zinc is limited to preventing the salt air corrosion effect, generally move 2.5 years after, need once paint processing.At the situation of coastal iron tower of power transmission line seriously corroded, the salt fog resistance corrosive power of protection and prolongation steel metal frame transmitting line is present problem demanding prompt solution.
Rare earth metal salt (cerium, lanthanum) can form precipitations such as rare earth oxide or oxyhydroxide and cover the galvanized workpiece surface in the metallic surface, completely cut off contacting of zinc coating and corrosive medium, reduces the bleed rate of zinc.Rare-earth substance can suppress the cathodic process of metallic corrosion simultaneously, reduces the erosion rate of zinc coating, improves zinc layer corrosion resisting property.Adopt single cerium solution to handle galvanized workpiece, obtain one deck passive film, and discover that it has good corrosion protection effect to zinc spare, but the passivation time of this method is long.
Summary of the invention
The object of the present invention is to provide a kind of rare earth chromium-free passivation liquid and application thereof for the processing of material coating.
At existing deficiency in the prior art, the technical solution used in the present invention is:
A kind of rare earth chromium-free passivation liquid for the processing of material coating, this passivating solution contains following component: boric acid, hydrogen peroxide, cerous salt, phytic acid, water, in the described passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1～50:24.5～245:1.66～83.2:0.62～62:1722～17220.
Preferably, in the described passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1～20:24.5～122.5:1.66～83.2:0.62～62:1722～17220.
Preferably, cerous salt is at least a in Cerium II Chloride, comprise cerium bromide, cerous nitrate, the cerous sulfate.
Preferably, described rare earth chromium-free passivation liquid mixes gained solution for each component.
The preparation method of the zinc-plated salt fog resistance passivating solution of the present invention may further comprise the steps: with boric acid (H
3BO
3), hydrogen peroxide (H
2O
2), cerous salt, water (H
2O), phytic acid (C
6H
18O
24P
6) mix, stir, both.
The zinc-plated salt fog resistance passivating solution of the present invention is yellow transparent solution.
The using method of above-mentioned rare earth chromium-free passivation liquid may further comprise the steps:
1) the galvanized metal material is soaked in the described rare earth chromium-free passivation liquid, under 10～80 ℃ of constant temperatures, leaves standstill passivation;
2) with the washing of the galvanized metal material after the passivation, leave standstill then and treat that passive film is aging.
Preferably, leaving standstill passivation time is 5 s～20 min.
After the passivation of the zinc-plated salt fog resistance passivating solution of galvanized metal material process the present invention, the galvanized metal material surface can present rare earth ion gloss.Galvanized metal material of the present invention can be steel plate galvanized, zinc-plated coil of strip etc.
The invention has the beneficial effects as follows:
The technology that the present invention takes rare earth to be combined with organic passivation, zinc surface can generate the organic and inorganic composite film of dense densification at its surface in situ through after the surface treatment.The present invention has added H in the rare earth cerium solution
2O
2And phytic acid, the passivating solution salt fog resistance of making, the solidity to corrosion of passive film significantly improves, because the surface topography of film has material impact to solidity to corrosion, phytic acid and H
2O
2Participate in the formation of rare-earth salt passive film, crystallization of refinement crystal grain is improved corrosion resisting property.Steel plate galvanized after treatment, the anti-corrosion time of Dichlorodiphenyl Acetate lead solution rises to 35～360s by the average 31s before the passivation not, the salt fog resistance time rises to 6～180h by the average 6h before the passivation not.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment, but be not limited thereto.
Embodiment 1
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1:24.5:1.66:0.62:1722.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 25 ℃ of constant temperatures, leaves standstill passivation 5min.
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 2
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1:24.5:1.66:62:1722.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 30 ℃ of constant temperatures, leaves standstill passivation 2min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 3
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1:24.5:1.66:0.62:17220.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 50 ℃ of constant temperatures, leaves standstill passivation 1min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 4
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1:24.5:83.2:0.62:1722.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 20 ℃ of constant temperatures, leaves standstill passivation 50s;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 5
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, comprise cerium bromide, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 50:245:83.2:62:17220.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 30 ℃ of constant temperatures, leaves standstill passivation 5min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 6
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 50:24.5:1.66:0.62:1722.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 25 ℃ of constant temperatures, leaves standstill passivation 5min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 7
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, cerous nitrate, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 50:245:1.66:0.62:1722.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 50 ℃ of constant temperatures, leaves standstill passivation 50s;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 8
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 50:24.5:83.2:62:17220.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 25 ℃ of constant temperatures, leaves standstill passivation 5min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 9
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 50:24.5:1.66:62:17220.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 30 ℃ of constant temperatures, leaves standstill passivation 6min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 10
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 50:245:83.2:0.62:17220.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 25 ℃ of constant temperatures, leaves standstill passivation 5min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 11
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, cerous sulfate, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1:245:83.2:0.62:17220.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 25 ℃ of constant temperatures, leaves standstill passivation 5min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 12
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1:24.5:83.2:62:17220.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 60 ℃ of constant temperatures, leaves standstill passivation 30s;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 13
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 50:24.5:83.2:62:1722.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 10 ℃ of constant temperatures, leaves standstill passivation 20min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 14
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 50:24.5:83.2:0.62:17220.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 25 ℃ of constant temperatures, leaves standstill passivation 5min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 15
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1:245:83.2:62:1722.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 80 ℃ of constant temperatures, leaves standstill passivation 5s;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 16
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1:245:83.2:0.62:1722.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 25 ℃ of constant temperatures, leaves standstill passivation 5min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 17
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, cerous sulfate, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 50:24.5:1.66:62:1722.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 25 ℃ of constant temperatures, leaves standstill passivation 5min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
Embodiment 18
A kind of rare earth chromium-free passivation liquid for the processing of material coating, its component is: boric acid, hydrogen peroxide, Cerium II Chloride, phytic acid, water; In the passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1:245:1.6:0.62:1722.
A kind of process of surface treatment of galvanized metal material may further comprise the steps:
1) steel plate galvanized is immersed in the above-mentioned rare earth chromium-free passivation liquid, under 25 ℃ of constant temperatures, leaves standstill passivation 5min;
2) with the washing of the steel plate galvanized after the passivation, leave standstill then and treat that passive film is aging.
The zinc-plated salt fog resistance passivating solution of above embodiment mixes by each component, and the formation yellow transparent solution stirs.
The process of surface treatment of embodiment 1～17 is carried out in employing respectively with the steel plate galvanized of condition, steel plate galvanized after the processing carries out the following experiment of plumbic acetate drop and neutral salt spray test respectively, the steel plate galvanized that adopts is the qualified homemade steel plate galvanized of quality test, specification be 50cm * 5 cm * 2cm(long * wide * thick), simultaneously, with the steel plate galvanized of the same condition handled without passivating solution product in contrast, The performance test results sees Table 1.Before steel plate galvanized was treated, be 31s the anti-corrosion mean time of Dichlorodiphenyl Acetate lead solution, and salt fog resistance mean time is 6h.
The experiment of plumbic acetate drop
According to the quick detection passive film solidity to corrosion method that proposes in the middle of the GB 9791-88, namely plumbic acetate solution volumetry is 50 g L with concentration
-1Pb (Ac)
2Solution carries out titration experiments at sample surfaces, notes the titration position and begins the time used when turning black fully from titration, and each sample variable color time is represented with the mean value of 3 test point, the corrosion resistance nature of judgement sample passive film.
Neutral salt spray test
According to GB 6458-86 in salt fog cabinet to the test piece experiment of spraying continuously.Spraying fluid is the NaCl solution of massfraction 5%, and pH controls between 6.5-7.2, and the tested face of sample is 30o, and temperature is controlled about 35 ℃.Spray pattern adopts periodically spray method, adopts the time that occurs corrosion for the first time, and namely time of corroding appears in specimen surface for the first time, thus corrosion resistance nature relatively.
The experiment of plumbic acetate drop and neutral salt spray test the results are shown in Table 1, as seen from table, steel plate galvanized after treatment, the anti-corrosion time of Dichlorodiphenyl Acetate lead solution rises to 35～360s by the average 31s before the passivation not, the salt fog resistance time rises to 6～180h by the average 6h before the passivation not.
Claims (6)
1. one kind is used for the rare earth chromium-free passivation liquid that material coating is handled, and this passivating solution contains following component: boric acid, hydrogen peroxide, cerous salt, phytic acid, water, and in the described passivating solution, boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1～50:24.5～245:1.66～83.2:0.62～62:1722～17220.
2. rare earth chromium-free passivation liquid according to claim 1 is characterized in that: in the described passivating solution, and boric acid: H
2O
2: Ce
3+: phytic acid: the mol ratio of water is 1～20:24.5～122.5:1.66～83.2:0.62～62:1722～17220.
3. rare earth chromium-free passivation liquid according to claim 1 and 2 is characterized in that: cerous salt is at least a in Cerium II Chloride, comprise cerium bromide, cerous nitrate, the cerous sulfate.
4. rare earth chromium-free passivation liquid according to claim 1 and 2, it is characterized in that: described rare earth chromium-free passivation liquid mixes gained solution for each component.
5. any using method of a described rare earth chromium-free passivation liquid of claim 1～4 may further comprise the steps:
1) the galvanized metal material is soaked in the described rare earth chromium-free passivation liquid, under 10～80 ℃ of constant temperatures, leaves standstill passivation;
2) with the washing of the galvanized metal material after the passivation, leave standstill then and treat that passive film is aging.
6. using method according to claim 5, it is characterized in that: leaving standstill passivation time is 5 s～20 min.
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