CN101343736A - Method for parkerizing of light metal material surface - Google Patents
Method for parkerizing of light metal material surface Download PDFInfo
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- CN101343736A CN101343736A CNA2007101280993A CN200710128099A CN101343736A CN 101343736 A CN101343736 A CN 101343736A CN A2007101280993 A CNA2007101280993 A CN A2007101280993A CN 200710128099 A CN200710128099 A CN 200710128099A CN 101343736 A CN101343736 A CN 101343736A
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Abstract
Disclosed is a light metal material surface phosphorizing treatment method. The method comprises the following steps: the surface of the light metal material is contacted with a phosphorizing fluid, wherein, the pH value of the phosphorizing fluid is larger than 0.1 and less than 1. The pH value of the phosphorizing fluid is controlled to be larger than 0.1 and less than 1, so the light metal material has adequate corrosion resistance and lower surface resistance. Meanwhile, the corrosion resistance of the products manufactured by the method is qualified, and the common utilizing requirements can be satisfied.
Description
Technical field
The invention relates to a kind of surface treatment method, especially parkerized method is carried out on the light metal material surface about a kind of.
Background technology
Light metal, for example aluminium, magnesium, titanium, aluminium alloy, magnesium alloy and titanium alloy etc., but have that density is little, the conductive and heat-conductive ability is strong, mechanical property is excellent and advantage such as secondary processing, therefore in national economy, obtained using widely.But light metal material itself is a kind of corrosion-prone material, therefore in order to utilize light metal material better, normally by light metal material is carried out the corrosion that the surface-treated method is avoided light metal material.
The chemistry bonderizing is comparatively commonly used in the light metal material surface treatment.Described bonderizing generally is material to be contacted with phosphatization liquid get final product.Behind bonderizing, form phosphate coating on the light metal material surface, make light metal material have superior corrosion resistance.As phosphatization liquid, can be divided into multiple different phosphatization liquid according to the difference of metallic cation, at present, using more is calcium series phosphatating liquid, manganese phosphating liquor, barium based phosphatization liquid and aluminium based phosphatization liquid, the excellent corrosion resistance of the phosphate coating of these phosphatization liquid formation.It has been generally acknowledged that phosphatization liquid pH value is low excessively, can suppress the formation of phosphate coating, make the corrosion resistance nature of phosphate coating reduce.Therefore, under normal conditions, these phosphatization liquid in use, the pH value of described phosphatization liquid requires at 2.0-3.0.
CN 1314836C discloses a kind of magnesium alloy phosphating liquid, this phosphatization liquid is the aqueous solution that is grouped into by following one-tenth, contains in promptly every premium on currency: the promotor SODIUMNITRATE of the phosphoric acid of the zinc oxide of 1-4.5 gram, 10-45 gram, the complexing agent sodium tartrate of 0-20 gram, 0.1-6 gram, the corrosion inhibitor Sodium Fluoride of 0.5-4.5 gram.In this invention, when phosphatization, though the pH value of affiliated phosphatization liquid is 1-4.5,, in this inventive embodiment, the pH value of the minimum of use is 1.9.
The phosphate coating that aforesaid existing parkerizing method forms is all comparatively fine and close, but has the higher problem of resistance value on the surface of the light metal material that obtains behind bonderizing, is generally tens ohm to tens ohm.
Yet, in electronics, the communications field, require used light metal material to have lower resistance, the general requirement resistance value is lower than 2 ohm, and more requires resistance value to be lower than 1 ohm in some applications, even lower.
Therefore, in order to make light metal material, need do more deep research to the surface treatment method of light metal material further in electronics, the bigger effect of communications field performance.
Summary of the invention
The present invention is in order to overcome the excessive shortcoming of surface resistivity of the light metal material that the method handled by existing alramenting obtains, provide a kind of after light metal material is carried out bonderizing, the method that the alramenting that the surface resistivity of the light metal material with phosphate coating that obtains is little is handled.
The present inventor finds after deliberation, under the lower situation of phosphatization liquid pH value, the erosion resistance that forms phosphate coating after the phosphatization can decrease, as long as the pH value is controlled at suitable scope, promptly controls less than 1 greater than in 0.1 the scope, when just can guarantee that light metal material after the phosphatization has enough erosion resistances, has less surface resistivity, thereby make light metal material satisfy and require the low-resistance requirement of material surface, further enlarge the range of application of light metal material at electronics, communication etc.
The invention provides and a kind of parkerized method is carried out on the light metal material surface, this method comprises that the surface with light metal material contacts with phosphatization liquid, wherein, and pH value＜1 of 0.1＜described phosphatization liquid.
The present invention is controlled at less than 1 greater than in 0.1 the scope by the pH value with phosphatization liquid, thereby makes when light metal material has enough erosion resistances to have less surface resistivity.For example, the surface resistivity of the product that obtains after with magnesium alloy phosphating by method of the present invention is all less than 1 ohm, and the surface resistivity of the table plague that the method that adopts prior art obtains is 21 ohm, and therefore, method of the present invention can reduce the surface resistivity of the light metal material after the phosphatization significantly.In addition, the erosion resistance of the product that the present invention obtains is all below 5%, and it is qualified to be, and can satisfy common service requirements.
Embodiment
Of the present inventionly parkerized method is carried out on the light metal material surface comprise that the surface with light metal material contacts with phosphatization liquid, is characterized in that pH value＜1 of 0.1＜described phosphatization liquid.
The present invention is controlled at scope less than 1 by the pH value with phosphatization liquid, can reduce the resistance on light metal material surface effectively on the basis that guarantees the light metal material erosion resistance.Improve the pH value of described phosphatization liquid, can improve the erosion resistance on light metal material surface.Therefore, under the preferable case, pH value＜1 of 0.5≤described phosphatization liquid.
Described pH value can be regulated by adding acid, and described acid is preferably phosphoric acid.As long as the amount of the phosphoric acid that adds in the described phosphatization liquid makes the pH value of phosphatization liquid meet above-mentioned scope.
Phosphatization liquid of the present invention can be various phosphatization liquid.The erosion resistance on described light metal material surface considers that described phosphatization liquid preferably uses one or more in calcium series phosphatating liquid, manganese phosphating liquor, barium based phosphatization liquid and the aluminium based phosphatization liquid after the phosphatization.Described calcium series phosphatating liquid is meant the aqueous solution that contains calcium ion and dihydrogen phosphate ions.Described manganese phosphating liquor is meant the aqueous solution that contains mn ion and dihydrogen phosphate ions.Described barium based phosphatization liquid is meant the aqueous solution that contains barium ion and dihydrogen phosphate ions.Described aluminium based phosphatization liquid is meant and contains the aluminum ion and and the aqueous solution of dihydrogen phosphate ions.Can contain two or more in calcium ion, mn ion, barium ion and the aluminum ion in the described phosphatization liquid simultaneously.Above-mentioned phosphatization liquid can prepare, and also can be commercially available.For example, described calcium series phosphatating liquid can be that the JA0604A calcium series phosphatating liquid of Shanghai clean peace Fine Chemical Co., Ltd, the model of the permanent prompt Chemical Industry Science Co., Ltd in Kunshan, Jiangsu system are PZ-610A; Described manganese phosphating liquor can be the GH-7005 manganese phosphating liquor of Guanghua Science ﹠ Technology Co., Ltd., Shanghai; The preparation method of described barium based phosphatization liquid is that conventional preparation method gets final product, and can the various compositions that the barium based phosphatization liquid is required be dissolved in the water and makes.Described barium based phosphatization liquid contains the Ba of 0.05-0.5mol/L usually
2+, the dihydrogen phosphate ions of 0.05-0.5mol/L and the H of 1-10ml/L
2O
2The preparation method of described aluminium based phosphatization liquid is identical with the preparation method of barium based phosphatization liquid, contains the Al of 0.05-0.5mol/L in the described aluminium based phosphatization liquid usually
3+, the dihydrogen phosphate ions of 0.05-0.5mol/L, the H of 1-10ml/L
2O
2
The process of phosphatization of the present invention is as long as directly contact light metal material with described phosphatization liquid.Described contact temperature is preferably 20-45 ℃, and the time of described contact is preferably 20-70 second.
Described light metal material can be aluminium, magnesium, titanium, aluminium alloy, magnesium alloy and titanium alloy etc. for example, and method of the present invention is suitable for these light metal materials, and method of the present invention is particularly suitable for magnesium alloy materials.
In addition, in the method for the invention, before carrying out phosphatization, this method can also comprise carries out pre-treatment with described light metal material.Described pre-treatment can be conventional the light metal material phosphatization before the pre-treatment process.For example, can be that light metal material is carried out degreasing, activation, adjustment etc.The method of described degreasing is conventionally known to one of skill in the art.For example light metal material directly can be contacted with degreasing fluid and get final product, described degreasing fluid for example can be the aqueous solution of the sodium phosphate of the yellow soda ash of the sodium hydroxide that contains the 5-10 grams per liter, 10-15 grams per liter and 5-15 grams per liter.Described activatory method is the conventional preceding method for activating surface of light metal material phosphatization.For example can directly light metal material be contacted with described activation solution and get final product.Described activation solution for example can contain the 10-20 milliliter/liter acetate and the aqueous solution of the AEO-9 (fatty alcohol polyethenoxy ether class) of 0.5-2 grams per liter.Described adjustment is meant light metal material is contacted with alkaline solution that described alkaline solution for example can be the aqueous sodium hydroxide solution of 30-50 grams per liter.In addition, the present invention comprises that also water cleans light metal material between any two steps of described degreasing, activation, adjustment and phosphatization.
Illustrate in greater detail the present invention below by embodiment.The light metal material that uses in following embodiment and the Comparative Examples is the magnesium alloy materials of the model of producer of Nanjing Yunhai Special Metals Co., Ltd. product as AZ91D.
Embodiment 1
Present embodiment illustrates the method that alramenting of the present invention is handled.
[flow process]
Degreasing → washing → activation → washing → adjustment → washing → phosphatization → oven dry → product
Described degreasing is that described light metal material was soaked 5 minutes in 55 ℃ degreasing fluid, and described degreasing fluid is the aqueous solution of the sodium phosphate of the yellow soda ash of the sodium hydroxide that contains 10 grams per liters, 15 grams per liters and 10 grams per liters.
Described activation is that described light metal material was soaked 3 minutes in 35 ℃ activation solution, and described activation solution is the aqueous solution that contains the AEO-9 of 15 milliliters/liter acetate and 1 grams per liter.
Described adjustment is that described light metal material was soaked 3 minutes in 85 ℃ adjustment liquid, and described adjustment liquid is the aqueous sodium hydroxide solution of 40 grams per liters.
Described phosphatization is that described light metal material was soaked 20 seconds in 45 ℃ phosphatization liquid, and described phosphatization liquid is to be that the pH value of the phosphatization liquid of PZ-610A is adjusted to 0.9 phosphatization liquid with phosphoric acid with the model of the permanent prompt Chemical Industry Science Co., Ltd in Kunshan, Jiangsu system.
Described washing is with 0.5 liter water light metal material to be cleaned twice respectively.
Embodiment 2
Carry out alramenting according to the method for embodiment 1 and handle, different is, described phosphatization liquid is to be that the pH value of the phosphatization liquid of PZ-610A is adjusted to 0.5 phosphatization liquid with phosphoric acid with the model of the permanent prompt Chemical Industry Science Co., Ltd in Kunshan, Jiangsu system.
Embodiment 3
Carry out alramenting according to the method for embodiment 1 and handle, different is, described phosphatization liquid is to be that the pH value of the phosphatization liquid of PZ-610A is adjusted to 0.4 phosphatization liquid with phosphoric acid with the model of the permanent prompt Chemical Industry Science Co., Ltd in Kunshan, Jiangsu system.
Embodiment 4
Carry out alramenting according to the method for embodiment 1 and handle, different is, described phosphatization liquid is to be that the pH value of the phosphatization liquid of PZ-610A is adjusted to 0.7 phosphatization liquid with phosphoric acid with the model of the permanent prompt Chemical Industry Science Co., Ltd in Kunshan, Jiangsu system.
Embodiment 5
Carry out alramenting according to the method for embodiment 1 and handle, different is that the time of described phosphatization is 40 seconds.
Embodiment 6
Carry out alramenting according to the method for embodiment 1 and handle, different is, the temperature of described phosphatization liquid is 25 ℃, and the time of described phosphatization is 70 seconds.
Embodiment 7
Carry out alramenting according to the method for embodiment 1 and handle, different is, described phosphatization liquid is the barium based phosphatization liquid, and this phosphatization liquid is by mixing barium dihydrogen phosphate, phosphoric acid, hydrogen peroxide and water, and wherein, this phosphatization liquid contains the Ba of 0.1mol/L
2+, the H of 0.15mol/L dihydrogen phosphate ions, 5ml/L
2O
2, adjusting the pH value with phosphoric acid then is 0.9, and the temperature of immersion is 25 ℃, and the time of immersion is 20 seconds.
Embodiment 8
Carry out alramenting according to the method for embodiment 1 and handle, different is, the GH-7005 manganese phosphating liquor of described phosphatization liquid Guanghua Science ﹠ Technology Co., Ltd., Shanghai.
Comparative Examples 1
Carry out alramenting according to the method for embodiment 1 and handle, different is that the pH value of described phosphatization liquid is 2.5.
Embodiment 9-16
The performance of the product that present embodiment explanation embodiment 1-8 obtains.
(1) surface resistivity
Use resistance meter (the UT51 MULTIMETER digital multimeter that UNI-T produces) carries out resistance measurement to the surface of the product that embodiment 1-8 obtains.The result is as shown in table 1.
(2) erosion resistance
In temperature is 35 ℃ laboratory, the product that embodiment 1-8 is made places in the salt fog cabinet, under 46 ℃, spray with the air pressure of 1.0 ± 0.025 kilogram force/square centimeters with the sodium chloride brine that pH is 7.0, temperature is 35 ℃ 5 ± 0.5 weight %.At spraying sample after 8 hours, taking out and placing the another one temperature is that 22.5 ℃, relative humidity are the climatic chamber of 47.3%RH, places after 8 hours, and observation sample, the corroded area that writes down sample surfaces accounts for the per-cent of the product total area.Wherein, corroded area be considered as below 5% qualified.The result is as shown in table 1.
Comparative Examples 2
The performance of the product that this Comparative Examples explanation Comparative Examples 1 obtains.
According to the method for embodiment 9 product of Comparative Examples 1 is carried out performance test.The result is as shown in table 1.
Table 1
| Rule of origin | Surface resistivity (ohm) | Erosion resistance (%) |
| Embodiment 1 | 0.8 | 3 |
| Embodiment 2 | 0.6 | 4 |
| Embodiment 3 | 0.3 | 5 |
| Embodiment 4 | 0.4 | 4 |
| Embodiment 5 | 0.5 | 4 |
| Embodiment 6 | 0.4 | 4 |
| Embodiment 7 | 0.6 | 3 |
| Embodiment 8 | 0.7 | 3 |
| Comparative Examples 1 | 21.0 | 1 |
As can be seen from Table 1, the surface resistivity of the product that obtains of embodiment 1-8 will be starkly lower than the product that Comparative Examples 1 obtains.In addition, the erosion resistance of the product that embodiment 1-8 obtains is all below 5%, and it is qualified to be.In addition from embodiment 1-3 as can be seen, the pH value of phosphatization liquid is lower than at 0.5 o'clock, and erosion resistance reduces, and therefore, the pH value of the preferred described phosphatization liquid of the present invention is between 0.5-0.9.
Claims (6)
1, a kind of parkerized method is carried out on the light metal material surface, this method comprises that the surface with light metal material contacts with phosphatization liquid, is characterized in that pH value＜1 of 0.1＜described phosphatization liquid.
2, method according to claim 1, wherein, pH value＜1 of 0.5≤described phosphatization liquid.
3, method according to claim 1, wherein, described contact temperature is 20-45 ℃, be 20-70 second duration of contact.
4, method according to claim 1, wherein, described phosphatization liquid is one or more in calcium series phosphatating liquid, manganese phosphating liquor, barium based phosphatization liquid and the aluminium based phosphatization liquid.
5, method according to claim 1, wherein, described light metal material is a magnesium alloy.
6, method according to claim 1, wherein, the acid of regulating described phosphatization liquid pH value is phosphoric acid.
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| CN200710128099A CN100588739C (en) | 2007-07-13 | 2007-07-13 | Method for parkerizing of light metal material surface |
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|---|---|---|---|
| CN200710128099A CN100588739C (en) | 2007-07-13 | 2007-07-13 | Method for parkerizing of light metal material surface |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824614A (en) * | 2010-04-15 | 2010-09-08 | 吉林大学 | Magnesium alloy surface conversion coating treating fluid and treating process thereof |
| CN102753714A (en) * | 2009-09-11 | 2012-10-24 | 株式会社三德 | Magnesium-lithium alloy, rolled material, molded article, and process for producing same |
| CN102808169A (en) * | 2011-05-31 | 2012-12-05 | 比亚迪股份有限公司 | Lubricating method for aluminum alloy |
| CN103451639A (en) * | 2013-09-29 | 2013-12-18 | 句容市石狮冲压件厂 | Phosphorization method of aluminum alloy outdoor goods |
| CN107779855A (en) * | 2017-11-25 | 2018-03-09 | 蚌埠市福沃特车轮制造科技有限公司 | Phosphating solution for automotive hub phosphatization |
| CN108018545A (en) * | 2017-11-25 | 2018-05-11 | 蚌埠市福沃特车轮制造科技有限公司 | A kind of preparation method of automotive hub high temperature phosphorization liquid |
| CN108867988A (en) * | 2018-05-15 | 2018-11-23 | 安徽德斯兰卡铝业科技有限公司 | A kind of production technology of wood-grain aluminum board |
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2007
- 2007-07-13 CN CN200710128099A patent/CN100588739C/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102753714A (en) * | 2009-09-11 | 2012-10-24 | 株式会社三德 | Magnesium-lithium alloy, rolled material, molded article, and process for producing same |
| US9702033B2 (en) | 2009-09-11 | 2017-07-11 | Santoku Corporation | Magnesium-lithium alloy, rolled material, molded article, and process for producing same |
| CN101824614A (en) * | 2010-04-15 | 2010-09-08 | 吉林大学 | Magnesium alloy surface conversion coating treating fluid and treating process thereof |
| CN102808169A (en) * | 2011-05-31 | 2012-12-05 | 比亚迪股份有限公司 | Lubricating method for aluminum alloy |
| CN102808169B (en) * | 2011-05-31 | 2014-12-10 | 比亚迪股份有限公司 | Lubricating method for aluminum alloy |
| CN103451639A (en) * | 2013-09-29 | 2013-12-18 | 句容市石狮冲压件厂 | Phosphorization method of aluminum alloy outdoor goods |
| CN107779855A (en) * | 2017-11-25 | 2018-03-09 | 蚌埠市福沃特车轮制造科技有限公司 | Phosphating solution for automotive hub phosphatization |
| CN108018545A (en) * | 2017-11-25 | 2018-05-11 | 蚌埠市福沃特车轮制造科技有限公司 | A kind of preparation method of automotive hub high temperature phosphorization liquid |
| CN108867988A (en) * | 2018-05-15 | 2018-11-23 | 安徽德斯兰卡铝业科技有限公司 | A kind of production technology of wood-grain aluminum board |
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|---|---|
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