CN1268582A - Chemical surface treatment liquid composition for magnesium contd. metallic material, surface treatment method and surface treatment matter thereof - Google Patents
Chemical surface treatment liquid composition for magnesium contd. metallic material, surface treatment method and surface treatment matter thereof Download PDFInfo
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Abstract
The present invention relates to protective film capable of long time retaining good corrosion resistant, rust resistant and coating layer adhesion properties, and processing liquid composition capable of processing chrome free magnesium containing metallic material in short time, and surface treatment method and susface treated object. The processing liquid composition is characterized by that is contains calcium ion, manganese ion, phosphate ion and oxidation accelerator.
Description
The Chrome-free that the present invention relates to contain the magnesium metallic substance is the chemical synthesis treatment liquid composition, surface treatment method and surface treatment thing.
Magnesium is a kind of metal lighter than aluminium, and the alloy great majority that form with other metals are used as the higher structured material use of intensity.But, have and the characteristic that is etched easily after the water that contains oxydised component contact owing to contain the magnesium metallic substance, so, after clean, need change into processing, and then carry out processing such as coating at its surperficial formation chemoproection film.
Therefore, the surface treatment that contains the magnesium metallic substance comprises skimming treatment, washes, changes into and handle washing and this several steps of drying treatment.Then, generally carry out processing such as coating again.And, carry out above-mentioned change into processing before, also be immersed in sometimes and corrode processing in the alkali bath.
When carrying out surface treatment to containing the magnesium metallic substance, owing to constitute the aforementioned difference that changes into the composition that changes into treatment agent of handling body lotion, performances such as the erosion resistance of treat surface, rustless property, coating binding property will have very big difference, so people have carried out various research and development to changing into treatment agent.
In the past, the above-mentioned main component that changes into treatment agent was that chromium is metal, because it is harmful to human body and global environment, so, also carried out Chrome-free system is changed into the research and the practical exploitation of treatment agent recently.
The conventional art that Chrome-free system changes into treatment agent comprises the sodium hydroxide solution that makes under the condition of high temperature and contains the method (the clear 61-90776 of Japanese patent application number) that the magnesium metal material surface contacts; The method of handling containing the magnesium metal material surface with pyrophosphate salt solution and alkaline hydrated oxide (open the flat 6-116740 of communique number of Japanese Patent); Under acid ph value, make the aqueous solution that contains phosphoric acid, mn ion and amine compound and contain the method (open the flat 7-126858 of communique number of Japanese Patent) that the magnesium metal material surface contacts; Under acid ph value, make the aqueous solution that contains phosphoric acid, calcium ion or aluminum ion and amine compound and contain method (open the flat 8-176842 of communique number of Japanese Patent) that the magnesium metal material surface contacts etc.
In the above-mentioned example in the past; utilize method 1 and method 2 to form the protective membrane that contains magnesium hydroxide containing the magnesium metal material surface; utilize method 3 to form the protective membrane that contains phosphorus-manganic compound and manganese-nitrogen compound, utilize 4 of methods to form the protective membrane that contains phosphorus-calcium cpd and phosphorus-aluminum compound.By forming said protection film, make the performances such as erosion resistance, rustless property and coating binding property that contain the magnesium metallic substance that bigger improvement arranged.
But; the protective membrane containing the formation of magnesium metal material surface that utilizes above-mentioned traditional method to obtain is abundant not enough to the improvement of performances such as above-mentioned erosion resistance; with the erosion resistance is example; if in the brine spray time is in 100～200 hours such short period of time; then can keep performance effectively; but if the longer time, its performance just can not keep well.This is for containing the magnesium metal products, and practicality is not strong.
Therefore, the purpose of this invention is to provide can handle performances such as being equal to, can guaranteeing for a long time erosion resistance, rustless property and coating binding property with in the past chromium and under lower temperature conditions and the Chrome-free that can handle in short period of time system contain the magnesium metallic substance with chemical synthesis treatment liquid composition, surface treatment method and surface treatment thing.
In order to achieve the above object, the magnesium metal that contains of the present invention is with being constructed as follows of chemical synthesis treatment liquid composition, that is, the feature of said composition is to be made of the aqueous solution that contains calcium ion, mn ion and phosphate anion and oxidation promotor.
The magnesium metal that contains of the present invention also comprises magnesium itself except magnesium alloy such as Mg-Al-Zn alloy, Mg-Zn alloy, Mg-Al-Zn-Mn alloy.
In addition, contain the magnesium metallic substance except metallic substance itself, also comprise the die casting goods.
Calcium ion in the aqueous solution is provided by the mixture more than a kind or 2 kinds in nitrocalcite, calcium nitrite, calcium thiosulfate, lime acetate, the monocalcium phosphate etc.
Mn ion in the aqueous solution is provided by the mixture more than a kind or 2 kinds in manganous carbonate, manganous nitrate, manganous sulfate, manganese hydrogen phosphate, phosphate dihydrogen manganese, the boron manganous fluoride etc.
Phosphate anion in the aqueous solution is then provided by the mixture more than a kind or 2 kinds in ortho-phosphoric acid, condensed phosphoric acid, phosphorous acid, the Hypophosporous Acid, 50 etc.
Oxidation promotor can use oxygenants such as sodium chlorate, clorox.
The magnesium metal that contains of the present invention is at normal temperatures with the chemical synthesis treatment liquid composition, the above-mentioned raw materials reagent mix is dissolved in the water and the aqueous solution that obtains.
In addition, of the present invention contain the magnesium metal with each component ionic content in the chemical synthesis treatment liquid composition for described later in that to contain the amount that changes into protective membrane that the magnesium metal material surface forms extremely important.In order to improve performances such as erosion resistance, rustless property and coating binding property; particularly can be in the relatively short time form the good protective membrane that changes into containing the magnesium metal material surface; calcium ion content in the aqueous solution is preferably 1～20 weight part, mn ion is that 1～4 weight part, phosphate anion are more than 20 weight parts; and the content of oxidation promotor is in the scope of 0.02～2 weight part.
If each component forms composition according to aforementioned proportion, then can be with lower cost, obtain contain the magnesium metal material surface can stably form possess that changing into of superperformance handle film change into the processing body lotion.
More than the magnesium metal that contains of Xing Chenging is applicable to the surface treatment method that contains the magnesium metallic substance of the present invention with the chemical synthesis treatment liquid composition.
The feature that contains the surface treatment method of magnesium metallic substance of the present invention is; mix the aqueous solution that contains calcium ion, mn ion and phosphate anion and oxidation promotor; then its pH value is adjusted to 1.0～3.0 and constituted body lotion; this body lotion is contacted, at the aforementioned hybrid protection film that contains magnesium metal material surface formation calcium, manganese and phosphorus with the magnesium metal material surface that contains of process skimming treatment.
Surface treatment method of the present invention comprises the water-washing step after the skimming treatment; Aforementionedly contain the aqueous solution of calcium ion etc. and changing into of forming handles that body lotion contacts changes into water-washing step after the processing with mixing; And the pure water washing step that according to circumstances carries out subsequently.In addition, also have treatment steps such as passing through of not necessarily comprising in the method for the present invention drying that general method carries out, coating.The common coatings method that is applicable to the inventive method is to electroplate or epoxypaint is sprayed as the bottom paint with epoxypaint, uses melamine resin paint coating etc. more thereon.
Aforementioned changing in the treatment step, the aforementioned aqueous solution that contains calcium ion etc. is about changing into of 6 weight % with concentration in the water, and to handle body lotion be example, wherein calcium ion content be preferably 0.5～10g/l, mn ion be 0.5～2.0g/l, phosphate anion more than 10g/l, the content of oxidation promotor is in the scope of 0.01～1.1g/l.
Handle in the body lotion each component ionic content in above-mentioned scope if change into; then can change into processing to containing magnesium based metal at short notice, can also obtain the hybrid protection film of all good calcium, manganese and phosphorus of performances such as erosion resistance, rustless property, coating binding property simultaneously.
In addition, aforementionedly change into that to handle in the body lotion calcium ion concn not enough or when not containing fully, can cause variation such as erosion resistance and coating binding property, if mn ion or phosphate anion are not enough or do not contain fully, then can make the remarkable variation of coating binding property, contact with the water that contains chlorion, white rust staining can occur, cause outward appearance not good.
In addition, contained oxidation promotor can improve the reactivity that aforementioned each component ion pair contains the magnesium metal material surface when changing into processing, improve performances such as erosion resistance, promotes to change into the formation of protective membrane.So,, just can not obtain to possess the protective membrane that changes into of above-mentioned superperformance if the aforementioned oxidation promotor that changes in the processing body lotion contains quantity not sufficient or do not contain fully.
The aforementioned pH value of handling body lotion that changes into was adjusted to 1.0～3.0 o'clock, can be in that to contain the magnesium metal material surface effective and form the above-mentioned protective membrane that changes into without barrier.
If the pH value of body lotion is lower than 1.0, then erosion amount is excessive, can go wrong on the dimensional precision of metallic substance, and simultaneously the erosion resistance on surface also can reduce, if pH value above 3.0, then can not the obtained performance good protective membrane that changes into.
In addition, aforementioned change into the temperature of handling body lotion better be remain on more than 30 ℃, below 75 ℃.If bath temperature is lower than 30 ℃, the then aforementioned formation that changes into protective membrane needs the long period, and it is not good that gained changes into the performance of protective membrane, if surpass 75 ℃, then overreact can make the degradation that changes into protective membrane of formation on the contrary.
In addition, it is relevant with the duration of contact on body lotion and treated material surface to change into the temperature condition of handling body lotion.That is, when bath temperature was low, duration of contact is long, and bath temperature was higher for good, and then duration of contact is short in well.
Specifically, when bath temperature is controlled at below 50 ℃, be preferably 10～20 minutes duration of contact,, then be preferably 5～10 minutes duration of contact if bath temperature maintains more than 50%.In addition, longer if bath temperature surpasses 50 ℃ and duration of contact, then can cause the stripping again of formed protective membrane, performance such as erosion resistance is reduced.If it is shorter that bath temperature is lower than 50 ℃ and duration of contact, then can not the obtained performance good protective membrane that changes into.
Surface treatment method of the present invention comprises the step that corrodes processing after skimming treatment with acid bath as pre-treatment.Acid bath can use phosphoric acid class, nitrose, hydrofluoric acid class solution.Even above-mentioned erosion handle to as if having the magnesium alloy die casting of certain releasing agent on the surface, also can utilize the following treatment step that changes into to form the well behaved protective membranes that change into such as erosion resistance on its surface.
Above-mentioned erosion is handled and is exceeded spot not occur, if set excessive concentration, then erosion amount is excessive, more spot can occur, if it is low excessively to set concentration, then corrosion treatment is abundant inadequately.
In addition, surface treatment method of the present invention also comprises in order to carry out skimming treatment the method for body lotion pH value being adjusted to more than 13.Utilize this method to make to contain the magnesium metallic substance and accept skimming treatment, just can obtain the protective membrane that changes into that has good stability in the treatment step in following changing in its passive state.Particularly when process object be die casting goods etc. when containing the material of releasing agent, do not handle even do not carry out aforementioned erosion, also can obtain performances such as good anti-corrosion.In addition, for the pH value of degreasing body lotion is adjusted to more than 13, can increase the combined amount of highly basic etc.
The mixing that the magnesium metal material surface formed calcium, manganese and phosphorus that contains that utilizes that above-mentioned surface treatment method obtains changes into protective membrane.Utilize this to change into protective membrane and can make and contain the magnesium metallic substance and possess performances such as good anti-corrosion, rustless property and coating binding property, and can not bubble, outward appearance is preferable.
When the above-mentioned calcium contents that changes in the protective membrane is 1～500mg/m
2, manganese is 1～500mg/m
2, phosphorus is 1～1000mg/m
2The time, can obtain above-mentioned performance.
(test example 1)
Make the castings that the JISH5303MC2 alloy is a raw material (10cm * 5cm * 2mm), with it as test film.
With the order that skimming treatment → wash → change into processing → washing → pure water washs → dehydrates above-mentioned test film is carried out surface treatment.The details for the treatment of processes is as follows.
(1) the used reagent of skimming treatment is made up of the sodium hydroxide of 10～15g/l and the tensio-active agent of 2～3g/l, and its pH is 11.5～12, and temperature is 40～45 ℃, test film is soaked therein handled in 3 minutes.
(2) changing into processing is that the temperature of handling body lotion that respectively changes into that the sample No.1 shown in the table 1～23 are formed is adjusted to 60～70 ℃, test film is soaked respectively in above-mentioned body lotion handled in 2 minutes.
Table 1-(1)
| ???1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ????9 | ????10 | ????11 | ???12 | |
| ???Ca 2+ | ??1.3 | ???2.6 | ???3.9 | ???5.2 | ???2.6 | ???2.6 | ???2.6 | ???2.6 | ???2.6 | ???2.6 | ???2.6 | ???2.6 |
| ???Zn 2+ | ????- | ????- | ????- | ????- | ???1.25 | ???2.5 | ???3.75 | ???5.0 | ????- | ????- | ????- | ????- |
| ???Ni 2+ | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ???0.55 | ???1.1 | ???1.65 | ???2.2 |
| ???Mn 2+ | ????- | ????- | ????- | ????- | ????- | ????- | ????- | ?????- | ????- | ????- | ????- | ????- |
| ???PO 4 3- | ??13.8 | ???13.8 | ???13.8 | ???13.8 | ???13.8 | ???13.8 | ???13.8 | ???13.8 | ???13.8 | ???13.8 | ???13.8 | ???13.8 |
| ???NaClO 3 | ??0.42 | ???0.42 | ???0.42 | ???0.42 | ???0.42 | ???0.42 | ???0.42 | ???0.42 | ???0.42 | ???0.42 | ???0.42 | ???0.42 |
Table 1-(2)
| ????13 | ????14 | ????15 | ????16 | ????17 | ????18 | ????19 | ????20 | ???21 | ????22 | |
| ????Ca 2+ | ???2.6 | ????2.6 | ???2.6 | ???2.6 | ???2.6 | ????2.6 | ???2.6 | ????2.6 | ???2.6 | ????2.6 |
| ????Zn 2+ | ????- | ?????- | ????- | ????- | ?????- | ?????- | ????- | ?????- | ????- | ????0.6 |
| ????Ni 2+ | ????- | ?????- | ????- | ????- | ?????- | ?????- | ????- | ?????- | ???1.1 | ????1.1 |
| ????Mn 2+ | ???0.3 | ????0.6 | ???0.9 | ???1.2 | ?????- | ?????- | ????- | ?????- | ???0.6 | ????0.6 |
| ????PO 4 3- | ???13.8 | ????13.8 | ???13.8 | ???13.8 | ????6.9 | ????20.7 | ???27.6 | ???13.8 | ???13.8 | ???13.8 |
| ????NaClO 3 | ???0.42 | ????0.42 | ???0.42 | ???0.42 | ????0.42 | ????0.42 | ????- | ???0.84 | ???0.42 | ???0.42 |
(3) washing and all carry out at normal temperatures with the step that the deionization pure water washs lasts 0.5 minute.
Temperature when (4) dry is 100～120 ℃, dewaters 20 minutes.
Then, on above-mentioned surface treated test film, utilize cation electroplating method separate application Resins, epoxy.
Utilize common method to be provided with cross cut on above-mentioned surface, then with it as sample, according to JIS-Z2371, carry out 480 hours salt spray testing (SST) respectively.Then, again same sample is carried out 240 hours salt water immersion tests (15～25 ℃ of 3% salt solutions) respectively, observe the degrees of expansion of filming around the cross cut, the part extent of exfoliation of filming, the binding property of filming and whether adularescent rust staining and outward appearance situation such as whether bubble in addition, its result is as shown in table 2.
Table 2
| Test No. | SST (480 hours) | Salt water retting (240 hours) | (remarks) | ||||||||
| Degrees of expansion | Extent of exfoliation | Binding property | Outward appearance | Degrees of expansion | Extent of exfoliation | ||||||
| ??n 1 | ??n 2 | ??n 3 | ??n 4 | ??n 5 | ??n 6 | ??n 7 | ??n 8 | ||||
| ???1 | ???2.5 | ???4.5 | All | ???4.0 | ???× | ???× | Do not have | ???1.5 | ???1.5 | ???1.5 | |
| ???2 | ???2.5 | ???3.0 | ???7.0 | ???9.0 | ???× | ???△ | ??3.0 | ???2.0 | ???4.0 | ???1.5 | |
| ???3 | (144 hours) are corroded more serious | ???○ | ???- | ??1.5 | ???1.0 | ???0.5 | ???1.5 | ||||
| ???4 | ????- | ???5.0 | ???7.0 | ???9.0 | ???○ | ???× | ??1.0 | ???1.5 | ???1.5 | ???1.0 | |
| ???5 | (144 hours) are corroded more serious | ???- | ???- | ??1.5 | ???3.5 | All | All | A large amount of bubbles appear | |||
| ???6 | Because the CED outward appearance is not good, does not test | ||||||||||
| ???7 | The same | ||||||||||
| ???8 | The same | ||||||||||
| ???9 | ???3.5 | ???3.5 | ???2.0 | ???3.0 | ???○ | ???× | Do not have | ????4.0 | ???1.0 | ???4.0 | |
| ???10 | ???2.5 | ???2.5 | ???3.5 | ???1.5 | ???○ | ???× | Do not have | ?????* | ???1.5 | ????* | *, a large amount of white rust stainings appear |
| ???11 | (240 hours) are corroded more serious | ???- | ???- | ??0.5 | ?0.5＞ | ???2.0 | Do not have | Corrode serious | |||
| ???12 | (144 hours) are corroded more serious | ???- | ???× | (72 hours) all have rust staining | |||||||
| ???13 | ???3.0 | ???5.0 | ???4.0 | ???7.5 | ???○ | ???× | 0.5＞ | ???1.0 | ???1.5 | ???1.5 | |
| ???14 | ???2.0 | ????- | ???1.5 | ????- | ???○ | ???○ | ??1.0 | ????- | ???2.0 | ????- | |
| ???15 | ???3.0 | ???2.5 | ???3.0 | ???2.5 | ???○ | ???△ | ??1.0 | ???0.5 | ???1.0 | ???0.5 | Corrode serious |
| ???16 | ???2.0 | ???3.0 | ???2.0 | ???1.5 | ???○ | ???△ | ??0.5 | ???1.0 | ???2.0 | ???1.5 | |
| ???17 | All | ???5.0 | All | ???5.5 | ???○ | ???× | ??2.5 | ???1.5 | ???2.0 | ???2.0 | |
| ???18 | ???2.0 | ???1.5 | ???2.0 | ???1.0 | ???○ | ???○ | ??0.5 | ???0.5 | Do not have | ???1.0 | |
| ???19 | Do not have | ???1.0 | Do not have | ???1.5 | ???○ | ???○ | ??0.5 | ???1.0 | ???1.0 | ???1.0 | Corrode serious |
| ???20 | ???3.0 | ???8.5 | ???8.0 | ???8.5 | ???× | ???× | ??1.0 | ???0.5 | ???1.0 | ???0.5 | Corrode serious |
| ???21 | All | ???5.0 | All | All | ???× | ???× | ??2.0 | ???0.5 | ???2.5 | ???3.0 | A large amount of bubbles appear |
| ???22 | (144 hours) are corroded more serious | ???- | ???- | ??0.5 | ???1.0 | ???2.0 | ???1.5 | ||||
| ???23 | Because the CED outward appearance is not good, does not test | ||||||||||
(unit of numerical value is mm in the table)
In addition, binding property is carried out according to JIS-K5400, specimen surface be provided with 100 chessboard grid (10 * 10 * 1mm), measure pull off again with taping up after also remaining grid number, this numerical value is 100, just counts zero, in addition be *.In appearance, no matter white rust staining appears in specimen surface, bubble appears still, all count *, if little or nothings is all then counted △, if above-mentioned a kind of situation only occurs, and little or nothing, then count zero, if either way do not take place, then count ◎.In addition, can not carrying out after aforementioned plating or the coating the not good situation of outward appearance, all to be considered to the CED outward appearance not good.
Can find out Ni in the Ca-Zn system of sample No.5～8, the Ca-Ni system of sample No.10～12 from the result shown in the table 2
2+When concentration is higher, changing into of the Zn-Ni-Mn system of the Ni-Mn of sample No.22 system and sample No.23 handle body lotion and all have problems aspect erosion resistance.Corresponding to this, the Ca-Mn of sample No.13～16 is that the body lotion that component forms possesses good anti-corrosion and coating binding property, from outside watch, at the Mn of sample No.14
2+Near the concentration, can obtain result preferably.So just can confirm, be body lotion to after containing the magnesium metallic substance and changing into processing with Ca-Mn-P, can improve performances such as erosion resistance effectively.Can find out from the result of sample No.6～8 and No.23, at Zn
2+Exist the protective membrane of priming operation coating not so good.
(embodiment 1)
The die casting goods that the magnesium alloy materials of JIS-H5303-MC2 is made carry out following surface treatment.Add man-hour carrying out die casting, having used Chrome-free is releasing agent.
Above-mentioned die casting goods are carried out the processing same with afore-mentioned test example 1, but after skimming treatment, again it is immersed in the erosion that contains the etchant of each component shown in the following table 3 and handles in the body lotion and corrode processing, as pre-treatment.Change into and handle used changing into to handle body lotion be the aqueous solution that contains 15.2g/l nitrocalcite 4 hydrates, 2.1g/l manganous carbonate, 19.2g/l 75% phosphoric acid and 0.4g/l sodium chlorate, be adjusted into 1.65～1.70 70 ℃ of pH values then this body lotion.Changing into the treatment time is 3 or 5 minutes.After the processing, Resins, epoxy is sprayed on the goods as the bottom paint, coating melamine resin thereon then, other each points are identical with test example 1.
Table 3
| Implement No. | Corrode treatment agent | Change into the treatment time (branch) | The SST time (time) | ||||
| ??120 | ??200 | ???312 | ???????312 | ????312 | |||
| Degrees of expansion (mm) | Extent of exfoliation (mm) | Outward appearance | |||||
| ???1 | Do not have | ?????3 | Do not have | ???2.5 | ??3.0 | ???????7.0 | ????× |
| ???2 | ?????5 | ???1.0 | ???1.0 | ??1.0 | ???????0.5 | ????○ | |
| ???3 | Nitric acid (0.6%) | ?????3 | ??0.5＞ | ???0.5 | ??1.0 | ???????1.0 | ????○ |
| ???4 | ?????5 | ???0.5 | ???0.5 | ??1.0 | ???????1.0 | ????◎ | |
| ???5 | Phosphoric acid (0.5%) | ?????3 | ???0.5 | ???1.0 | ??1.0 | ???????1.0 | ????○ |
| ???6 | ?????5 | ???0.5 | ???0.5 | ??0.5 | ???????1.0 | ????○ | |
| ???7 | Hydrofluoric acid (0.2%)+sulfuric acid (0.7%) | ?????3 | ???1.0 | ???1.0 | ??2.0 | ???????2.0 | ????○ |
| ???8 | ?????5 | ???1.0 | ???1.5 | ??2.5 | ???????2.5 | ????△ | |
Under these conditions, will be through the surface-treated die casting goods that comprise top coat as sample, the result who each sample is carried out salt spray testing is as shown in table 3.The appraisal procedure of this test is identical with test example 1.Can find out from table 3, for the die casting goods, when not carrying out the erosion treatment project as pre-treatment, the SST erosion resistance of implementing No.1 and No.2 is by changing into the treatment time decision, particularly can find out that from the result who implements No.1 the time is short more, performances such as erosion resistance are bad more.So the treated state under the above-mentioned situation may be unstable,, can find out that after having carried out corroding processing, the SST erosion resistance is all better, and is not subjected to time effects, and is in stable condition during processing corresponding to this from the result who implements No.3～No.8.
(embodiment 2)
Can find out from the result of embodiment 1; under the situation of also carrying out when magnesium alloy die casting goods are carried out surface treatment handling as the erosion of pre-treatment; if Ca-Mn-P hybrid protection film; even the treatment time is shorter so; also can obtain well behaved filming such as erosion resistance; no matter handle technically but additionally corrode, or all be disadvantageous on the economy.
So, in this test example, the result that reference table 3 is implemented No.2 does not corrode processing, handle body lotion with changing into similarly to Example 1 magnesium alloy die casting product surface is carried out the processing that changes into more than 5 minutes, in this case, the treatment time is as shown in table 4 to the test result enforcement No.9～No.18 of the influence of the film performance after handling with the temperature that changes into the processing body lotion.Other treatment condition are identical with test example 1.
Table 4
| Implement No. | Change into processing | The SST time (hour) | ||||
| Treatment temp | Treatment time | ???100 | ??200 | ???300 | ?????300 | |
| ???(℃) | (minute) | Degrees of expansion (mm) | Extent of exfoliation (mm) | |||
| ???9 | ????30 | ????5 | ??0.5＞ | ??1.0 | ??1.0 | ?????1.0 |
| ???10 | ????20 | ??0.5＞ | ??0.5 | ??1.0 | ?????1.0 | |
| ???11 | ????40 | ????5 | ??0.5 | ??1.5 | ??3.0 | ?????2.0 |
| ???12 | ????15 | ??0.5＞ | ??0.5 | ??0.5 | ?????0.5 | |
| ???13 | ????50 | ????5 | ??0.5 | ??1.0 | ??2.5 | ?????2.0 |
| ???14 | ????15 | ??0.5 | ??1.0 | ??1.5 | ?????1.0 | |
| ???15 | ????60 | ????5 | ??0.5 | ??1.5 | ??1.5 | ?????1.5 |
| ???16 | ????15 | ??0.5 | ??1.5 | ??2.0 | ?????3.0 | |
| ???17 | ????70 | ????10 | ??0.5 | ??0.5 | ??0.5 | ?????0.5 |
| ???18 | ????15 | ??0.5 | ??2.0 | ??3.0 | ?????1.5 | |
Can find out from the result of table 4,, then can obtain good the filming of SST erosion resistance if change in the scope of 30～70 ℃ of temperature handling body lotion.Implement the SST performance of No.11 and No.13 and test No.16 and No.18 and all hang down than other test examples, the former is that the latter is then caused by overreact because reaction is insufficient.That is, if treatment temp below 50 ℃, the treatment time is more than 5 minutes, or treatment temp surpasses 50 ℃, the treatment time, then result was with even more ideal below 15 minutes.
(embodiment 3)
Then, magnesium alloy die casting goods are carried out surface treatment, because the performances such as erosion resistance of filming, the weather resistance under exacting terms more should be better, and surface treatment process is as follows.
That is, surface treatment process is identical with afore-mentioned test example 1, but formation changes into each moiety that changes into treatment agent of processing body lotion shown in the proportional quantity of the enforcement No.19～No.26 of following table 5.In addition, implement changing into of No.26 and handle the magnesium ion that comprises the 1.0g/l concentration that magnesium alloy die casting goods generate in the surface treatment process in the body lotion sometimes.
Table 5
| Change into the moiety of treatment agent | Embodiment | Comparative example | |||||||||||
| ????19 | ???20 | ????21 | ????22 | ???23 | ????24 | ????25 | ???26 | ?????1 | ?????2 | ???3 | ????4 | ???5 | |
| Nitrocalcite (Ca 2+) | ???15.2 ???(2.6) | ??21.2 ??(3.6) | ????2.2 ???(0.4) | ????34.7 ???(5.9) | ??15.2 ?(2.6) | ?15.2 ?(2.6) | ???0.6 ??(0.1) | ?34.7 ?(5.7) | ???15.2 ???(2.6) | ????- | ??15.2 ??(2.6) | ???21.2 ??(3.6) | ???- |
| Manganous carbonate (Mn 2+) | ????2.1 ???(1.0) | ???2.9 ??(1.3) | ????2.1 ???(1.0) | ????2.1 ???(1.0) | ??0.5 ?(0.2) | ???9.1 ??(4.3) | ????0.1 ??(0.05) | ??2.1 ?(1.0) | ????2.1 ???(1.0) | ????2.1 ???(1.0) | ???- | ???2.1 ??(1.0) | ???- |
| (75%) phosphoric acid (PO 4 3-) | ???19.2 ???(14. ????0) | ??26.7 ??(19. ???4) | ???19.2 ???(14. ????0) | ???38.4 ???(28. ????0) | ??19.2 ??(14. ???0) | ??38.4 ??(28. ???0) | ???0.7 ??(0.5) | ??48.8 ??(35. ???6) | ???19.2 ???(14. ????0) | ???28.3 ???(20. ????6) | ??19.2 ??(14. ???0) | ???21.0 ??(15.3 ????) | ???- |
| Sodium chlorate | ???0.4 | ??0.4 | ???0.4 | ???0.4 | ??0.4 | ???0.4 | ???0.4 | ??0.4 | ???0.4 | ???0.4 | ??0.4 | ???0.4 | ???- |
| ??Mg 2+ | ????- | ???- | ????- | ????- | ???- | ????- | ????- | ??1.0 | ????- | ????- | ???- | ???1.0 | ???- |
| Water | Residual | Residual | Residual | Residual | Residual | Residual | Residual | Residual | Residual | Residual | Residual | Residual | ???- |
(numerical value unit is g/l in the table)
In addition, the foregoing description is as shown in table 6, in the treating processes during skimming treatment pH of body lotion be adjusted to 13～14 respectively, other treatment condition comprise that coating process is the cation electroplating method, and are identical with test example 1.By this treating processes, process object is carried out surface treatment, and carried out coating, the result who carries out 1000 hours salt spray testings is as shown in table 6.
Table 6
| Implement | The degreasing condition | Change into the processing body lotion | Change into protective membrane (mg/m 2) | SST (1000 hours) | Binding property | ||||
| ?????No. | ????(pH) | The pH value | ?????Ca | ?????Mn | ?????P | Degrees of expansion (mm) | Whether bubble is arranged | ||
| Embodiment | ??19 | ???13～14 | ????1.65～1.70 | ??140～180 | ????80～110 | ??580～650 | ????1.0～1.5 | Do not have | ?○ |
| ??20 | ???13～14 | ????1.50～1.55 | ??200～250 | ???100～150 | ??800～900 | ????0.5～1.0 | Do not have | ?○ | |
| ??21 | ???13～14 | ????1.65～1.70 | ????5～40 | ????80～110 | ??580～650 | ????1.5～2.0 | Do not have | ?○ | |
| ??22 | ???13～14 | ????1.40～1.45 | ??300～400 | ???100～150 | ??800～900 | ????0.5～1.0 | Do not have | ?○ | |
| ??23 | ???13～14 | ????1.65～1.70 | ??140～180 | ?????5～40 | ??580～650 | ????1.0～1.5 | Do not have | ?○ | |
| ??24 | ???13～14 | ????1.15～1.20 | ??140～180 | ???300～450 | ??800～900 | ????0.5～1.0 | Do not have | ?○ | |
| ??25 | ???13～14 | ????2.85～2.90 | ????5～40 | ?????5～40 | ????5～40 | ????2.5～3.0 | Do not have | ?○ | |
| ??26 | ???13～14 | ????2.25～2.30 | ??140～180 | ????80～110 | ??580～650 | ????1.0～1.5 | Do not have | ?○ | |
| Comparative example | ???1 | ??11.5～12 | ????1.65～1.70 | ??140～180 | ????80～110 | ??300～500 | ????3.0～5.0 | (in a large number) arranged | ?○ |
| ???2 | ???13～14 | ????1.55～1.60 | ?????- | ???100～150 | ??580～650 | 2.0～3.0 (480 hours) | Have | ?△ | |
| ???3 | ???13～14 | ????1.65～1.70 | ??140～180 | ??????- | ??580～650 | ????1.0～2.0 | Do not have | ?× | |
| ???4 | ???13～14 | ????3.01～3.05 | ????5～40 | ????5～40 | ???5～40 | All (480 hours) | Have | ?× | |
| ???5 | ???13～14 | ???????- | ?????- | ??????- | ?????- | All (480 hours) | ????- | ?× | |
| ???6 | ???13～14 | ???????- | ?????- | ??????- | ?????- | 2.0～3.0 (480 hours) | Have | ?△ | |
The evaluation criteria of each performance is identical with test example 1 in the table 6.
In aforementioned table 5 and the table 6, the one-tenth that changes into treatment agent of comparative example No.1 is grouped into to implement No.19 identical, but the degreasing condition is pH11.5～12.
As shown in table 6, under the treatment condition of comparative example 1, if envrionment conditions is more harsh, then film performance can reduce, and has particularly produced a large amount of bubbles.Corresponding to this, under the treatment condition of implementing No.19～25, the weather resistance in the performance of filming all increases.
Table 6 has been listed respectively and has been changed into the content that changes into calcium contained in the protective membrane, manganese and phosphorus of handling the back gained.From shown in containing of each composition element take temperature, implement all to have used the hybrid protection film of calcium, manganese and phosphorus under the treatment condition of No.19～26.
In table 5 and the table 6, what change in the treatment agent calcium ions not is comparative example 2, and what do not contain mn ion is comparative example 3, and what do not change into processing is comparative example 5.
Under the above-mentioned treatment condition, all have problems aspect the bubble in the erosion resistance and produce of filming that comprises binding property, the weather resistance of filming is also not so good.Corresponding to this, if use the hybrid protection film of aforementioned calcium, manganese and phosphorus, as implementing No.19～No.25, its weather resistance just effectively improves.Can find out from the result who implements No.20, No.22 and No.24, increase any in the composition elements such as calcium, manganese and phosphorus that gained changes into protective membrane and can both improve weather resistance.
The result of enforcement No.26 in the table 6 compares with comparative example 4, of the present inventionly changes into the processing body lotion if use, even a large amount of magnesium ions of stripping in the same body lotion consider also can obtain effective treated protective membrane from the angle of handling load.
The comparative example 6 of table 6 is the results that utilize chromium facture in the past to handle.That is, changing into treatment agent is the solution that contains 150g/l sodium dichromate 99 and 2.5g/l magnesium fluoride, with it as changing into the processing body lotion.The degreasing condition is that body lotion pH13～14, bath temperature are that 90～100 ℃, treatment time are 10 minutes, and changing into when handling bath temperature and be 90～100 ℃, treatment time is 30 minutes, identical with the treating processes of afore-mentioned test example 1.Can find out from result shown in the table 6, utilize the treatment condition of comparative example 5, can not bear 1000 hours salt spray testing.
As mentioned above, utilize above formation, the present invention possesses following effect.
The magnesium metal that contains of the present invention is handled body lotion use as changing into changing into when handling with changing into treatment agent after skimming treatment, can obtain to possess good corrosion resistance, the handled thing of the hybrid protection film of calcium, manganese and the phosphorus of performances such as rustless property, coating binding property.
Treatment process of the present invention is a chromium-free treatment, so just can thereby not cause public hazards because of the former of chromium ion, and the security when operation also guarantees to some extent.
In addition, utilize the treatment process that comprises as the erosion engineering of pre-treatment of the present invention, the surface treatment that the magnesium alloy die casting goods that adhered to releasing agent are carried out can keep good film performance etc. effectively.In addition, skimming treatment condition of the present invention is more than the pH13, so, even handle, also can carry out the better surface treatments of weather resistance such as erosion resistance to above-mentioned die casting goods without corroding.
Claims (8)
1. one kind contains magnesium metal chemical synthesis treatment liquid composition, it is characterized in that, by comprising calcium ion, mn ion and phosphate anion, and the aqueous solution of oxidation promotor constitutes.
2. the magnesium metal chemical synthesis treatment liquid composition that contains as claimed in claim 1, its feature is that also in the above-mentioned aqueous solution, calcium ion is that 1～20 weight part, mn ion are 1～4 weight part, phosphate anion is more than 20 weight parts, and oxidation promotor is 0.02～2 weight part.
3. the surface treatment method that contains the magnesium metallic substance; it is characterized in that; mix the aqueous solution that contains calcium ion, mn ion and phosphate anion and oxidation promotor; then its pH value is adjusted to 1.0～3.0 and constituted body lotion; this body lotion is contacted, at the aforementioned hybrid protection film that contains magnesium metal material surface formation calcium, manganese and phosphorus with the magnesium metal material surface that contains of process skimming treatment.
4. the surface treatment method that contains the magnesium metallic substance as claimed in claim 3, its feature also is, mix the aqueous solution that contains calcium ion, mn ion and phosphate anion and oxidation promotor, then its pH value is adjusted into 1.0～3.0 and constitutes body lotion, again the temperature of this body lotion is adjusted to more than 30 ℃ below 75 ℃, body lotion is contacted with containing the magnesium metal material surface, and duration of contact is more than 5 minutes below 15 minutes.
5. as claim 3 or the 4 described surface treatment methods that contain the magnesium metallic substance, its feature also is, after the skimming treatment, utilizes acid bath to corrode processing as pre-treatment.
6. as claim 3 or the 4 described surface treatment methods that contain the magnesium metallic substance, its feature also is, for carrying out skimming treatment, the pH value of body lotion is adjusted to more than 13.
7. surface treatment thing that contains the magnesium metallic substance; it is characterized in that; after comprising skimming treatment; mix the aqueous solution that contains calcium ion, mn ion and phosphate anion and oxidation promotor; its pH value is adjusted to 1.0～3.0 constitutes body lotions, make again this body lotion with contain the magnesium metal material surface contact and form change into protective film.
8. the surface treatment thing that contains the magnesium metallic substance as claimed in claim 7, its feature also are, change into and contain 1～500mg/m in the protective film
2Calcium, 1～500mg/m
2Manganese and 1～1000mg/m
2Phosphorus.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99104745 CN1220791C (en) | 1999-03-30 | 1999-03-30 | Chemical surface treatment liquid composition for magnesium contd. metallic material, surface treatment method and surface treatment matter thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99104745 CN1220791C (en) | 1999-03-30 | 1999-03-30 | Chemical surface treatment liquid composition for magnesium contd. metallic material, surface treatment method and surface treatment matter thereof |
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| CN1268582A true CN1268582A (en) | 2000-10-04 |
| CN1220791C CN1220791C (en) | 2005-09-28 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303248C (en) * | 2001-11-21 | 2007-03-07 | 日本油漆株式会社 | Method of surface treatment for magnesium and/or magnesium alloy, and magnesium and/or magnesium alloy product |
| CN102899656A (en) * | 2012-08-31 | 2013-01-30 | 北方工业大学 | Preparation method of nano alumina particle reinforced conversion film |
| CN104018149A (en) * | 2014-06-11 | 2014-09-03 | 张家港保税区冠祥贸易有限公司 | Phosphating solution for surface pretreatment of metal product and preparation method of phosphating solution |
| CN106544663A (en) * | 2016-10-26 | 2017-03-29 | 博罗县东明化工有限公司 | Magnesium alloy Ca W Mn conversion film treating agents and magnesium alloy Ca W Mn processing methods |
-
1999
- 1999-03-30 CN CN 99104745 patent/CN1220791C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303248C (en) * | 2001-11-21 | 2007-03-07 | 日本油漆株式会社 | Method of surface treatment for magnesium and/or magnesium alloy, and magnesium and/or magnesium alloy product |
| CN102899656A (en) * | 2012-08-31 | 2013-01-30 | 北方工业大学 | Preparation method of nano alumina particle reinforced conversion film |
| CN102899656B (en) * | 2012-08-31 | 2014-07-30 | 北方工业大学 | Preparation method of nano alumina particle reinforced conversion film |
| CN104018149A (en) * | 2014-06-11 | 2014-09-03 | 张家港保税区冠祥贸易有限公司 | Phosphating solution for surface pretreatment of metal product and preparation method of phosphating solution |
| CN106544663A (en) * | 2016-10-26 | 2017-03-29 | 博罗县东明化工有限公司 | Magnesium alloy Ca W Mn conversion film treating agents and magnesium alloy Ca W Mn processing methods |
| CN106544663B (en) * | 2016-10-26 | 2019-04-19 | 博罗县东明化工有限公司 | Magnesium alloy Ca-W-Mn conversion film treating agent and magnesium alloy Ca-W-Mn processing method |
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| Publication number | Publication date |
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| CN1220791C (en) | 2005-09-28 |
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