CN100569999C - Chemically coating nickel by magnesium-alloy Chrome-free pre-treating technology and inhibition treatment soln thereof - Google Patents
Chemically coating nickel by magnesium-alloy Chrome-free pre-treating technology and inhibition treatment soln thereof Download PDFInfo
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- CN100569999C CN100569999C CNB2008100610365A CN200810061036A CN100569999C CN 100569999 C CN100569999 C CN 100569999C CN B2008100610365 A CNB2008100610365 A CN B2008100610365A CN 200810061036 A CN200810061036 A CN 200810061036A CN 100569999 C CN100569999 C CN 100569999C
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Abstract
The invention discloses a kind of chemically coating nickel by magnesium-alloy Chrome-free pre-treating technology and used inhibition treatment soln thereof, belong to the Mg alloy surface process field.The operation steps of this technology is: (1) mechanical pretreatment: mechanical grinding is carried out on the surface to magnesium alloy; (2) acetone degreasing; Carry out ultrasonic cleaning with acetone; (3) inhibition is handled: carry out inhibition with the aqueous solution that contains oleoyl sarcosine and sodium hydroxide as the inhibition treatment soln and handle; (4) diluted acid pickling: carry out pickling with dilute acid soln; (5) hydrofluoric acid activation: activate as activation solution with hydrofluoric acid aqueous solution; (6) chemical nickel plating.Used inhibition treatment soln is solvent with water, contains 0.2～20 milliliter of oleoyl sarcosine, sodium hydroxide 0.02～10 gram in every liter of inhibition treatment soln.This technology has that technology is simple, the advantage of Chrome-free element environmental pollution.
Description
Technical field
The present invention relates to a kind of chemical nickel plating process on magnesium alloy, especially a kind of chemically coating nickel by magnesium-alloy Chrome-free pre-treating technology and used inhibition treatment soln thereof belong to the Mg alloy surface process field.
Background technology
Magnesium alloy is as the lightest structural timber, have many good physical and mechanical properties, good as specific tenacity height, good rigidly, damping property, can bear feature performance benefits such as bigger impact shock load, good, the anti-electromagnetic interference of electrical and thermal conductivity and shielding be good, it is widely used in fields such as automobile, aerospace, electronics, communication, military affairs, opticinstrument and computer manufacturing.But because magnesium is the extremely strong metal of a kind of electronegativity, so magnesium alloy has very strong chemically reactive, under normal atmospheric or solution environmental oxidation and corrosion can take place, and influences the application of magnesium alloy in every field.Handle as on magnesium alloy, carrying out chemical nickel plating, not only can obtain high rigidity, abrasion resistant and corrosion resistant, and can on complex-shaped plating piece, obtain surface-brightening, thickness is even, protection effect is good coating, have a good application prospect.
Because the chemical property of magnesium alloy is active, in traditional chemical plating fluid that is applicable to matrix such as steel, can't form Ni-P coating, now developed the multiple method that is suitable for chemically coating nickel by magnesium-alloy.Be that DOWShi soaks the zinc method the earliest: after in containing the zinc solution of pyrophosphate salt, soaking zinc,, carry out electroless plating then by the cyanide copper plating bottoming.There is certain shortcoming in this method, and is complicated as technology, be not suitable for safe in utilization and liquid waste disposal problem of the higher alloy of aluminium content, prussiate or the like.Therefore the method without the direct chemical nickel plating of soaking zinc and cyanide copper plating comes into one's own gradually, for example A.K.Sharma etc. (reference [1]) has proposed the magnesium alloy direct chemical nickel-plating technology of nickelous carbonate bath system, the bavin Tian Guangnan of Japan has proposed the bath system (reference [2]) of single nickel salt as main salt, and notification number is the nickelous sulfate plating liquid system that the Chinese invention patent of CN1563488 has proposed a kind of fluoride.These methods are undertaken by following technical process mostly: Mg alloy surface polishing → oil removing → chromic acid+nitric acid acidwashing → hydrofluoric acid aqueous solution activation → chemical nickel plating, the chromyl chromic acid solution of its many uses causes serious harm to the mankind and environment.
Based on above consideration, press for and develop the magnesium alloy direct chemical nickel-plating technology that adopts the Chrome-free pre-treatment.About the Chrome-free pre-treating process, pertinent literature report is also arranged, for example W.X.Zhang etc. (reference [3]) proposes behind Mg alloy surface conversion processing one deck phosphate layer, to carry out chemical nickel plating with phosphoric acid and phosphate dihydrogen manganese again.But this method complex process, the use of heavy metal ion manganese simultaneously can cause problems such as reclaiming difficulty, environmental pollution.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of technology is simple, the chemically coating nickel by magnesium-alloy Chrome-free pre-treating technology of Chrome-free element environmental pollution, also provides a kind of this technology used inhibition treatment soln prescription simultaneously.
The present invention addresses the above problem the technical scheme that is adopted: this technology is operated according to the following steps:
(1) mechanical pretreatment: mechanical grinding is carried out on the surface to magnesium alloy;
(2) acetone degreasing; Carry out ultrasonic cleaning with acetone;
(3) inhibition is handled: carry out inhibition with the aqueous solution that contains oleoyl sarcosine and sodium hydroxide as the inhibition treatment soln and handle;
(4) diluted acid pickling: carry out pickling with dilute acid soln;
(5) hydrofluoric acid activation: activate as activation solution with hydrofluoric acid aqueous solution;
(6) chemical nickel plating.
Contain 0.2～20 milliliter of oleoyl sarcosine, sodium hydroxide 0.02～10 gram in every liter of inhibition treatment soln of the present invention, surplus is a water.
Inhibition of the present invention is treated under 20～80 ℃ temperature, handles 2～60 minutes with the inhibition treatment soln, under 30～120 ℃ temperature, dries 10～60 minutes then.
Dilute acid soln of the present invention is one or more in dilute hydrochloric acid, dilute sulphuric acid, the rare nitric acid, and its weight concentration is 0.1%～5%.
Diluted acid pickling of the present invention is with dilute acid soln pickling at room temperature 5～30 minutes.
Hydrofluoric acid containing solution is 50～380 milliliters in every liter of activation solution of the present invention, and surplus is a water, and the weight concentration of hydrofluoric acid solution is 40%.
Hydrofluoric acid activation of the present invention is at room temperature to activate 10～30 minutes with activation solution.
The used inhibition treatment soln of this technology is solvent with water, contains 0.2～20 milliliter of oleoyl sarcosine, sodium hydroxide 0.02～10 gram in every liter of inhibition treatment soln.
The present invention compared with prior art, have following beneficial effect: 1, this process using " inhibition processing+pickling " substitutes pre-treatment employed " chromic acid+nitric acid " pickling in the conventional chemically coating nickel by magnesium-alloy, with the aqueous solution that contains oleoyl sarcosine and sodium hydroxide as the inhibition treatment soln, thereby in whole process, do not use the chromium element, reduced harm environment and human body; 2, adopt the resulting chemical Ni-plating layer of this technology to have metalluster, coating even compact, good with matrix bond, solidity to corrosion is also better; 3, the treatment process of this technology is simple, easy to operate, cost is low.
Description of drawings
Fig. 1 is the coating cross section metallograph of the embodiment of the invention 1.
Fig. 2 is for adopting the coating cross section metallograph of chromic acid and nitric acid acidwashing.
Fig. 3 is the coating cross section metallograph without inhibition processing, direct dilute hydrochloric acid pickling.
Embodiment
Embodiment 1:
Sample is a die casting AZ91D magnesium alloy.Operation by the following method:
1, mechanical pretreatment: use the 600# sand papering, remove the burr, releasing agent on cast magnesium alloys surface, the cold working metal bits that adhere to of loosing, oxide compound etc.
2, acetone degreasing: use acetone ultrasonic cleaning 10 minutes.
3, inhibition is handled: the inhibition treatment soln is solvent with water; every liter of this solution contains 2 milliliters of oleoyl sarcosines and 0.2 gram sodium hydroxide; under 30 ℃ of temperature, handled 30 minutes; dried 15 minutes under 80 ℃ of temperature again; Mg alloy surface is covered by the silvery white inhibiter protective membrane of layer of even fully, and the protection magnesium alloy is not corroded.
4, diluted acid pickling: dilute acid soln is the hydrochloric acid of weight concentration 0.5%; at room temperature handled 10 minutes; the inhibiter protective membrane of Mg alloy surface also can generating unit branch point-like be corroded under the situation of uniform corrosion; the roughness of matrix increases, and reaches to replace chromic acid and nitric acid acidwashing to make the coarse effect of magnesium alloy substrate.
5, hydrofluoric acid activation: activation solution is a hydrofluoric acid aqueous solution, with water is solvent, contains 50 milliliters of hydrofluoric acid solutions in every liter of activation solution, and the weight concentration of hydrofluoric acid solution is 40%, at room temperature activate 15 minutes, coarse magnesium alloy substrate and hydrofluoric acid are reacted generate MgF
2Film, the protection magnesium alloy substrate is not corroded in plating bath.
6, chemical nickel plating: carry out chemical nickel plating with the basic nickel carbonate system shown in the table 1.
The plating bath of table 1 chemical nickel plating is formed and the plating parameter
| 2NiCO3·3Ni(OH)2·4H2O | 12g/L |
| HF(40％) | 10g/L |
| C6H8O7·H2O | 5g/L |
| NH4·HF2 | 10g/L |
| NaH2 PO2·H2O | 20g/L |
| NH3·H2O(25％) | Regulate pH |
| The pH value | 6.5 |
| Temperature | 80℃ |
| The plating time | 2h |
Clean and tidy in order to the resulting electroless nickel plating on magnesium light of last method, scratch experiment detection coating and basal body binding force are good, (Fig. 2 is for adopting the coating cross section metallograph of chromic acid and nitric acid acidwashing as shown in Figure 1 for its coating cross section metallograph, Fig. 3 is the coating cross section metallograph without inhibition processing, direct dilute hydrochloric acid pickling), by metallographicobservation and comparison shows that: the interface roughness of coating and matrix, mechanical riveted effect between the two is strong, reaches the effect that improves binding force of cladding material.The solidity to corrosion that detects coating through neutral salt spray test is suitable with the corrosion resistance of coating that adopts chromic acid and nitric acid acidwashing.
Embodiment 2:
Sample is a die casting AZ91D magnesium alloy.Operation by the following method:
1, mechanical pretreatment, acetone degreasing and inhibition processing are identical with embodiment 1.
2, diluted acid pickling: dilute acid soln is the dilute sulphuric acid of weight concentration 0.5%, at room temperature handles 15 minutes.
3, hydrofluoric acid activation: activation solution is a hydrofluoric acid aqueous solution, is solvent with water, contains 150 milliliters of hydrofluoric acid solutions in every liter of activation solution, and the weight concentration of hydrofluoric acid solution is 40%, at room temperature activates 10 minutes.
4, the plating bath composition of chemical nickel plating is identical with embodiment 1 with processing parameter.
Clean and tidy in order to the resulting electroless nickel plating on magnesium of last method light, scratch experiment detect and metallographicobservation coating cross section result similar to embodiment 1, combining between coating and the matrix is good.The solidity to corrosion that detects coating through neutral salt spray test is suitable with the corrosion resistance of coating that adopts chromic acid and nitric acid acidwashing.
Embodiment 3:
Sample is extruding AM60B magnesium alloy.Operation by the following method:
1, mechanical pretreatment, acetone degreasing and inhibition processing are identical with embodiment 1.
2, diluted acid pickling: dilute acid soln is rare nitric acid of weight concentration 0.5%, handles 15 minutes under the room temperature.
3, hydrofluoric acid activation: activation solution is a hydrofluoric acid aqueous solution, is solvent with water, contains 250 milliliters of hydrofluoric acid solutions in every liter of activation solution, and the weight concentration of hydrofluoric acid solution is 40%, at room temperature activates 10 minutes.
4, the plating bath composition of chemical nickel plating is identical with embodiment 1 with processing parameter.
Clean and tidy in order to the resulting electroless nickel plating on magnesium of last method light, scratch experiment detect and metallographicobservation coating cross section result similar to embodiment 1, combining between coating and the matrix is good.The solidity to corrosion that detects coating through neutral salt spray test is suitable with the corrosion resistance of coating that adopts chromic acid and nitric acid acidwashing.
Reference:
[1]A.K.Sharma，M.R.Suresh，H.Bhojraj，H.Narayanamurthy，and R.ESahu.Electroless Nickel Plating on Magnesium Alloy[J].Metal Finishing，1998，(3)：10-16
[2] bavin Tian Guangnan .Direct electroless nickel plating on magnesium alloys. sufacing, 1997; 48 (4): 413～416
[3]W.X.Zhang，J.G.He，Z.H.Jiang，Q.Jiang and J.S.Lian.Electroless Ni-P layer with a chromium-free pretreatment on AZ91Dmagnesium alloy，Surface and Coatings Technology，2007，201(8)：4594-4600
Claims (8)
1, a kind of chemically coating nickel by magnesium-alloy Chrome-free pre-treating technology is characterized in that: operation according to the following steps:
(1) mechanical pretreatment: mechanical grinding is carried out on the surface to magnesium alloy;
(2) acetone degreasing; Carry out ultrasonic cleaning with acetone;
(3) inhibition is handled: carry out inhibition with the aqueous solution that contains oleoyl sarcosine and sodium hydroxide as the inhibition treatment soln and handle;
(4) diluted acid pickling: carry out pickling with dilute acid soln;
(5) hydrofluoric acid activation: activate as activation solution with hydrofluoric acid aqueous solution;
(6) chemical nickel plating.
2, chemically coating nickel by magnesium-alloy Chrome-free pre-treating technology according to claim 1 is characterized in that: contain 0.2～20 milliliter of oleoyl sarcosine, sodium hydroxide 0.02～10 gram in every liter of inhibition treatment soln, surplus is a water.
3, chemically coating nickel by magnesium-alloy Chrome-free pre-treating technology according to claim 1 and 2, it is characterized in that: described inhibition is treated under 20～80 ℃ temperature, handled 2～60 minutes with the inhibition treatment soln, under 30～120 ℃ temperature, dried 10～60 minutes then.
4, chemically coating nickel by magnesium-alloy Chrome-free pre-treating technology according to claim 1 is characterized in that: described dilute acid soln is one or more in dilute hydrochloric acid, dilute sulphuric acid, the rare nitric acid, and its weight concentration is 0.1%～5%.
5, according to claim 1 or 4 described chemically coating nickel by magnesium-alloy Chrome-free pre-treating technologies, it is characterized in that: described diluted acid pickling is with dilute acid soln pickling at room temperature 5～30 minutes.
6, chemically coating nickel by magnesium-alloy Chrome-free pre-treating technology according to claim 1, it is characterized in that: hydrofluoric acid containing solution is 50～380 milliliters in every liter of activation solution, and surplus is a water, and the weight concentration of hydrofluoric acid solution is 40%.
7, according to claim 1 or 6 described chemically coating nickel by magnesium-alloy Chrome-free pre-treating technologies, it is characterized in that: described hydrofluoric acid activation is at room temperature to activate 10～30 minutes with activation solution.
8, a kind of chemically coating nickel by magnesium-alloy Chrome-free pre-treating technology inhibition treatment soln is characterized in that: be solvent with water, contain 0.2～20 milliliter of oleoyl sarcosine, sodium hydroxide 0.02～10 gram in every liter of inhibition treatment soln.
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| CN101831644A (en) * | 2010-06-12 | 2010-09-15 | 哈尔滨工业大学 | Chemical nickel plating method for pretreating magnesium alloy by chrome-free acid-wash activation one-step process |
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| N-油酰肌氨酸及其十八胺盐通讨中试鉴定. 夏水银等.浙江化工. 1983 |
| N-油酰肌氨酸及其十八胺盐通讨中试鉴定. 夏水银等.浙江化工. 1983 * |
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