CN1294203A - High corrosion resistant surface treated magnesium alloy product and its mfg. process - Google Patents
High corrosion resistant surface treated magnesium alloy product and its mfg. process Download PDFInfo
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Abstract
Disclosed is a method for processing high corrosion resistance surface treated magnesium alloy product, the surface of an aluminum-containing magnesium alloy is subjected to chemical treatment for 0.3 to 10 min with a treating solution in which the concentration of the water soluble salt of permanganic acid or manganic acid is >= 2 g/L expressed in terms of the content of KMnO4 and also less than the solubility thereof, the concentration of the water soluble salt of phosphoric acid is 0.05 to 100 g/L expressed in terms of the content of Na3PO4, the concentration of acetic acid is 0.05 to 100 ml/L, the concentration of sodium acetate is 0.05 to 50 g/L, pH is <= 7, and solution temperature is 288 to 368 K, and the high corrosion resistance surface treated magnesium alloy product is obtained by the producing method. A magnesium alloy product having a high corrosive resistance surface produced according to the present invention has a Mn adhesion of 100 to 600 mg/m2, P adhesion of < 200 mg/m2, CH3COO-adhesion of 0.01 to 1000 mg/m2.
Description
The present invention relates to aluminiferous Mg alloy surface is made by chemical treatment the surface treated magnesium alloy product and the manufacture method thereof of high corrosion resistance, in more detail, what relate to is the treatment solution that does not contain deleterious 6 valency chromium by adopting, carry out the chemical treatment manufacturing but have equal or higher erosion resistance with the chromate treating product that carry out chemical treatment with the treatment solution that contains 6 valency chromium, and, high corrosion resistant surface treated magnesium alloy that recirculation is high and manufacture method thereof.
As used for magnesium alloy, particularly bathe as the chemical treatment of aluminiferous used for magnesium alloy, known 3 kinds that JIS H 8651 standards are arranged, and the special chromic acid salt bath of opening record such as flat 8-225954 communique, 11 kinds of JIS H 8651 standards in addition, and the spy opens flat 8-35073 communique, Jan Ivar Skar, et al_SAE Technical PaperSeries, 970324, pp-7-11,1997, David Hawke, et al_MetalFinishing 93,10, pp34-38, the chemical treatment of the water-soluble salt that contains permanganic acid or mangaic acid of records such as 1955 is bathed also known, in addition, the spy opens clear 57-41376 communique, the water-soluble salt that contains permanganic acid and the titanium salt of records such as Te Kaiping 11-36082 communique, and/or the chemical treatment of zirconates is bathed also known.
By carrying out chemical treatment, can obtain high corrosion resistant surface treated magnesium alloy product, yet 6 contained in chromic acid salt bath valency chromium are objectionable impuritiess with the chromic acid salt bath.
With the chemical treatment bath that contains heavy metallic salt magnesium alloy is being carried out chemically treated occasion, its erosion resistance degree is insufficient, and, when recirculation, when these heavy metals become impurity, difficult to the adjustment change of alloy composition.
Also have, manganiferous situation is arranged in magnesium alloy, for example, employed AZ is an alloy in the electronic machine field, and the AZ that uses in automobile component is in the aluminiferous magnesium alloy such as alloy, contains about manganese 0.1-0.5% (quality).Therefore, employing contains the chemical treatment bath of the water-soluble salt of permanganic acid or mangaic acid magnesium alloy is carried out chemically treated occasion, can obtain the high erosion resistance surface treated magnesium alloy of recirculation, yet, its erosion resistance degree may not necessarily meet the demands, and therefore also requires further to improve.
Problem of the present invention is, constitute the heavy metal of impurity when not containing as 6 valency chromium of objectionable impurities and recirculation by adopting, and can reach with to adopt the chromic acid salt bath to carry out chemical treatment equal or than a kind of non-chromate treatment solution of its better erosion resistance, thereby the manufacture method of high corrosion resistant surface treated magnesium alloy product can be provided, and the high corrosion resistant surface treated magnesium alloy product that makes with this treatment solution.
Found that of the concentrated research in order to reach above-mentioned problem such as the inventor, by in the treatment solution of water-soluble salt that contains permanganic acid or mangaic acid and water-soluble phosphate, add acetic acid and sodium-acetate again as the pH regulator agent, the pH of treatment solution is remained on 7 when following, even aluminiferous Mg alloy surface is carried out chemical treatment in lower treatment temp and relatively shorter treatment time, also can make high corrosion resistant surface treated magnesium alloy product, and, also find the life-span long (area that can treatablely contain the aluminum magnesium alloy surface of the treatment solution of per unit volume is big) of such treatment solution, so finished the present invention.
That is to say that the manufacture method of high corrosion resistant surface treated magnesium alloy product of the present invention is characterized in that the surface usefulness that contains aluminum magnesium alloy,
The concentration of the water-soluble salt of permanganic acid or mangaic acid is converted into KMnO
4Amount is more than 2g/L, and below the solubleness, ideal is 3～60g/L, and that better is 5～55g/L,
The concentration of the water-soluble salt of phosphoric acid is converted into Na
3PO
4Amount is 0.05～100g/L, and ideal is 0.05～30g/L, and that better is 0.1～10g/L,
The concentration of acetic acid is 0.05～100ml/L, and ideal is 0.1～50ml/L, and that better is 1～20ml/L,
The concentration of sodium-acetate is 0.05～50g/L, and ideal is 0.1～50g/L, and that better is 1～20g/L,
PH is below 7, and ideal is 2.3～6, and better is 3～5,
The liquid temperature is 288～368K, and ideal is 293～353K, and the treatment solution of better is 300～333K carried out 0.3～10 minute, and ideal is 0.4～7 minute, 0.5～3 minute chemical treatment that better is.
In addition, high corrosion resistant surface treated magnesium alloy product of the present invention adopts above-mentioned manufacture method to make, and it is characterized in that the Mn adhesion amount is 100～600mg/m
2, the P adhesion amount is 200mg/m
2, CH
3COO
-Adhesion amount is 0.01～1000mg/m
2
In manufacture method of the present invention, as carrying out the chemically treated aluminum magnesium alloy that contains, can enumerate all practical in various technical fields aluminiferous magnesium alloy, for example, comprise that AZ system, AM system, AM (containing Ca) are, the AS series magnesium alloy, yet wherein aluminium content is generally about 2～12% (quality).In addition, as carrying out the chemically treated form that contains the aluminum magnesium alloy goods among the present invention, can list die cast product, sand mold casting product, die casting and ductile material etc.
Before chemical treatment is carried out on the surface that contains aluminum magnesium alloy, this be contained the aluminum magnesium alloy surface and carry out solvent degreasing, in addition pre-treatment is an ideal and carry out drying after chemical treatment.
Solvent degreasing for example, is carried out 15 minutes ultrasonic washings and is implemented in acetone.
In addition, pre-treatment was for example flooded 1 minute in 60 ℃ of aqueous solution of potassium pyrophosphate concentration 35g/L, then, wash and the pure water washing, then, dipping is 3 minutes in 60 ℃ of aqueous solution of caustic soda concentration 50g/L, washes then and pure water washs and implements.
Above-mentioned solvent degreasing condition and pre-treatment condition, but be one of solvent degreasing and pre-treatment example, and other any solvent degreasing conditions and pre-treatment condition also can adopt.
Used chemical pretreatment solution in the manufacture method of the present invention contains the water-soluble salt of permanganic acid or mangaic acid, and suitable is to contain an alkali metal salts such as sylvite, sodium salt, lithium salts, and alkali earth metal salt such as magnesium salts, in addition, can also contain ammonium salt.The water-soluble salt concentration of permanganic acid in the chemical pretreatment solution or mangaic acid is converted into KMnO
4Amount below the solubleness, it is desirable to 3～60g/L for more than the 2g/L, and that better is 5～55g/L, and especially ideal is 15～45g/L.The water-soluble salt concentration of permanganic acid in the chemical pretreatment solution or mangaic acid is converted into KMnO
4Amount is during less than 2g/L, the inadequate tendency that becomes of the Mg alloy surface erosion resistance after the chemical treatment.In addition, the water-soluble salt of permanganic acid or mangaic acid, the amount in chemical treatment can reach its solubleness, yet,, do not find the raising of its corresponding erosion resistance even when the water-soluble salt concentration height of permanganic acid in the chemical pretreatment solution or mangaic acid is above to a certain degree yet, so, be converted into KMnO
4Amount it is desirable to 60g/L, and that better is 55g/L, and especially ideal is below the 45g/L.
Used chemical pretreatment solution in the manufacture method of the present invention contains water-soluble phosphate, it is desirable to contain Na
3PO
4, Na
2HPO
4, NaH
2PO
4, NH
4H
2PO
4, Mn (H
2PO
4)
2, Zn (H
2PO
4)
2Deng.The concentration of water-soluble phosphate is converted into Na in the chemical pretreatment solution
3PO
4Amount is 0.05～100g/L, and ideal is 0.05～30g/L, and that better is 0.1～10g/L.Water-soluble phosphoric acid salt concn in the chemical pretreatment solution is converted into Na
3PO
4Amount is during less than 0.05g/L, the inadequate tendency that becomes of the Mg alloy surface erosion resistance after the chemical treatment.In addition, the water-soluble phosphoric acid salt concn in the chemical pretreatment solution, even do not see the raising of its corresponding erosion resistance more than bringing up to a certain degree yet, so, be converted into Na
3PO
4Amount, generally below 100g/L, ideal is below 30g/L, and is better below 10g/L.
Used chemical pretreatment solution also contains acetic acid and the sodium-acetate as the pH regulator agent in the manufacture method of the present invention.Acetate concentration in the chemical pretreatment solution is 0.05～100ml/L, and ideal is 0.1～50ml/L, and that better is 1～20ml/L; Sodium-acetate concentration is 0.05～50g/L, and ideal is 0.1～50g/L, and that better is 1～20g/L.When the acetate concentration in the chemical pretreatment solution less than 0.05ml/L and/or sodium-acetate concentration during less than 0.05g/L, the inadequate tendency that becomes of the Mg alloy surface erosion resistance after the chemical treatment.In addition, acetic acid in the chemical pretreatment solution and sodium-acetate concentration height are not seen the raising of its corresponding erosion resistance to a certain degree yet, so, acetate concentration is below the 100ml/L, ideal is 50ml/L, and better is below the 20ml/L, and sodium-acetate concentration is below the 50g/L, ideal is below the 50g/L, and better is below the 20g/L.
The pH of used chemical pretreatment solution remains on below 7 in the manufacture method of the present invention.When the pH of chemical pretreatment solution greater than 7 the time, the chemical treatment reaction is extremely slow, the needed treatment time is extremely long, and is inapplicable.On the other hand, when the pH of chemical pretreatment solution crosses when low, the tendency of easy generation meal is arranged, in addition, when only adopting acetic acid and sodium-acetate as the pH regulator agent, can reach minimum pH value is about 2.3, so the pH ideal of chemical pretreatment solution is 2.3～6, better is 3～5.Also have, when the pH that makes chemical pretreatment solution reduces to 2.3 when following, can add mineral acid etc. as ancillary component.
The temperature of used chemical pretreatment solution remains on 288～368K in the manufacture method of the present invention.When the temperature of chemical pretreatment solution was lower than 288K, the chemical treatment reaction was slack-off, and needed treatment time lengthening is impracticable.On the other hand, even when the temperature of chemical pretreatment solution is higher than 368K, the raising of the erosion resistance of the Mg alloy surface after the chemical treatment is not identified, the tendency of the variation that woulds be better.Therefore, considering from this point of production cost, is disadvantageous.In manufacture method of the present invention, the temperature of chemical pretreatment solution it is desirable to 293～353K, and that better is 303～333K.
In manufacture method of the present invention, the chemical treatment time is 0.3～10 minute.When chemical treatment time during less than 0.3 minute, the erosion resistance of the Mg alloy surface after the chemical treatment inadequate tendency that becomes, in addition, even the chemical treatment time was above 10 minutes, do not find the raising of its corresponding erosion resistance, so production cost rises.In manufacture method of the present invention, the chemical treatment time, ideal is 0.4～7 minute, and better is 0.5～3 minute.
After the chemical treatment, wash and the pure water washing under these conditions, then, carry out drying,, generally implemented 10～120 minutes in 10～80 ℃ about drying.
Used chemical pretreatment solution among the present invention, in the chemical treatment under these conditions, its life-span is extremely long, that is to say, the per unit volume treatment solution, the surface-area that can treatablely contain aluminum magnesium alloy is very big.
The lip-deep Mn adhesion amount of surface treated magnesium alloy that obtains with manufacture method of the present invention is 100～600mg/m
2, the P adhesion amount is 200mg/m
2Below, CH
3COO
-Adhesion amount is 0.01～1000mg/m
2, be considered to make the erosion resistance of alloy product to improve as this result.
In addition, the surface of the surface treated magnesium alloy product that obtains with manufacture method of the present invention, when covering with paint, lacquer, colour wash, etc., cover with paint, lacquer, colour wash, etc. binding property might as well, have equal covering with paint binding property with the chromate treating product.
Also have, adhere to Mn, because be that the possibility of adhering to as Manganse Dioxide is big, thus it is contemplated that it is that the impedance of protective membrane is low, thus also can produce effect even can be susceptible to for desired electromagnetic wave shieldings such as electronic machines.
In manufacture method of the present invention, employing becomes the heavy metal of impurity when not containing as 6 valency chromium of objectionable impurities and recirculation, and, the non-chromate treatment solution that life-span is long, can reach and adopt the chromic acid salt bath to carry out the identical or better erosion resistance of chemical treatment, and, can provide recirculation high high corrosion resistant surface treated magnesium alloy product, when covering with paint, lacquer, colour wash, etc., good covering with paint binding property is arranged also, can reach the covering with paint bond properties equal with the chromate treating product.
Below, specifically describe the present invention by embodiment and comparative example.
Embodiment 1～9
15 minutes ultrasonic washings are implemented in a plurality of test pieces that magnesium alloy (AZ 91) is made in room temperature acetone, in drying at room temperature 5 minutes.Then, dipping is 1 minute in the potassium pyrophosphate aqueous solution (35g/L, 60 ℃), then, washs for 30 seconds and washs for 30 seconds with the pure water of room temperature with the tap water under the room temperature.Then, dipping is 3 minutes in the caustic soda aqueous solution (50g/L, 60 ℃), then, washs for 30 seconds and washs for 30 seconds with the pure water under the room temperature with the tap water under the room temperature.
Each test piece through above-mentioned processing is immersed in respectively in the chemical pretreatment solution successively, and this treatment solution contains the KMnO of the concentration shown in the table 1 of respectively doing for oneself
4, Na
3PO
4, CH
3COOH and CH
3COONa also has pH value and the treatment temp shown in the table 1, and the dip treating time is also as shown in table 1.Then, washed for 30 seconds, and washed for 30 seconds with the pure water under the room temperature with the tap water under the room temperature, last, in drying at room temperature 2 hours.
To through above-mentioned chemical treatment, dry each test piece of crossing, carry out corrosion resistance test according to JIS Z 2371, the state after 24 hours is estimated with the nominal number method.Its result is as shown in table 1.
In addition, on surface through above-mentioned chemical treatment, dry each test piece of crossing, with dipping covering with paint method coating acrylic acid or the like baked paint, leave standstill 10 minutes after, in 150 ℃ of heat dryings 20 minutes.Then, according to the 8.5.2 of JIS K 5400, implement to cover with paint, lacquer, colour wash, etc. bond test with checker band method (1mm at interval).The results are shown in table 1.Comparative example 1
The test piece that magnesium alloy (AZ 91) is made, similarly carry out solvent degreasing with the foregoing description, carry out pre-treatment, after the washing, according to JIS H 8651 standards 3 kinds promptly carry out chemical treatment under the treatment condition shown in the table 1.Then, hot water wash is washed drying equally with the foregoing description.Also carry out corrosion resistance test equally and cover with paint, lacquer, colour wash, etc. bond test with the test piece that this comparative example obtains with the foregoing description.The results are shown in table 1.Comparative example 2
The test piece that magnesium alloy (AZ 91) is made, similarly carry out solvent degreasing with the foregoing description, carry out pre-treatment, after the washing, open the method for flat 8-225954 communique record according to the spy, promptly under the treatment condition shown in the table 1, carry out chemical treatment, then, wash drying equally with the foregoing description.These comparative example 2 resulting test pieces are also carried out corrosion resistance test equally and covered with paint, lacquer, colour wash, etc. bond test with the foregoing description.These the results are shown in table 1.Comparative example 3
The test piece that magnesium alloy (AZ 91) is made, carry out with the foregoing description solvent degreasing similarly, pre-treatment, washing after, open the method for flat 8-35073 communique record according to the spy, promptly under the treatment condition shown in the table 1, carry out chemical treatment, then, wash drying equally with the foregoing description.These comparative example 3 resulting test pieces are also carried out corrosion resistance test equally and covered with paint, lacquer, colour wash, etc. bond test with the foregoing description.The results are shown in table 1.Comparative example 4
The test piece that magnesium alloy (AZ 91) is made, carry out with the foregoing description solvent degreasing similarly, pre-treatment, washing after, according to Jan Ivar Skar, et a1_SAE TechnicalPaper Series, 970324, pp7-11, the method of record is promptly carried out chemical treatment, then in 1997 under the treatment condition shown in the table 1, wash drying equally with the foregoing description.The test piece that this comparative example 4 obtains is also carried out corrosion resistance test equally and covered with paint, lacquer, colour wash, etc. bond test with the foregoing description.The results are shown in table 1.Comparative example 5～6
The test piece that magnesium alloy (AZ 91) is made, carry out with the foregoing description solvent degreasing similarly, pre-treatment, washing after, according to David Hawke, et al_Metal Finishing93,10, PP34-38, the method of record in 1995, promptly under the treatment condition shown in the table 1, carry out chemical treatment, then, carry out similarly washing, drying with the foregoing description.The test piece that obtains in this comparative example 5～6 is also carried out corrosion resistance test equally and covered with paint, lacquer, colour wash, etc. bond test with the foregoing description.The results are shown in table 1.
Embodiment 10
15 minutes ultrasonic washings are carried out in a plurality of test pieces that magnesium alloy (AZ 91) is made in the acetone of room temperature, in drying at room temperature 5 minutes.Then, dipping is 1 minute in the potassium pyrophosphate aqueous solution (35g/L, 60 ℃), then, washs for 30 seconds and washs for 30 seconds with the pure water under the room temperature with the tap water under the room temperature.Secondly, dipping is 3 minutes in the caustic soda aqueous solution (50g/L, 60 ℃), then, washs for 30 seconds and washs for 30 seconds with the pure water under the room temperature with the tap water under the room temperature.
Each test piece of above-mentioned processing, in the foregoing description 1, flooded successively respectively 1 minute in the used chemical pretreatment solution, then, washed for 30 seconds and washed for 30 seconds with the pure water under the room temperature with the tap water under the room temperature.At last, in drying at room temperature 2 hours.The total area of chemical treatment test piece reaches 0,25,50,75,100,125,150,175 and 200dm respectively
2During/L, corrosion resistance test is carried out in test piece and the foregoing description equally.The results are shown in table 2.
In addition, Mn, P and the CH through adhering on above-mentioned chemical treatment, each test piece surface of exsiccant
3COO
-Adhesion amount, obtain with following method.
That is to say, each test piece is immersed in 3% (quality) 200ml aqueous sulfuric acid 3 minutes, then, analyze the Mn amount and the P amount of stripping in this aqueous solution, calculate the adhesion amount of Mn and P.These the results are shown in the table 2.
In addition, each test piece in the mixed base aqueous solution (Na
2CO
32.7mM+NaHCO
30.3mM) in 30 ℃ of dippings 1 hour, analyze the CH be dissolved in this aqueous solution
3COO
-Amount is calculated CH
3COO
-Adhesion amount.The results are shown in table 2.Comparative example 7
15 minutes ultrasonic washings are carried out in a plurality of test pieces that magnesium alloy (AZ 91) is made in the acetone of room temperature, at room temperature dry 5 minutes.Then, dipping is 1 minute in the potassium pyrophosphate aqueous solution (35g/L, 60 ℃), then, washs for 30 seconds and washs for 30 seconds with pure water under the room temperature with the tap water under the room temperature.Then, dipping is 3 minutes in the caustic soda aqueous solution (50g/L, 60 ℃), then, washs for 30 seconds and washs for 30 seconds with the pure water under the room temperature with the tap water under the room temperature.
Through each test piece of above-mentioned processing, in above-mentioned comparative example 2, flooded successively 1 minute in the used chemical pretreatment solution, then, washed for 30 seconds and washed for 30 seconds with the pure water under the room temperature with the tap water under the room temperature.At last, under room temperature dry 2 hours.Reach 0,25,50,75,100,125,150,175 and 200dm respectively for the total area of chemical treatment test piece again
2Test piece during/L is carried out and the same corrosion resistance test of the foregoing description.The results are shown in table 2.
Table 1
| Treatment condition | Assessment item | |||||||||
| ????KMnO 4????g/l | ????Na 3PO 4????g/l | ??CH 3COOH ????ml/l | ?CH 3COONa ????g/l | ???pH ????-- | Treatment temp ℃ | The treatment time branch | Degree of corrosion R.N. | Binding property | ||
| Embodiment | ?1 ?2 ?3 ?4 ?5 ?6 ?7 ?8 ?9 | ????31.6 ????31.6 ????31.6 ????31.6 ????31.6 ????5.0 ????55.0 ????31.6 ????31.6 | ?????0.5 ?????0.5 ?????0.5 ?????0.5 ?????0.5 ?????0.5 ?????0.5 ?????0.5 ?????0.1 | ????10 ????10 ????10 ????10 ????10 ????10 ????10 ????100 ????0.1 | ????4.1 ????4.1 ????4.1 ????4.1 ????4.1 ????4.1 ????4.1 ????0.1 ????8.0 | ????4 ????4 ????4 ????4 ????4 ????4 ????4 ????2.3 ????7 | ????45 ????45 ????45 ????30 ????95 ????45 ????45 ????45 ????60 | ????1 ????0.5 ????10 ????1 ????1 ????1 ????1 ????1 ????10 | ????9.8 ????9.8 ????9.1 ????9.5 ????9.1 ????9.8 ????9.8 ????9.8 ????9.0 | ????100/100 ????100/100 ????100/100 ????100/100 ????100/100 ????100/100 ????100/100 ????100/100 ????100/100 |
| Comparative example | ?1 | 46%HF 250ml/l, 30 ℃, 3 minutes → washing → Na 2CrO 7?125g/l、CaF 22.5g/l, 95 ℃, 45 minutes → hot water wash | ????9.5 | ????100/100 | ||||||
| ?2 | ?Na 2CrO 7?60g/l、HNO 345g/l, Zn powder 0.5g/l, 45 ℃, 3 minutes | ????9.8 | ????100/100 | |||||||
| ?3 | ?KMnO 4?30g/l、HNO 33ml/l, 45 ℃, 1 minute | ????8.5 | ????95/100 | |||||||
| ?4 | ?KMnO 4?30g/l、NaH 2?PO 4100g/l, 45 ℃, 1 minute | ????8.6 | ????97/100 | |||||||
| ?5 | Use KMnO 4?20g/l、NH 4H 2?PO 4?100g/l、H 3PO 4Be adjusted to 40 ℃ of pH3.5,1 minute | ????8.7 | ????99/100 | |||||||
| ?6 | Use KMnO 4?20g/l、NH 4H 2?PO 4?100g/l、H 3PO 4Be adjusted to 45 ℃ of pH3.5,1 minute | ????8.7 | ????99/100 | |||||||
Table 2
| Total surface area (the dm of chemical treatment test piece 2/l) | |||||||||||
| ????0 | ????25 | ????50 | ????75 | ???100 | ???125 | ???150 | ????175 | ???200 | |||
| Embodiment 10 | R.N. Mn adhesion amount, mg/m 2P adhesion amount, mg/m 2????CH 3COO-adhesion amount, mg/m 2 | ????9.8 ????212 ????16 ????3.6 | ????9.8 ????184 ????7 ????3.0 | ????9.7 ????254 ????6 ????4.0 | ????9.7 ????211 ????＜6 ????3.8 | ????9.6 ????241 ????7 ????3.9 | ????9.5 ????272 ????＜6 ????4.3 | ????9.4 ????262 ????＜6 ????4.1 | ????9.3 ????228 ????＜6 ????3.7 | ????9.2 ????233 ????＜6 ????4.0 | |
| Comparative example 7 | ??R.N. | ????9.8 | ????9.3 | ????9.2 | ????9.0 | ????8.8 | ????8.6 | ????8.5 | ????8.5 | ????8.5 | |
Claims (4)
1. the manufacture method of a high corrosion resistant surface treated magnesium alloy product is characterized in that, the surface usefulness that contains aluminum magnesium alloy,
The concentration of the water-soluble salt of permanganic acid or mangaic acid is converted into KMnO
4Amount is more than the 2g/L, below the solubleness,
The water-soluble salt concentration of phosphoric acid is converted into Na
3PO
4Amount is 0.05～100g/L,
Acetate concentration is 0.05～100ml/L,
Sodium-acetate concentration is 0.05～50g/L,
PH is below 7,
The liquid temperature is 288～368K
Treatment solution carry out 0.3～10 minute chemical treatment.
2. the manufacture method of high corrosion resistant surface treated magnesium alloy product of record in the claim 1 is characterized in that, containing the surperficial usefulness of aluminum magnesium alloy,
The concentration of the water-soluble salt of permanganic acid or mangaic acid is converted into KMnO
4Amount is 3～60g/L,
The water-soluble salt concentration of phosphoric acid is converted into Na
3PO
4Amount is 0.05～30g/L,
Acetate concentration is 0.1～50ml/L,
Sodium-acetate concentration is 0.1～50g/L,
PH is 2.3～6,
The liquid temperature is 293～353K
Treatment solution carry out 0.4～7 minute chemical treatment.
3. the manufacture method of the high corrosion resistant surface treated magnesium alloy product of record in the claim 2 is characterized in that, the surface usefulness that contains aluminum magnesium alloy,
The concentration of the water-soluble salt of permanganic acid or mangaic acid is converted into KMnO
4Amount is 5～55g/L,
The water-soluble salt concentration of phosphoric acid is converted into Na
3PO
4Amount is 0.1～10g/L,
Acetate concentration is 1～20ml/L,
Sodium-acetate concentration is 1～20g/L,
PH is 3～5,
The liquid temperature is 303～333K
Treatment solution carry out 0.5～3 minute chemical treatment.
4. a high corrosion resistant surface treated magnesium alloy product is characterized in that, make according to the manufacture method of any one record in the claim 1～3, the Mn adhesion amount is 100～600mg/m
2, the P adhesion amount is 200mg/m
2Below, CH
3COO
-Adhesion amount is 0.01～1000mg/m
2
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|---|---|---|---|
| JP302499/1999 | 1999-10-25 | ||
| JP30249999A JP2001123274A (en) | 1999-10-25 | 1999-10-25 | High corrosion resistance surface treated magnesium alloy product and producing method therefor |
| JP302499/99 | 1999-10-25 |
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|---|---|
| CN1294203A true CN1294203A (en) | 2001-05-09 |
| CN1238556C CN1238556C (en) | 2006-01-25 |
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| ES2178917B1 (en) * | 2000-04-05 | 2004-03-16 | Fundacion Inasmet | CHEMICAL CONVERSION TREATMENT FOR THE MAGNESIUM AND ITS ALLOYS. |
| US6887320B2 (en) * | 2002-02-11 | 2005-05-03 | United Technologies Corporation | Corrosion resistant, chromate-free conversion coating for magnesium alloys |
| KR101115786B1 (en) | 2006-12-06 | 2012-03-09 | 다이세이 플라스 가부시끼가이샤 | Process for production of highly corrosion-resistant composite |
| CN101463475A (en) | 2007-12-19 | 2009-06-24 | 鸿富锦精密工业（深圳）有限公司 | Magnesium alloy phosphating method and formation solution thereof |
| JP7030510B2 (en) * | 2017-12-27 | 2022-03-07 | 三井化学株式会社 | Manufacturing method of surface roughened magnesium alloy member |
| JP2022022774A (en) * | 2020-07-06 | 2022-02-07 | Ykk株式会社 | Aluminum alloy fastening member, fastener chain and method for producing aluminum alloy fastening member |
-
1999
- 1999-10-25 JP JP30249999A patent/JP2001123274A/en active Pending
-
2000
- 2000-10-13 TW TW089121420A patent/TW499502B/en not_active IP Right Cessation
- 2000-10-25 CN CN 00133152 patent/CN1238556C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1990546B (en) * | 2005-12-30 | 2010-12-08 | 上海杰事杰新材料股份有限公司 | Punching-resistant reinforced polyester blending engineering material and method for preparing same |
| CN110172700A (en) * | 2019-06-26 | 2019-08-27 | 匡云叶 | A kind of Mg alloy surface treatment fluid and surface treatment method |
| CN110204358A (en) * | 2019-06-26 | 2019-09-06 | 匡云叶 | A kind of ceramics pretreatment fluid and preprocess method |
| CN110204358B (en) * | 2019-06-26 | 2021-11-09 | 匡云叶 | Ceramic pretreatment liquid and pretreatment method |
| CN113897606A (en) * | 2020-07-06 | 2022-01-07 | 日本表面化学株式会社 | Metal coloring liquid for chemical conversion treatment and metal coloring treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1238556C (en) | 2006-01-25 |
| JP2001123274A (en) | 2001-05-08 |
| TW499502B (en) | 2002-08-21 |
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