CN101608306A - The surface treatment method of a kind of passivating solution and zinc-plating material - Google Patents
The surface treatment method of a kind of passivating solution and zinc-plating material Download PDFInfo
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- CN101608306A CN101608306A CN 200810125728 CN200810125728A CN101608306A CN 101608306 A CN101608306 A CN 101608306A CN 200810125728 CN200810125728 CN 200810125728 CN 200810125728 A CN200810125728 A CN 200810125728A CN 101608306 A CN101608306 A CN 101608306A
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- passivating solution
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
Abstract
A kind of passivating solution, wherein, this passivating solution is the aqueous solution that contains water-soluble molybdenum compound, boric acid, water soluble organic substance and silicon sol, wherein, described water soluble organic substance is the mixture of pure and mild organic carboxyl acid.The present invention also provides a kind of surface treatment method of zinc-plating material, and wherein, this method comprises passivating solution provided by the invention is contacted with zinc-plating material.Described passivating solution provided by the invention contacts with zinc-plating material, can carry out passivation to zinc coating, makes zinc-plating material have excellent erosion resistance.In addition, described coating composition provided by the invention does not contain chromium, satisfies the requirement of RoHS instruction.
Description
Technical field
The invention relates to the surface treatment method of a kind of passivating solution and zinc-plating material.
Background technology
Zinc-plating material for example one of the main application of zinc-based metal plated steel sheet or coil of strip is used for electric apparatus manufacture, such as air-conditioning, computer housing etc.Before storage, transportation or using, zinc-plating material generally will pass through Passivation Treatment.Passivation Treatment generally comprises passivating solution is contacted with zinc-plating material, and as passivating solution being sprayed the surface of zinc-plating material, passivating solution comprises chromyl passivating solution and not chromyl passivating solution.
Parliament of European Union and board of management have passed through " The Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment " on February 13rd, 2003, be called for short the RoHS instruction, i.e. 2002/95/EC number instruction of European Union.In this command request later electronic and electrical equipment of newly putting on market on July 1st, 2006, forbid or limit the material that uses that lead (Pb), mercury (Hg), cadmium (Cd), sexavalent chrome (Cr are arranged
6+).Wherein, plumbous (Pb), sexavalent chrome (Cr
6+), cadmium (Cd), mercury (Hg) belong to steel plate composition or Coating composition or the coated component that limits.
Therefore, the use of chromyl passivating solution is restricted, and developing focus is transferred to not chromyl environment-friendly type passivation liquid.
CN 1268583A discloses a kind of chromium-free passivation liquid and coating method thereof that is used to protect zinc coating, and the compound method of this passivating solution is as follows: (1) presses the water soluble acrylate resin: the volume ratio dilution of water=1: 1-4; (2) the water soluble acrylate resin's solution after every liter of dilution adds 1-5 gram molybdate, obtains passivating solution colourless, transparent, pH=6-9.This passivating solution is coated in the galvanized workpiece surface equably.
Though the thin film layer that forms by aforesaid method can make zinc-plating material have certain erosion resistance, but but can not substitute existing chromyl passivating solution, because it is coated in the zinc coating surface, formation is resin molding, rather than the real zinc coating passivation that makes, and the erosion resistance of the zinc-plating material after handling is still not high.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming that there is corrosion-resistant in existing zinc-plating material, a kind of passivating solution that can be used for improving the erosion resistance of zinc-plating material is provided.
Another object of the present invention provides a kind of surface treatment method of zinc-plating material.
The invention provides a kind of passivating solution, wherein, this passivating solution is the aqueous solution that contains water-soluble molybdenum compound, boric acid, water soluble organic substance and silicon sol, and wherein, described water soluble organic substance is the mixture of pure and mild organic carboxyl acid.
The present invention also provides a kind of surface treatment method of zinc-plating material, and wherein, this method comprises passivating solution provided by the invention is contacted with zinc-plating material.
Described passivating solution provided by the invention contacts with zinc-plating material, can carry out passivation to zinc coating, makes zinc-plating material have excellent erosion resistance.In addition, described coating composition provided by the invention does not contain chromium, satisfies the requirement of RoHS instruction.
Embodiment
Passivating solution provided by the invention is the aqueous solution that contains water-soluble molybdenum compound, boric acid, water soluble organic substance and silicon sol, and wherein, described water soluble organic substance is the mixture of pure and mild organic carboxyl acid.
In passivating solution provided by the invention, above-mentioned various components contents can change within a large range, and under the preferable case, the content of described molybdenum compound can be the 0.5-50 grams per liter, is preferably the 1-20 grams per liter, more preferably the 2-10 grams per liter; The content of described boric acid can be 0.1-20 weight %, is preferably 0.5-10 weight %, more preferably the 1-5 grams per liter; The content of the mixture of described pure and mild organic carboxyl acid can be 0.2-30 weight %, is preferably 1-15 weight %, more preferably the 2-8 grams per liter; The content of described silicon sol can be the 1-100 grams per liter, is preferably the 5-50 grams per liter, more preferably the 8-30 grams per liter.
Described water-soluble molybdenum compound can be the various compounds that contain molybdenum that at normal temperatures can be water-soluble, is preferably in molybdate, para-molybdic acid, paramolybdate, two molybdic acids, two molybdates, four molybdic acids, four molybdates, seven molybdic acids and seven molybdates one or more.
Described molybdate can be the ammonium salt and an alkali metal salt of molybdic acid, is preferably selected from Sodium orthomolybdate, potassium molybdate and the ammonium molybdate one or more.
Described paramolybdate can be the ammonium salt and an alkali metal salt of para-molybdic acid, is preferably selected from sodium paramolybdate, para-molybdic acid potassium and the ammonium paramolybdate one or more.
Described two molybdates can be the ammonium salt and an alkali metal salt of two molybdic acids, are preferably selected from two Sodium orthomolybdates, two potassium molybdates and the ammonium dimolybdate one or more.
Described four molybdates can be the ammonium salt and an alkali metal salt of four molybdic acids, are preferably selected from four Sodium orthomolybdates, four potassium molybdates and the ammonium tetramolybdate one or more.
Described seven molybdates can be the ammonium salt and an alkali metal salt of seven molybdic acids, are preferably selected from seven Sodium orthomolybdates, seven potassium molybdates and the Ammonium Heptamolybdate one or more.
In the mixture of described pure and mild organic carboxyl acid, alcohol can in very large range change with the ratio of organic carboxyl acid, and under the preferable case, alcohol can be 1 with the weight ratio of organic carboxyl acid: 0.2-10 is preferably 1: 0.5-5.The weight ratio of alcohol and organic carboxyl acid is 1: can make in the scope of 0.2-10 through the zinc-plating material after this passivating solution processing to have higher erosion resistance.
Described alcohol can be the various liquid alcohol that can dissolve each other with water at normal temperatures, for example can be for having the alcohol of 1-6 carbon atom.Example with alcohol of 1-6 carbon atom includes but not limited to methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, neopentyl alcohol and n-hexyl alcohol.
Described organic carboxyl acid can be the various liquid organic carboxyl acids that can dissolve each other with water at normal temperatures, for example can be for having the polycarboxylic acid of 2-15 carbon atom, preferred 2-8 carbon atom, more preferably one or more in tartrate, oxalic acid, citric acid, Succinic Acid, toxilic acid and the gluconic acid.
Described silicon sol can be the various silicon sol of routine.Described silicon sol can be commercially available or the method by routine prepares, for example elemental silicon one goes on foot dissolution method, ion exchange method, peptisation and dispersion method, can be with reference to " the character preparation and the application of silicon sol ", Tian Hua etc., state's outdoor building materials science and technology, 2007 the 28th volume the 2nd phase 8-17 pages or leaves.Concentration of silicon dioxide can be 10-50 weight % in the described silicon sol.
Passivating solution provided by the invention can make by the preparation method of routine, for example, water-soluble molybdenum compound, boric acid, alcohol, organic carboxyl acid, silicon sol and water is mixed.There is no particular limitation to blended temperature and blended time, makes uniform solution as long as various compositions are mixed, and the blended temperature can be 20-80 ℃.Under the preferable case, the preparation method of passivating solution comprises: boric acid is joined in a part of water, treat after boric acid dissolves fully the temperature of solution to be risen to 60-80 ℃, the mixture that adds molybdenum compound and pure and mild organic carboxyl acid then, treat that solution becomes green transparent clarification postcooling to 20-35 ℃, add silicon sol, stir 2-10 minute (stirring velocity can be 10-200 rev/min), add the water of remainder then.
The surface treatment method of zinc-plating material provided by the invention comprises zinc-plating material is contacted with passivating solution provided by the invention.
The method of described contact can be for being immersed in zinc-plating material in the passivating solution, perhaps with the surface of passivating solution spray at zinc-plating material.The method of described contact preferably includes the surface of passivating solution spray at zinc-plating material.The condition of described contact can comprise: the consumption of passivating solution can be for more than 20 milliliters/square metre, be preferably the 50-1000 milliliter/square metre; The contact temperature can be 20-60 ℃, is preferably 25-50 ℃; Can be preferably 5 seconds to 30 minutes duration of contact for more than 1 second.
Zinc-plating material with after passivating solution contacts, can also be washed and dry zinc-plating material.
Preferably wash with water, the degree of washing preferably makes the pH of the water after the washing for neutral.
The exsiccant condition optimization all evaporates the moisture on zinc-plating material surface, and for example the exsiccant temperature is preferably 40-100 ℃, and the exsiccant time is preferably 1-20 minute.
Passivating solution provided by the invention can be used for various zinc-plating materials, is particularly useful for steel plate galvanized, for example electrogalvanizing steel plate, hot-dip galvanized steel sheet, 55% aluminum-zinc alloy steel plate and 5% aluminum-zinc alloy steel plate.Described zinc-plating material can comprise base material and attached to the zinc coating on the surface of this base material, described base material is preferably steel plate.
Below by embodiment the present invention is described in more detail.
Embodiment 1
This embodiment is used to illustrate the surface treatment method of passivating solution provided by the invention and zinc-plating material.
1 gram boric acid is joined in 500 ml deionized water, treat that boric acid dissolving is finished after, solution is heated up most 65 ℃.Toward wherein adding 3 gram ammonium tetramolybdates, add the mixture (weight ratio of methyl alcohol and Succinic Acid is 1: 1) of 2 gram methyl alcohol and Succinic Acid again.After liquid becomes the green transparent clear soln, solution is naturally cooled to room temperature, add 20 gram silicon sol (concentration of silicon dioxide is 40 weight %) then, with 50 rev/mins of stirrings 3 minutes, add deionized water then, obtain 1 liter of passivating solution A1.
The above-mentioned passivating solution A1 that makes is sprayed on the surface of zinc-plated coil of strip (model DX51D+AZ) (consumption of passivating solution is 100 milliliters/square metre), contact 1 minute down at 30 ℃, the pH that is washed with water to the water after the washing then is 7, descended dry 5 minutes at 50 ℃ afterwards, obtain the zinc-plated coil of strip of surface passivation.
Embodiment 2
This embodiment is used to illustrate the surface treatment method of passivating solution provided by the invention and zinc-plating material.
2 gram boric acid are joined in 700 ml deionized water, treat that boric acid dissolving is finished after, solution is heated up most 70 ℃.Toward wherein adding 5 grams, two molybdic acids, add the mixture (weight ratio of methyl alcohol and toxilic acid is 1: 1.5) of 3 gram methyl alcohol and toxilic acid again.After liquid becomes the green transparent clear soln, solution is naturally cooled to room temperature, add 10 gram silicon sol (concentration of silicon dioxide is 40 weight %) then, with 100 rev/mins of stirrings 5 minutes, add deionized water then, obtain 1 liter of passivating solution A2.
The above-mentioned passivating solution A2 that makes is sprayed on the surface of zinc-plated coil of strip (model DX51D+AZ) (consumption of passivating solution is 200 milliliters/square metre), contact 10 seconds down at 40 ℃, the pH that is washed with water to the water after the washing then is 7, descended dry 2 minutes at 80 ℃ afterwards, obtain the zinc-plated coil of strip of surface passivation.
Embodiment 3
This embodiment is used to illustrate the surface treatment method of passivating solution provided by the invention and zinc-plating material.
3 gram boric acid are joined in 600 ml deionized water, treat that boric acid dissolving is finished after, solution is heated up most 70 ℃.Toward wherein adding 3 gram ammonium tetramolybdates and 3 gram Sodium orthomolybdates, add 6 gram Virahol and tartaric mixtures (Virahol and tartaric weight ratio are 1: 3) again.After liquid becomes the green transparent clear soln, solution is naturally cooled to room temperature, add 15 gram silicon sol (concentration of silicon dioxide is 40 weight %) then, with 200 rev/mins of stirrings 5 minutes, add deionized water then, obtain 1 liter of passivating solution A3.
The above-mentioned passivating solution A3 that makes is sprayed on the surface of zinc-plated coil of strip (model DX51D+AZ) (consumption of passivating solution is 500 milliliters/square metre), contact 10 minutes down at 25 ℃, the pH that is washed with water to the water after the washing then is 7, descended dry 2 minutes at 80 ℃ afterwards, obtain the zinc-plated coil of strip of surface passivation.
Embodiment 4
This embodiment is used to illustrate the surface treatment method of passivating solution provided by the invention and zinc-plating material.
1.5 gram boric acid are joined in 400 ml deionized water, treat that boric acid dissolving is finished after, solution is heated up most 70 ℃.Toward wherein adding 2 gram ammonium paramolybdates, add the mixture (weight ratio of methyl alcohol, citric acid and toxilic acid is 1: 1: 1) of 6 gram methyl alcohol, citric acid and toxilic acids again.After liquid becomes the green transparent clear soln, solution is naturally cooled to room temperature, add 25 gram silicon sol (concentration of silicon dioxide is 40 weight %) then, with 100 rev/mins of stirrings 5 minutes, add deionized water then, obtain 1 liter of passivating solution A4.
The above-mentioned passivating solution A4 that makes is sprayed on the surface of zinc-plated coil of strip (model DX51D+AZ) (consumption of passivating solution is 600 milliliters/square metre), contact 2 minutes down at 30 ℃, the pH that is washed with water to the water after the washing then is 7, descended dry 5 minutes at 80 ℃ afterwards, obtain the zinc-plated coil of strip of surface passivation.
Embodiment 5
This embodiment is used to illustrate the surface treatment method of passivating solution provided by the invention and zinc-plating material.
4 boric acid are joined in 800 ml deionized water, treat that boric acid dissolving is finished after, solution is heated up most 70 ℃.Toward wherein adding 5 gram Ammonium Heptamolybdates, add the mixture (weight ratio of methyl alcohol, Pentyl alcohol and oxalic acid is 1: 1: 2.4) of 3 gram methyl alcohol, Pentyl alcohol and oxalic acid again.After liquid becomes the green transparent clear soln, solution is naturally cooled to room temperature, add 15 gram silicon sol (concentration of silicon dioxide is 40 weight %) then, with 100 rev/mins of stirrings 5 minutes, add deionized water then, obtain 1 liter of passivating solution A5.
The above-mentioned passivating solution A5 that makes is sprayed on the surface of zinc-plated coil of strip (model DX51D+AZ) (consumption of passivating solution is 100 milliliters/square metre), contact 1 minute down at 25 ℃, the pH that is washed with water to the water after the washing then is 7, descended dry 3 minutes at 80 ℃ afterwards, obtain the zinc-plated coil of strip of surface passivation.
Embodiment 6
4 boric acid are joined in 800 ml deionized water, treat that boric acid dissolving is finished after, solution is heated up most 70 ℃.Toward wherein adding 5 gram Ammonium Heptamolybdates, add the mixture (weight ratio of methyl alcohol, Pentyl alcohol and oxalic acid is 1: 1: 0.3) of 3 gram methyl alcohol, Pentyl alcohol and oxalic acid again.After liquid becomes the green transparent clear soln, solution is naturally cooled to room temperature, add 15 gram silicon sol (concentration of silicon dioxide is 40 weight %) then, with 100 rev/mins of stirrings 5 minutes, add deionized water then, obtain 1 liter of passivating solution A6.
The above-mentioned passivating solution A6 that makes is sprayed on the surface of zinc-plated coil of strip (model DX51D+AZ) (consumption of passivating solution is 150 milliliters/square metre), contact 50 seconds down at 40 ℃, the pH that is washed with water to the water after the washing then is 7, descended dry 10 minutes at 80 ℃ afterwards, obtain the zinc-plated coil of strip of surface passivation.
Comparative Examples 1
This Comparative Examples is used to illustrate the surface treatment method of existing zinc-plating material.
According to disclosed method among the CN 1268583A, it is 8.0 passivating solution that 50ml water soluble acrylate resin (the hard reddening plant produced in Guangzhou, the trade mark is WS-1A), 50 gram water and 0.1 gram Sodium orthomolybdate are made into pH.
This passivating solution is coated on the zinc-plated coil of strip surface, 65 ℃ of dryings 1 second, the adhesion amount 500mg/m of formed photopolymer layer on galvanized steel
2
Embodiment 7-12
Embodiment 7-12 is used to measure the performance of the galvanized steel after the passivating solution passivation that is made by embodiment 1-6.
Corrosion resistance measurement
Method and condition according to regulation among the GB/T10125-1997 " artificial atmosphere corrosion test salt-fog test " are carried out corrosion test, according to GB 142335-90 " metal cladding is the sample grading after the tectum corrosion test of positive polarity to ground " Corrosion results is estimated then, the result is as shown in table 1.
Comparative Examples 2
This Comparative Examples is used to measure the performance of the zinc-plated coil of strip after Comparative Examples 1 is handled.
Measure zinc-plated coil of strip erosion resistance after Comparative Examples 1 is handled according to the method identical with embodiment 7-12, the result is as shown in table 1.
Table 1
| The embodiment numbering | The passivating solution numbering | Erosion resistance |
| Embodiment 7 | ??A1 | Corroded area after 96 hours is 16% of the total area |
| Embodiment 8 | ??A2 | Corroded area after 96 hours is 15% of the total area |
| Embodiment 9 | ??A3 | Corroded area after 96 hours is 17% of the total area |
| Embodiment 10 | ??A4 | Corroded area after 96 hours is 16% of the total area |
| Embodiment 11 | ??A5 | Corroded area after 96 hours is 14% of the total area |
| Embodiment 12 | ??A6 | Corroded area after 96 hours is 20% of the total area |
| Comparative Examples 2 | ??- | Corroded area after 96 hours is 25% of the total area |
From the measurement result shown in the table 1 as can be seen, the corroded area of zinc-plated coil of strip after 96 hours of handling with passivating solution A1-A6 all is no more than 20% of the total area, with erosion resistance after the sexavalent chrome passivation quite or better (corroded area after the sexavalent chrome passivation after 96 hours be generally the total area 20%), satisfy the requirement of household appliances manufacturing fully to the erosion resistance of galvanized steel, corroded area after promptly 96 hours is no more than 20% of the total area, illustrates that surface treatment method provided by the invention has significantly improved the erosion resistance of zinc-plated coil of strip.
Claims (10)
1, a kind of passivating solution is characterized in that, this passivating solution is the aqueous solution that contains water-soluble molybdenum compound, boric acid, water soluble organic substance and silicon sol, and wherein, described water soluble organic substance is the mixture of pure and mild organic carboxyl acid.
2, passivating solution according to claim 1, wherein, in the described aqueous solution, the content of described molybdenum compound is the 0.5-50 grams per liter, the content of described boric acid is the 0.1-20 grams per liter, the content of the mixture of described pure and mild organic carboxyl acid is the 0.2-30 grams per liter, and the content of described silicon sol is the 1-100 grams per liter.
3, passivating solution according to claim 2, wherein, in the described aqueous solution, the content of described molybdenum compound is the 1-20 grams per liter, the content of described boric acid is the 0.5-10 grams per liter, and the content of the mixture of described pure and mild organic carboxyl acid is the 1-15 grams per liter, and the content of described silicon sol is the 5-50 grams per liter.
4, according to any described passivating solution among the claim 1-3, wherein, described molybdenum compound is selected from one or more in molybdate, para-molybdic acid, paramolybdate, two molybdic acids, two molybdates, four molybdic acids, four molybdates, seven molybdic acids and seven molybdates.
5, passivating solution according to claim 4, wherein, described molybdate is selected from one or more in Sodium orthomolybdate, potassium molybdate and the ammonium molybdate, described paramolybdate is selected from one or more in sodium paramolybdate, para-molybdic acid potassium and the ammonium paramolybdate, described two molybdates are selected from one or more in two Sodium orthomolybdates, two potassium molybdates and the ammonium dimolybdate, described four molybdates are selected from one or more in four Sodium orthomolybdates, four potassium molybdates and the ammonium tetramolybdate, and described seven molybdates are selected from one or more in seven Sodium orthomolybdates, seven potassium molybdates and the Ammonium Heptamolybdate.
6, according to any described passivating solution among the claim 1-3, wherein, in the mixture of pure and mild organic carboxyl acid, alcohol is 1 with the weight ratio of organic carboxyl acid: 0.2-10.
7, according to any described passivating solution in claim 1-3 and 6, wherein, described alcohol is selected from one or more in n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, neopentyl alcohol and the n-hexyl alcohol; Described organic carboxyl acid is selected from one or more in tartrate, oxalic acid, citric acid, Succinic Acid, toxilic acid and the gluconic acid.
8, according to any described passivating solution among the claim 1-3, wherein, concentration of silicon dioxide is 10-50 weight % in the described silicon sol.
9, a kind of surface treatment method of zinc-plating material is characterized in that, this method comprises zinc-plating material is contacted with any described passivating solution among the claim 1-8.
10, method according to claim 9, wherein, the method for described contact comprises that with passivating solution spray on the surface of zinc-plating material, the condition of contact comprises that the consumption of passivating solution is more than 20 milliliters/square metre, the contact temperature is 20-60 ℃, and be more than 1 second duration of contact.
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| DE102012108562A1 (en) | 2011-09-28 | 2013-03-28 | Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. | Metal protective coating and Zn-fire-coated metallic material and Al-Zn-fire-coated metallic material using the same |
| CN103031061A (en) * | 2011-09-28 | 2013-04-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
| CN103031061B (en) * | 2011-09-28 | 2015-06-03 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
| US9181447B2 (en) | 2011-09-28 | 2015-11-10 | Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. | Metal protection coating, hot-dip Zn metallic material and hot-dip Al—Zn metallic material using the same |
| EP2644745A2 (en) | 2012-03-31 | 2013-10-02 | Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. | Metal protective coating, the use thereof, and hot-dip metallic material using the same |
| CN105887071A (en) * | 2016-05-30 | 2016-08-24 | 五河县黄淮粮油机械有限公司 | Passivation treatment technology for surface of knife roll of fine dried noodle machine |
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| CN101608306B (en) | 2010-12-22 |
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