CN102296259A - Aluminum plating liquid, hot dip aluminum plating method and metal device manufactured thereby - Google Patents
Aluminum plating liquid, hot dip aluminum plating method and metal device manufactured thereby Download PDFInfo
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- CN102296259A CN102296259A CN2010102073884A CN201010207388A CN102296259A CN 102296259 A CN102296259 A CN 102296259A CN 2010102073884 A CN2010102073884 A CN 2010102073884A CN 201010207388 A CN201010207388 A CN 201010207388A CN 102296259 A CN102296259 A CN 102296259A
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Abstract
The invention discloses aluminum plating liquid, a hot dip aluminum plating method and a metal device manufactured thereby. The aluminum plating liquid comprises 92 to 98 mass percent of aluminum and 2 to 8 mass percent of RE, wherein the RE is a mixture of 10 to 30 mass percent of yttrium (Y) and 70 to 90 mass percent of cerium (Ce). In the hot dip aluminum plating method, a workpiece is subjected to hot dip aluminum plating treatment by the aluminum plating liquid. Rare-earth elements are added into the aluminum plating liquid, so the aluminum plating liquid is purified, crystal grains are refined, and wettability between the aluminum plating liquid and the workpiece and flowability of the aluminum plating liquid are improved. The aluminum plating liquid is applied to the hot dip aluminum plating process, so that adhesivity between the plated workpiece and a plating layer is improved and corrosion resistance of the workpiece is enhanced.
Description
Technical field
The present invention relates to the thermo-chemical treatment technical field of metallic surface, relate in particular to the hot-dipping aluminium-plating method of a kind of liquid of aluminizing, the described liquid of aluminizing of use, and the metal device of this method preparation.
Background technology
When the device of metallic substance used in severe environment such as ocean, owing to be subjected to the influence of multiple corrosive naturees such as sunshine, wave erosion, salt fog simultaneously, the etching problem of device was quite serious, has caused serious economy loss.For a long time, people are seeking the whole bag of tricks to reduce the harm due to the corrosion always, generally adopt modes such as spraying paint, apply protective coating at device surface to protect.
For example, hot-dipping aluminium-plating method at present commonly used, it applies layer of aluminum or aluminum alloy coating to delay the corrosion of metal device on the metal device surface, generally comprise to workpiece carry out oil removing, cleaning, rust cleaning, cleaning, hot dip aluminum plating, post-treating and other steps.But, after the existing liquid of aluminizing of employing is handled device in the hot dip aluminum plating step, in most of the cases, the coating adhesion that device surface forms is poor, more easily come off from device surface, thereby cause the corrosion of device, people have to device is carried out a large amount of maintenances and patch work.
Summary of the invention
The technical problem to be solved in the present invention is, defective at the coating adhesion difference that forms at device surface after the liquid hot dip process of aluminizing in the prior art, a kind of liquid of aluminizing that is used for hot dipping aluminium plating technology is provided, the coating adhesion that forms through the metal device surface that this liquid of aluminizing was handled is strong, difficult drop-off has corrosion resistance preferably.
Another technical problem that the present invention will solve is, a kind of hot-dipping aluminium-plating method also is provided, and this method adopts the above-mentioned liquid of aluminizing that metal device is carried out surface treatment.
Another technical problem that the present invention will solve is, a kind of metal device of being handled by above-mentioned hot-dipping aluminium-plating method also is provided, and it has stronger corrosion resistance nature.
For reaching above-mentioned purpose, according to the present invention, a kind of liquid of aluminizing is provided, be used for hot-dipping aluminium-plating method, comprise the aluminium of massfraction 92～98% and the RE of massfraction 2～8%, described RE is the mixture of the Ce of the Y of massfraction 10～30% and massfraction 70～90%, wherein, preferably, described RE is the mixture of the Ce of the Y of massfraction 30% and massfraction 70%.
For reaching above-mentioned purpose, according to the present invention, a kind of hot aluminizing method is provided, comprise to workpiece carry out oil removing, cleaning, rust cleaning, clean, help plating, hot dip aluminum plating, post-processing step, described hot dip aluminum plating step is: described workpiece is immersed in the above-mentioned liquid of aluminizing, carry out hot dip aluminum plating in 650～750 ℃ and handle 2～8min.
Hot-dipping aluminium-plating method of the present invention, described hot dip aluminum plating step also comprises the melting step of the described liquid of aluminizing, the melting step of the described liquid of aluminizing comprises:
The Y of massfraction 30% and the Ce of massfraction 70% are mixed, under 850～950 ℃, be smelted into the RE alloy;
The described RE alloy of massfraction 2～8% and the aluminium of massfraction 92～98% are mixed, under 650～750 ℃, be smelted into the described liquid of aluminizing.
Hot-dipping aluminium-plating method of the present invention, in the described hot dip aluminum plating step, the described liquid surface of aluminizing also is coated with surface dopant, and described surface dopant comprises that massfraction is respectively 40～60% KCl, 30～50% NaCl and 10～20% NaF.
Hot-dipping aluminium-plating method of the present invention, the described plating step that helps is: place plating assistant agent to help plating 2～8min in 85～95 ℃ described workpiece; Described plating assistant agent is a mass concentration more than or equal to 5% potassium fluozirconate solution.
Hot-dipping aluminium-plating method of the present invention, described post-processing step is: described workpiece is placed the container that fills inactivating treatment liquid, sonic oscillation 5～20min; Described inactivating treatment liquid is nitric acid, phosphoric acid, distilled water according to 1: 1: 10～20 volume ratio blended mixing solutions.
For reaching above-mentioned purpose, according to the present invention, the metal device that also provides a kind of above-mentioned hot-dipping aluminium-plating method immersion plating to obtain.
The liquid of aluminizing of the present invention, with aluminium as main component, and added rare earth element, purified the liquid of aluminizing, refinement crystal grain, improve the wettability of aluminizing between liquid and the workpiece to be plated and the flowability of liquid of aluminizing, and then improved the adhesivity between the coating of workpiece and workpiece surface formation, strengthened the corrosion resistance nature of workpiece.
The liquid of aluminizing of the present invention is owing to added rare earth element, the oxidation that has also alleviated aluminium in the liquid of aluminizing effectively.
Hot-dipping aluminium-plating method of the present invention adopts the above-mentioned liquid of aluminizing that workpiece is carried out the surface processing of aluminizing, and has characteristics such as technology is simple, equipment requirements is low, easy handling, is suitable for the suitability for industrialized production that the metal works surface applies aluminum coating.
Metal device of the present invention adopts above-mentioned hot-dipping aluminium-plating method to handle forming layer of aluminum coating, and its surfacing, continuously has corrosion resistance nature preferably, has prolonged the work-ing life of workpiece in strong corrosive environments such as ocean environment.
Description of drawings
Fig. 1 is the schema of hot-dipping aluminium-plating method of the present invention.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention is further described in detail below in conjunction with drawings and Examples.
Fig. 1 is the schema of hot-dipping aluminium-plating method of the present invention, and as shown in Figure 1, hot-dipping aluminium-plating method of the present invention comprises oil removing, eliminates rust, helps plating, hot dip aluminum plating and passivation step, and detailed process is as follows:
One, pre-treatment
(1) oil removing (degreasing)
The degreasing fluid prescription is as follows:
Sodium hydroxide (NaOH) 20～50g/L
Yellow soda ash (Na
2CO
3) 30～50g/L
Sodium phosphate (Na
3PO
4) 20～40g/L
Water glass (Na
2SiO
3) 3～6g/L
Water surplus
According to the greasy dirt situation on metal works surface, use the degreasing fluid of above-mentioned prescription under 60～90 ℃ of conditions of temperature, workpiece to be handled 5～15min.
(2) clean
After the oil removal treatment, clean with the high-temperature water of normal-temperature water or 60～90 ℃, to remove the degreasing fluid of workpiece surface.
(3) rust cleaning
Rust removal liquid formula (massfraction) is as follows:
Hydrochloric acid 3～15%
Urotropine 0.2～1.0%
Water surplus
Wherein, urotropine prevents that as inhibiter hydrochloric acid to processed metal excessive corrosion, making the workpiece surface blackening.
The rust cleaning liquid that the workpiece that previous step is cleaned up is put into above-mentioned prescription carries out processing of rust removing, and the treatment time is 5～15min.
(4) clean
After processing of rust removing finished, cleaning workpiece was to remove its surperficial acid solution immediately.
(5) help plating
Plating assistant agent functional quality concentration is more than or equal to 5% K
2ZrF
6Solution, helping the plating treatment temp is 85～95 ℃, the time is 2～8min.
Helping plating is one vital operation in hot dipping method (flux method) aluminum plating process; whether the selection of plating assistant agent suitably is directly connected to the quality of protective coating quality; generally should possess following characteristics: plating assistant agent can form complete and imporous protective membrane on the workpiece substrate surface; both in the time of hot dip aluminum plating, can remove from matrix surface immediately; and absorption dissolved oxygen thing, can not pollute again the liquid of aluminizing.
Two, hot dip aluminum plating
The liquid of aluminizing of the present invention comprises the aluminium of massfraction 92～98% and the RE of massfraction 2～8%, and described RE is the mixture of the Ce of the Y of massfraction 10～30% and massfraction 70～90%.The liquid of aluminizing is selected commercial-purity aluminium for use with aluminium, and adds the lucium melting and form, and the melting step of the liquid of aluminizing comprises:
The Y of massfraction 30% and the Ce of massfraction 70% are mixed, under 850～950 ℃, be smelted into the RE alloy;
The described RE alloy of massfraction 2～8% and the aluminium of massfraction 92～98% are mixed, under 650～750 ℃, be smelted into the described liquid of aluminizing.
In addition, the aluminaization for the liquid that prevents to aluminize in the hot dip aluminum plating process also is added with surface dopant on the liquid surface of aluminizing, and the add-on of surface dopant is advisable to cover the liquid surface of aluminizing fully.The prescription of surface dopant (massfraction) is as follows:
KCl 40～60％
NaCl 30～50％
NaF 10～20％
Hot dip aluminum plating temperature be 650～750 ℃, its time is 2～8min.Hot dip aluminum plating temperature if low excessively, then can influence aluminium atom and the mutual diffusion mutually of being plated the device element, the coating fragility of formation is big, directly influenced the use properties of plating piece, but also can cause the mobile variation of liquid of aluminizing, thereby it is more to be plated device extension aluminium, rough, visual appearance is not good; Hot dip aluminum plating temperature if too high, though the flowability of the liquid of aluminizing makes moderate progress, the liquid of aluminizing volatilizees more.
Three, aftertreatment
Aftertreatment, promptly the purpose of Passivation Treatment is to form compact protective film on the surface of workpiece to be plated, to slow down the corrosion of plating piece.
Passivation Treatment liquid formula (volume ratio) is as follows:
Nitric acid 1
Phosphatase 11
Distilled water 10～20
After treating the work-piece cools after the hot dip aluminum plating, be placed in the container that fills inactivating treatment liquid, the 5～15min that vibrates in the ultra-sonic oscillation machine then makes the plating piece surface form continuous, fine and close passive film, cleans with clear water at last.
The liquid of aluminizing that hot-dipping aluminium-plating method of the present invention adopts, by adding rare earth element y, Ce in the liquid of aluminizing, improved the flowability of aluminium liquid, purify aluminium liquid and crystal grain thinning, reduced the degree of oxidation of the liquid of aluminizing, thereby strengthened the adhesivity between protective coating and the workpiece, improved the corrosion resistance nature of workpiece.
Embodiment 11Cr13 steel hot dip aluminum plating
Degreasing fluid: 35g/L sodium hydroxide, 40g/L yellow soda ash, 40g/L sodium phosphate, 5g/L water glass, surplus are water; Rust cleaning liquid: 15% hydrochloric acid, 1% urotropine, surplus are water; Plating assistant agent: 5% K
2ZrF
6Solution; Liquid 98%Al-2%RE (30%Y aluminizes, 70%Ce): massfraction is respectively 30%, 70% Y, Ce mixes, under 900 ℃, be smelted into the RE alloy, then massfraction be respectively 2%, 98% above-mentioned RE alloy, aluminium mixing, under 650 ℃, be smelted into the liquid of aluminizing; Surface dopant: 40%KCl, 45%NaCl, and 15%NaF; Inactivating treatment liquid: the volume ratio of nitric acid, phosphoric acid, distilled water is 1: 1: 20.
Workpiece is selected the 1Cr13 steel plate for use, utilize degreasing fluid under 80 ℃ to the workpiece oil removing, the degreasing fluid of clean back with normal-temperature water cleaning workpiece surface removed in visual inspection, then with rust cleaning liquid rust cleaning 10min, cleans up once more, utilizes plating assistant agent to help plating 4min at 90 ℃ then.
After helping plating to finish, place the liquid of aluminizing at 700 ℃ of immersion plating 4min workpiece.
After treating the work-piece cools after the immersion plating, be placed in the container that fills inactivating treatment liquid, place the ultra-sonic oscillation machine 10min that vibrates then, with clear water workpiece surface is cleaned up then.
1Cr13 steel plate after the hot dip aluminum plating, coating surface is smooth and continuous, and is good with the matrix bond degree.
Corrosion resistance nature test after the embodiment 21Cr13 steel hot dip aluminum plating
Carry out 800 ℃ of epoxidation experiments with the 1Cr13 steel plate after the hot dip aluminum plating that obtains among the embodiment 1.
Experimental basis smelting mark YB48264 carries out, and the 1Cr13 steel plate after the hot dip aluminum plating, the oxide film of its coating in the time of 800 ℃ are fine and close α-Al
2O
3, oxidation depth index R＜＜0.1mm/a, possess complete antioxidant anticorrosive performance at 800 ℃.Compare with the 1Cr13 steel plate of not immersion plating, the 1Cr13 steel plate after the hot dip aluminum plating has high temperature oxidation corrosion resistance performance preferably.
Embodiment 320CrMnTi steel hot dip aluminum plating
Degreasing fluid: 30g/L sodium hydroxide, 30g/L yellow soda ash, 30g/L sodium phosphate, 4g/L water glass, surplus are water; Rust cleaning liquid: 15% hydrochloric acid, 0.5% urotropine, surplus are water; Plating assistant agent: 5% K
2ZrF
6Solution; Liquid 98%Al-2%RE (20%Y aluminizes, 80%Ce): massfraction is respectively 20%, 80% Y, Ce mixes, under 850 ℃, be smelted into the RE alloy, then massfraction be respectively 2%, 98% above-mentioned RE alloy, aluminium mixing, under 700 ℃, be smelted into the liquid of aluminizing; Surface dopant: 50%KCl, 40%NaCl, and 10%NaF; Inactivating treatment liquid: the volume ratio of nitric acid, phosphoric acid, distilled water is 1: 1: 20.
Workpiece is selected the 20CrMnTi steel plate for use, utilize degreasing fluid under 90 ℃ to the workpiece oil removing, the degreasing fluid of clean back with 80 ℃ of water cleaning workpiece surfaces removed in visual inspection, then with the rust cleaning liquid 10min that eliminates rust, clean up once more, utilize plating assistant agent to help plating 3min at 90 ℃ then.
After helping plating to finish, place the liquid of aluminizing at 750 ℃ of immersion plating 2min device.
After treating the work-piece cools after the immersion plating, be placed in the container that fills inactivating treatment liquid, place the ultra-sonic oscillation machine 10min that vibrates then, with clear water workpiece surface is cleaned up then.
20CrMnTi steel plate after the hot dip aluminum plating, coating surface is smooth and continuous, and is good with the matrix bond degree.
Embodiment 420CrMnTi steel hot dip aluminum plating
Degreasing fluid: 35g/L sodium hydroxide, 40g/L yellow soda ash, 30g/L sodium phosphate, 3g/L water glass, surplus are water; Rust cleaning liquid: 15% hydrochloric acid, 1% urotropine, surplus are water; Plating assistant agent: 5% K
2ZrF
6Solution; Liquid 96%Al-4%RE (20%Y aluminizes, 80%Ce): massfraction is respectively 20%, 80% Y, Ce mixes, under 950 ℃, be smelted into the RE alloy, then massfraction be respectively 4%, 96% above-mentioned RE alloy, aluminium mixing, under 750 ℃, be smelted into the liquid of aluminizing; Surface dopant: 50%KCl, 40%NaCl, and 10%NaF; Inactivating treatment liquid: the volume ratio of nitric acid, phosphoric acid, distilled water is 1: 1: 20.
Workpiece is selected the 20CrMnTi steel plate for use, utilize degreasing fluid under 60 ℃ to the workpiece oil removing, the degreasing fluid of clean back with 60 ℃ of water cleaning workpiece surfaces removed in visual inspection, then with the rust cleaning liquid 10min that eliminates rust, clean up once more, utilize plating assistant agent to help plating 5min at 90 ℃ then.
After helping plating to finish, place the liquid of aluminizing at 700 ℃ of immersion plating 4min workpiece.
After treating the work-piece cools after the immersion plating, be placed in the container that fills inactivating treatment liquid, place the ultra-sonic oscillation machine 10min that vibrates then, with clear water workpiece surface is cleaned up then.
20CrMnTi steel plate after the hot dip aluminum plating, coating surface is smooth and continuous, and is good with the matrix bond degree.
Embodiment 51Cr13 steel hot dip aluminum plating
Degreasing fluid: 35g/L sodium hydroxide, 40g/L yellow soda ash, 40g/L sodium phosphate, 5g/L water glass, surplus are water; Rust cleaning liquid: 15% hydrochloric acid, 1% urotropine, surplus are water; Plating assistant agent: 8% K
2ZrF
6Solution; Liquid 92%Al-8%RE (10%Y aluminizes, 90%Ce): massfraction is respectively 10%, 90% Y, Ce mixes, under 900 ℃, be smelted into the RE alloy, then massfraction be respectively 8%, 92% above-mentioned RE alloy, aluminium mixing, under 650 ℃, be smelted into the liquid of aluminizing; Surface dopant: 60%KCl, 30%NaCl, and 10%NaF; Inactivating treatment liquid: the volume ratio of nitric acid, phosphoric acid, distilled water is 1: 1: 10.
Workpiece is selected the 1Cr13 steel plate for use, utilize degreasing fluid under 80 ℃ to the workpiece oil removing, the degreasing fluid of clean back with normal-temperature water cleaning workpiece surface removed in visual inspection, then with rust cleaning liquid rust cleaning 10min, cleans up once more, utilizes plating assistant agent to help plating 2min at 95 ℃ then.
After helping plating to finish, place the liquid of aluminizing at 650 ℃ of immersion plating 8min workpiece.
After treating the work-piece cools after the immersion plating, be placed in the container that fills inactivating treatment liquid, place the ultra-sonic oscillation machine 15min that vibrates then, with clear water workpiece surface is cleaned up then.
1Cr13 steel plate after the hot dip aluminum plating, coating surface is smooth and continuous, and is good with the matrix bond degree.
Embodiment 620CrMnTi steel hot dip aluminum plating
Degreasing fluid: 30g/L sodium hydroxide, 30g/L yellow soda ash, 30g/L sodium phosphate, 4g/L water glass, surplus are water; Rust cleaning liquid: 15% hydrochloric acid, 0.5% urotropine, surplus are water; Plating assistant agent: 10% K
2ZrF
6Solution; Liquid 96%Al-42%RE (30%Y aluminizes, 70%Ce): massfraction is respectively 30%, 70% Y, Ce mixes, under 950 ℃, be smelted into the RE alloy, then massfraction be respectively 6%, 94% above-mentioned RE alloy, aluminium mixing, under 700 ℃, be smelted into the liquid of aluminizing; Surface dopant: 40%KCl, 40%NaCl, and 20%NaF; Inactivating treatment liquid: the volume ratio of nitric acid, phosphoric acid, distilled water is 1: 1: 15.
Workpiece is selected the 20CrMnTi steel plate for use, utilize degreasing fluid under 90 ℃ to the workpiece oil removing, the degreasing fluid of clean back with 80 ℃ of water cleaning workpiece surfaces removed in visual inspection, then with the rust cleaning liquid 10min that eliminates rust, clean up once more, utilize plating assistant agent to help plating 2min at 85 ℃ then.
After helping plating to finish, place the liquid of aluminizing at 720 ℃ of immersion plating 4min device.
After treating the work-piece cools after the immersion plating, be placed in the container that fills inactivating treatment liquid, place the ultra-sonic oscillation machine 5min that vibrates then, with clear water workpiece surface is cleaned up then.
20CrMnTi steel plate after the hot dip aluminum plating, coating surface is smooth and continuous, and is good with the matrix bond degree.
Embodiment 7 light fixture hot dip aluminum platings
A kind of light fixture, its shell is made of metal, and treatment solution among the employing embodiment 1 and processing parameter carry out the hot dip aluminum plating processing to the shell of light fixture.
Light fixture after the hot dip aluminum plating, the coating surface that forms on its shell is smooth and continuous, and is good with the conjugation of shell.
The above only is representative embodiment of the present invention, does not limit the present invention in any way, and all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces or improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. the liquid of aluminizing is characterized in that, comprises the aluminium of massfraction 92～98% and the RE of massfraction 2～8%, and described RE is the mixture of the Ce of the Y of massfraction 10～30% and massfraction 70～90%.
2. the liquid of aluminizing according to claim 1 is characterized in that, described RE is the mixture of the Ce of the Y of massfraction 30% and massfraction 70%.
3. hot-dipping aluminium-plating method, comprise to workpiece carry out oil removing, cleaning, rust cleaning, clean, help plating, hot dip aluminum plating, post-processing step, it is characterized in that, described hot dip aluminum plating step is: described workpiece is immersed in the liquid of aluminizing, carry out hot dip aluminum plating in 650～750 ℃ and handle 2～8min, wherein, the described liquid of aluminizing comprises the aluminium of massfraction 92～98% and the RE of massfraction 2～8%, and described RE is the mixture of the Ce of the Y of massfraction 10～30% and massfraction 70～90%.
4. hot-dipping aluminium-plating method according to claim 3 is characterized in that, described RE is the mixture of the Ce of the Y of massfraction 30% and massfraction 70%.
5. hot-dipping aluminium-plating method according to claim 3 is characterized in that, described hot dip aluminum plating step also comprises the melting step of the described liquid of aluminizing, and the melting step of the described liquid of aluminizing comprises:
The Y of massfraction 30% and the Ce of massfraction 70% are mixed, under 850～950 ℃, be smelted into the RE alloy;
The described RE alloy of massfraction 2～8% and the aluminium of massfraction 92～98% are mixed, under 650～750 ℃, be smelted into the described liquid of aluminizing.
6. hot-dipping aluminium-plating method according to claim 3, it is characterized in that, in the described hot dip aluminum plating step, described hot dip aluminum plating liquid surface also is coated with surface dopant, and described surface dopant comprises that massfraction is respectively 40～60% KCl, 30～50% NaCl and 10～20% NaF.
7. hot-dipping aluminium-plating method according to claim 3 is characterized in that, the described plating step that helps is: place plating assistant agent to help plating 2～8min in 85～95 ℃ described workpiece; Described plating assistant agent is a mass concentration more than or equal to 5% potassium fluozirconate solution.
8. hot-dipping aluminium-plating method according to claim 3 is characterized in that, described post-processing step is: described workpiece is placed the container that fills inactivating treatment liquid, sonic oscillation 5～20min; Described inactivating treatment liquid is nitric acid, phosphoric acid, distilled water according to 1: 1: 10～20 volume ratio blended mixing solutions.
9. the metal device that each described hot-dipping aluminium-plating method immersion plating obtains according to claim 3～8.
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| CN103820667A (en) * | 2014-03-06 | 2014-05-28 | 大连理工大学 | Covering agent and aluminium-silicon alloy melt processing method |
| CN106676447A (en) * | 2016-12-28 | 2017-05-17 | 蚌埠南实科技有限公司 | Copper bar aluminizing process |
| CN109182944A (en) * | 2018-10-22 | 2019-01-11 | 安徽青润精密科技有限公司 | A kind of surface treatment method of non-ferrous metal workpiece |
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Cited By (4)
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| CN109182944A (en) * | 2018-10-22 | 2019-01-11 | 安徽青润精密科技有限公司 | A kind of surface treatment method of non-ferrous metal workpiece |
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| CN102296259B (en) | 2013-01-02 |
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