CN103173706B - The smokeless plating assistant agent of batch quantity hot dipping zinc and using method - Google Patents

The smokeless plating assistant agent of batch quantity hot dipping zinc and using method Download PDF

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CN103173706B
CN103173706B CN201310055814.0A CN201310055814A CN103173706B CN 103173706 B CN103173706 B CN 103173706B CN 201310055814 A CN201310055814 A CN 201310055814A CN 103173706 B CN103173706 B CN 103173706B
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plating
smokeless
assistant agent
zinc
hot dipping
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CN103173706A (en
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郑建
周汉涛
周德龙
邢丹丹
陈春雷
吕明春
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JIANGSU FEITUO INTERFACE ENGINEERING TECHNOLOGY Co Ltd
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Abstract

The invention discloses the smokeless plating assistant agent of batch quantity hot dipping zinc, composed of the following components: zinc chloride 70 ~ 300g/L, aluminum chloride 0 ~ 30? g/L, Sodium Silicofluoride 5 ~ 40g/L, ammonia carboxylation compound 0 ~ 15g/L, nonionogenic tenside? 2 ~ 10g/L, cats product? 2 ~ 12g/L.The invention also discloses the using method of the smokeless plating assistant agent of batch quantity hot dipping zinc, comprise the following steps: quickening liquid double salt total concn controls at 120 ~ 400g/L, quickening liquid temperature 40 ~ 80 DEG C, pH value 3 ~ 5.5; Workpiece, after pickling and washing, directly immerses quickening liquid, helps the plating time to be 5 ~ 10 minutes, and after helping plating, workpiece is dried, and bake out temperature is 60 ~ 120 DEG C.Smokeless plating assistant agent of the present invention, has wetting infiltration, when low temperature helps plating, can accelerate salt film attachment speed and adhesion amount, can control salt film adhesion amount when high temperature helps plating, reduce and produce ash quantity, avoids zinc chloride too much to produce the problem of the quick-fried zinc of moisture regain.

Description

The smokeless plating assistant agent of batch quantity hot dipping zinc and using method
Technical field
The present invention relates to metal surface treatment technology, particularly relate to the smokeless plating assistant agent of batch quantity hot dipping zinc.
The invention still further relates to a kind of using method of batch quantity hot dipping zinc plating assistant agent, belong to metallic substance technical field of anticorrosion.
Background technology
At metallic surface coated metal or other non-metallic coatings, the corrosion of matrix metal effectively can be prevented.Hot-dip plating metal technique comprise galvanizing, hot dip aluminum plating, hot dipping of zinc-aluminum alloy etc., mostly adopt solvent method, immerse by plating metal in the liquid metal bath of melting, after proposing work-piece cools, surface forms the very thin metal plating of one deck, thus corrosion resistance nature is improved greatly.
Solvent helps plating to be one important treatment process in galvanizing pre-treatment, and it not only can make up the deficiency that former procedure may exist, and can also activate steel surface, improves galvanizing quality.This is unexistent in other steel anti-corrosive techniques.Its quality, not only directly affects quality of coating, also has a significant impact zinc consumption cost.Tradition help depositing process be by pickling after steel piece immerse in the chloride zinc chloride ammonium quickening liquid of certain ingredients again, form the process of the thin zinc chloride ammonium salt film of one deck after proposition at article surface.Helping plating operation to play clean effect to steel piece surface, after removing pickling, remain in molysite or the oxide compound of article surface, making steel piece have larger surfactivity when entering zinc bath.The zinc chloride ammonium salt film that after helping plating, workpiece surface covers plays activation, is embodied in: time (1) lower than 200 DEG C, and workpiece surface forms a kind of approximate H 2[Zn (OH) 2cl 2] composite salt film, this is a kind of strong acid, thus ensures that workpiece surface cannot form oxide film and keep active state in drying process.(2) more than 200 DEG C, the NH in workpiece surface salt film 4cl at high temperature can resolve into NH 3and HCl, the now erosion of HCl to workpiece substrate accounts for leading, makes steel surface form oxide compound, keeps the active state of steel substrate.So be that ammonium chloride tool plays a very important role at galvanizing, proper use of ammonium chloride produces a very large impact galvanizing quality.
Although ammonium chloride helps plating to play a very important role, a large amount of flue dust can be produced owing to decomposing under the high temperature conditions, affect the health of workshop condition and workman.For the volume of smoke produced, most domestic enterprise does not adopt adequate measure to process.And in American-European countries, generally have employed the mode of flue dust collecting filtration treatment, produced flue dust is processed in the filter after air-bleed system is collected.This flue dust collecting treatment system equipment is huge, operation energy consumption is higher.More to smokeless plating assistant agent research both at home and abroad, have scholar to propose to substitute ammonium chloride with NaCl and KCl, but research is closely under test, does not have actual industrial application.Pot galvanize practice shows, containing impurity such as NaCl or KCl of massfraction more than 1% in quickening liquid, can cause and help plating effect to decline, and causing plating leakage to return plating workpiece increases greatly.At present, be more focus on the low ammonium of low cigarette to help plating research and industrialization.Korea S helps the product of plating with or without ammonium, is dissected and draws wherein also containing more ammonium chloride composition, can not reach completely smokeless effect by formula.
Invented a kind of phytate plating resisting agent for heat zinc coating in Chinese patent (CN101122000A), plating assistant agent is made up of PHYTIC ACID ZINC SALT, borax, Sodium Fluoride, citric acid, oxalic acid, not containing ammonium chloride in plating assistant agent, is conducive to the improvement of Working environment.And for example, invent multifunctional plating assistant agent used for hot dipping additive in Chinese patent (CN101328568A), the additive be made up of has been added in the plating assistant agent be made up of Sodium Fluoride, aluminum fluoride, zinc chloride, ammonium chloride, potassium chlorate fluozirconate, Potassium monofluoride, sodium-chlor when improving hot dip process help plating effect quaternary cationics and polyoxyethylene ether nonionic surfactant.In addition, some other patent excessive use sodium-chlor, Repone K etc., control with great difficulty not produce plating leakage and return the problems such as plating, should not promote the use of.For this reason, the present invention proposes a kind of smokeless plating assistant agent without chlorination ammonium salt, can greatly reduce the flue dust produced in hot galvanizing process, improve the environment in workshop.
Summary of the invention
The invention provides the smokeless plating assistant agent of a kind of batch quantity hot dipping zinc.
Present invention also offers the using method of the smokeless plating assistant agent of a kind of batch quantity hot dipping zinc.
This smokeless plating assistant agent can reduce the flue dust produced in batch quantity hot dipping zinc process, improves plating piece rate of drying, reduces the problem of quick-fried zinc and plating leakage, reduces unnecessary zinc consumption, saves production cost.
The technical solution used in the present invention is:
The smokeless plating assistant agent of batch quantity hot dipping zinc, composed of the following components: zinc chloride 70 ~ 300g/L, aluminum chloride 0 ~ 30 g/L, Sodium Silicofluoride 5 ~ 40 g/L, ammonia carboxylation compound 5 ~ 15 g/L, nonionogenic tenside 2 ~ 10 g/L, cats product 2 ~ 12 g/L.
Described ammonia carboxylation compound has following molecular structural formula:
R in formula 1molecular structure as follows:
wherein, the value of n is 0 ~ 10;
R in formula 2molecular structure as follows:
wherein, the value of m is 0 ~ 5.
Described nonionogenic tenside comprise in fatty alcohol-polyoxyethylene ether and alkyl glycoside one or both.
Described fatty alcohol-polyoxyethylene ether has following molecular structural formula:
Wherein, R 3for the one in methyl, ethyl, propyl group, methylol, hydroxyethyl, hydroxypropyl, R 4for C 2~ C 8chain alkyl, the value of m is the value of 0 ~ 3, n is 10 ~ 40.
The molecular formula of described alkyl glycoside is:
Wherein, R 5for C 8 ~c 10chain alkyl, the value of n is 1.4 ~1.8.
The structure of described cats product is:
Wherein, R 9for the one in methyl, ethyl, propyl group, butyl, methylol, hydroxyethyl, hydroxypropyl, benzyl, R 7for C 6~ C 14chain alkyl, R 6, R 8for methyl or methylol, X is halide-ions.
The using method of the smokeless plating assistant agent of batch quantity hot dipping zinc, comprises the following steps:
1, quickening liquid double salt total concn controls at 120 ~ 400g/L, quickening liquid temperature 40 ~ 80 DEG C, pH value 3 ~ 5.5;
2, workpiece is after pickling and washing, directly immerses quickening liquid, helps the plating time to be 5 ~ 10 minutes, and after helping plating, workpiece is dried, and bake out temperature is 60 ~ 120 DEG C.
In described step 2, pickling adopts is mass concentration 15%-20% hydrochloric acid, pickling time 15-60 minute.
Smokeless plating assistant agent of the present invention, there is wetting infiltration, to the scope helping plating composite salt to have certain saturation, first workpiece surface is attached on a small quantity helping active principle of the present invention in plated journey, formation speed difference according to salt film plays the effect accelerated or limit respectively, play the effect of adjustment, thus effectively the adhesion amount of composite salt is controlled in certain scope; When low temperature helps plating, salt film attachment speed and adhesion amount can be accelerated, when avoiding low temperature, produce the problem of plating leakage because salt film concentration is not enough; Meanwhile, salt film adhesion amount can be controlled when high temperature helps plating, reduce and produce ash quantity, avoid zinc chloride too much to produce the problem of the quick-fried zinc of moisture regain.
Embodiment
The following examples can make the present invention of those skilled in the art comprehend, but do not limit the present invention in any way.
Embodiment 1
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 70g/L, aluminum chloride 30 g/L, Sodium Silicofluoride 5 g/L, ammonia carboxylation compound 5 g/L, nonionogenic tenside 2g/L, cats product 2g/L.Wherein, R in ammonia carboxylation compound 1n=0, R in molecular structural formula 2m=0 in molecular structural formula; When nonionogenic tenside is fatty alcohol-polyoxyethylene ether, R 3for methyl, R 4for C 2chain alkyl, m value 2, n value 25; R in cats product 9for methyl, R 7for C 6chain alkyl, R 6, R 8for methyl, X is halide-ions.
Embodiment 2
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 70g/L, aluminum chloride 30 g/L, Sodium Silicofluoride 5 g/L, ammonia carboxylation compound 10 g/L, nonionogenic tenside 2g/L, cats product 3g/L.Wherein, R in ammonia carboxylation compound 1n=1, R in molecular structural formula 2m=1 in molecular structural formula; When nonionogenic tenside is fatty alcohol-polyoxyethylene ether, R 3for ethyl, R 4for C 3chain alkyl, m value 1, n value 15; R in cats product 9for ethyl, R 7for C 7chain alkyl, R 6, R 8for methyl, X is halide-ions.
Embodiment 3
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 70g/L, aluminum chloride 30 g/L, Sodium Silicofluoride 5 g/L, ammonia carboxylation compound 20 g/L, nonionogenic tenside 2g/L, cats product 4g/L.Wherein, R in ammonia carboxylation compound 1n=2, R in molecular structural formula 2m=2 in molecular structural formula; When nonionogenic tenside is fatty alcohol-polyoxyethylene ether, R 3for propyl group, R 4for C 4chain alkyl, m value 0, n value 10; R in cats product 9for propyl group, R 7for C 8chain alkyl, R 6, R 8for methyl, X is halide-ions.
Embodiment 4
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 100g/L, aluminum chloride 15 g/L, Sodium Silicofluoride 10g/L, ammonia carboxylation compound 5g/L, nonionogenic tenside 4g/L, cats product 5g/L.Wherein, nonionogenic tenside 2g/L, cats product 2g/L.Wherein, R in ammonia carboxylation compound 1n=3, R in molecular structural formula 2m=3 in molecular structural formula; When nonionogenic tenside is alkyl glycoside, R 5for C 8chain alkyl, n value 1.4; R in cats product 9for butyl, R 7for C 9chain alkyl, R 6, R 8for methylol, X is halide-ions.
Embodiment 5
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 150g/L, aluminum chloride 10 g/L, Sodium Silicofluoride 10g/L, ammonia carboxylation compound 10g/L, nonionogenic tenside 6g/L, cats product 6g/L.Wherein, nonionogenic tenside 2g/L, cats product 2g/L.Wherein, R in ammonia carboxylation compound 1n=4, R in molecular structural formula 2m=4 in molecular structural formula; When nonionogenic tenside is alkyl glycoside, R 5for C 9chain alkyl, n value 1.6; R in cats product 9for methylol, R 7for C 10chain alkyl, R 6, R 8methylol, X is halide-ions.
Embodiment 6
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 200g/L, aluminum chloride 20 g/L, Sodium Silicofluoride 15g/L, ammonia carboxylation compound 15 g/L, nonionogenic tenside 8g/L, cats product 7g/L.Wherein, nonionogenic tenside 2g/L, cats product 2g/L.Wherein, R in ammonia carboxylation compound 1n=5, R in molecular structural formula 2m=5 in molecular structural formula; When nonionogenic tenside is alkyl glycoside, R 5for C 10chain alkyl, n value 1.8; R in cats product 9for hydroxyethyl, R 7for C 11chain alkyl, R 6, R 8for methylol, X is halide-ions.
Embodiment 7
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 250g/L, aluminum chloride 25 g/L, Sodium Silicofluoride 20 g/L, ammonia carboxylation compound 20 g/L, nonionogenic tenside 10g/L, cats product 8g/L.Wherein, R in ammonia carboxylation compound 1n=6, R in molecular structural formula 2m=0 in molecular structural formula; When nonionogenic tenside is fatty alcohol-polyoxyethylene ether, R 3for methyl, R 4for C 2chain alkyl, m value 1, n value 20; R in cats product 9for in benzyl, R 7for C 12chain alkyl, R 6, R 8for methyl, X is halide-ions.
Embodiment 8
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 300g/L, aluminum chloride 30 g/L, Sodium Silicofluoride 25g/L, ammonia carboxylation compound 20 g/L, nonionogenic tenside 10g/L, cats product 9g/L.Wherein, R in ammonia carboxylation compound 1n=7, R in molecular structural formula 2m=1 in molecular structural formula; When nonionogenic tenside is fatty alcohol-polyoxyethylene ether, R 3for ethyl, R 4for C 4chain alkyl, m value 2, n value 30; R in cats product 9for methyl, R 7for C 13chain alkyl, R 6, R 8for methyl, X is halide-ions.
Embodiment 9
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 300g/L, Sodium Silicofluoride 5 g/L, ammonia carboxylation compound 20 g/L, nonionogenic tenside 2g/L, cats product 8g/L.Wherein, R in ammonia carboxylation compound 1n=8, R in molecular structural formula 2m=2 in molecular structural formula; When nonionogenic tenside is fatty alcohol-polyoxyethylene ether, R 3for propyl group, R 4for C 6chain alkyl, m value 3, n value 40; R in cats product 9for ethyl, R 7for C 14chain alkyl, R 6, R 8for methyl, X is halide-ions.
Embodiment 10
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 70g/L, aluminum chloride 5 g/L, Sodium Silicofluoride 5 g/L, ammonia carboxylation compound 5 g/L, nonionogenic tenside 2g/L, cats product 10g/L.Wherein, nonionogenic tenside 2g/L, cats product 2g/L.Wherein, R in ammonia carboxylation compound 1n=9, R in molecular structural formula 2m=3 in molecular structural formula; When nonionogenic tenside is alkyl glycoside, R 5for C 2chain alkyl, n value 1.5; R in cats product 9for propyl group, R 7for C 6chain alkyl, R 6, R 8for methyl, X is halide-ions.
Embodiment 11
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 150g/L, aluminum chloride 15 g/L, Sodium Silicofluoride 25 g/L, ammonia carboxylation compound 12g/L, nonionogenic tenside 6g/L, cats product 11g/L.Wherein, R in ammonia carboxylation compound 1n=10, R in molecular structural formula 2m=4 in molecular structural formula; When nonionogenic tenside is alkyl glycoside, R 5for C 4chain alkyl; R in cats product 9for butyl, R 7for C 7chain alkyl, n value 1.7, R 6, R 8for methyl, X is halide-ions.
Embodiment 12
The smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention, composed of the following components: zinc chloride 300g/L, Sodium Silicofluoride 40 g/L, ammonia carboxylation compound 5 g/L, nonionogenic tenside 10g/L, cats product 12g/L.Wherein, R in ammonia carboxylation compound 1n=10, R in molecular structural formula 2m=5 in molecular structural formula; When nonionogenic tenside is alkyl glycoside, R 5for C 6chain alkyl; R in cats product 9for methylol, R 7for C 14chain alkyl, n value 1.8, R 6, R 8for methylol, X is halide-ions.
Following examples 13-15 is the embodiment of the using method of the smokeless plating assistant agent of batch quantity hot dipping zinc of the present invention.
Embodiment 13
The using method of the smokeless plating assistant agent of batch quantity hot dipping zinc, comprises the following steps:
1, quickening liquid double salt total concn controls at 120g/L, quickening liquid temperature 40 DEG C, pH value 3;
2, workpiece is after pickling and washing, and it is mass concentration 15% hydrochloric acid that pickling adopts, and pickling time 15 minutes, directly immerses quickening liquid, helps the plating time to be 5 minutes, and after helping plating, workpiece is dried, and bake out temperature is 60 DEG C.
Embodiment 14
The using method of the smokeless plating assistant agent of batch quantity hot dipping zinc, comprises the following steps:
1, quickening liquid double salt total concn controls at 260g/L, quickening liquid temperature 60 C, pH value 4.2;
2, workpiece is after pickling and washing, and it is mass concentration 17% hydrochloric acid that pickling adopts, and pickling time 40 minutes, directly immerses quickening liquid, helps the plating time to be 7 minutes, and after helping plating, workpiece is dried, and bake out temperature is 90 DEG C.
Embodiment 15
The using method of the smokeless plating assistant agent of batch quantity hot dipping zinc, comprises the following steps:
1, quickening liquid double salt total concn controls at 400g/L, quickening liquid temperature 80 DEG C, pH value 5.5;
2, workpiece is after pickling and washing, and it is mass concentration 20% hydrochloric acid that pickling adopts, and pickling time 60 minutes, directly immerses quickening liquid, helps the plating time to be 10 minutes, and after helping plating, workpiece is dried, and bake out temperature is 120 DEG C.
Test without ammonium quickening liquid of the present invention, when quickening liquid temperature 40 DEG C, plating leakage rate only has 3.3%, but smoke dust, plating piece smooth surface, without list edge; When quickening liquid temperature 80 DEG C, plating leakage rate is 0, but has a small amount of flue dust, plating piece surface unusual light smooth, without list edge.
Note: above data are the statistics of every 30 batches.Zinc-plated temperature 440 DEG C, workpiece is tubing.
Smokeless plating assistant agent of the present invention, there is wetting infiltration, to the scope helping plating composite salt to have certain saturation, first workpiece surface is attached on a small quantity helping active principle of the present invention in plated journey, formation speed difference according to salt film plays the effect accelerated or limit respectively, play the effect of adjustment, thus effectively the adhesion amount of composite salt is controlled in certain scope.
When low temperature helps plating, salt film attachment speed and adhesion amount can be accelerated, when avoiding low temperature, produce the problem of plating leakage because salt film concentration is not enough.Meanwhile, salt film adhesion amount can be controlled when high temperature helps plating, reduce and produce ash quantity, avoid zinc chloride too much to produce the problem of the quick-fried zinc of moisture regain.

Claims (7)

1. the smokeless plating assistant agent of batch quantity hot dipping zinc, is characterized in that, composed of the following components: zinc chloride 70 ~ 300g/L, aluminum chloride 0 ~ 30 g/L, Sodium Silicofluoride 5 ~ 40 g/L, ammonia carboxylation compound 5 ~ 15 g/L, nonionogenic tenside 2 ~ 10 g/L, cats product 2 ~ 12 g/L; Described ammonia carboxylation compound has following molecular structural formula:
R in formula 1molecular structure as follows:
wherein, the value of n is 0 ~ 10;
R in formula 2molecular structure as follows:
wherein, the value of m is 0 ~ 5.
2., according to the smokeless plating assistant agent of the batch quantity hot dipping zinc described in claim 1, it is characterized in that, described nonionogenic tenside comprise in fatty alcohol-polyoxyethylene ether and alkyl glycoside one or both.
3. the smokeless plating assistant agent of batch quantity hot dipping zinc according to claim 2, is characterized in that, described fatty alcohol-polyoxyethylene ether has following molecular structural formula:
Wherein, R 3for the one in methyl, ethyl, propyl group, methylol, hydroxyethyl, hydroxypropyl, R 4for C 2~ C 8chain alkyl, the value of m is the value of 0 ~ 3, n is 10 ~ 40.
4. according to the smokeless plating assistant agent of the batch quantity hot dipping zinc described in claim 2, it is characterized in that, the molecular formula of described alkyl glycoside is:
Wherein, R 5for C 8 ~c 10chain alkyl, the value of n is 1.4 ~1.8.
5. according to the smokeless plating assistant agent of the batch quantity hot dipping zinc described in claim 1, it is characterized in that, the structure of described cats product is:
Wherein, R 9for the one in methyl, ethyl, propyl group, butyl, methylol, hydroxyethyl, hydroxypropyl, benzyl, R 7for C 6~ C 14chain alkyl, R 6, R 8for methyl or methylol, X is halide-ions.
6. according to any one of claim 1-5the using method of the smokeless plating assistant agent of batch quantity hot dipping zinc, is characterized in that, comprise the following steps:
1, quickening liquid double salt total concn controls at 120 ~ 400g/L, quickening liquid temperature 40 ~ 80 DEG C, pH value 3 ~ 5.5;
2, workpiece is after pickling and washing, directly immerses quickening liquid, helps the plating time to be 5 ~ 10 minutes, and after helping plating, workpiece is dried, and bake out temperature is 60 ~ 120 DEG C.
7. the using method of the smokeless plating assistant agent of described batch quantity hot dipping zinc according to claim 6, is characterized in that, in step 2, pickling adopts is mass concentration 15%-20% hydrochloric acid, pickling time 15-60 minute.
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CN111876708A (en) * 2020-07-15 2020-11-03 杨吉 Improved process for reducing zinc consumption of hot-dip galvanized steel pipe by controlling uniformity of zinc layer
CN115537698B (en) * 2022-09-29 2024-05-14 华南理工大学 Hot-dip galvanizing smokeless plating assistant and hot-dip galvanizing method

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