CN113088856B - Deep eutectic solvent hot galvanizing additive and preparation method and application thereof - Google Patents

Deep eutectic solvent hot galvanizing additive and preparation method and application thereof Download PDF

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CN113088856B
CN113088856B CN202110346084.4A CN202110346084A CN113088856B CN 113088856 B CN113088856 B CN 113088856B CN 202110346084 A CN202110346084 A CN 202110346084A CN 113088856 B CN113088856 B CN 113088856B
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eutectic solvent
deep eutectic
additive
hot galvanizing
salt
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CN113088856A (en
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卢宝阳
吴荣方
谢孝文
郅西敬
马虎德
吴之心
赵奇
徐景坤
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Ningbo Mingyi Metal Surface Treatment Co.,Ltd.
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Jiangxi Science and Technology Normal University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon

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Abstract

The invention belongs to the technical field of plating assistant additives, and discloses a deep eutectic solvent hot galvanizing additive, a preparation method and an application thereof, wherein the deep eutectic solvent hot galvanizing additive is prepared by mixing the following components in parts by weight of 30-70:1-20:3-8:1-10 parts of deep eutectic solvent, nonionic surfactant, inorganic salt and deionized water, heating, uniformly mixing, and standing. The additive is suitable for being directly added into the plating assistant agent, is applied to a hot galvanizing process, can effectively prevent zinc liquid from splashing in the galvanizing process, reduces the loss of the zinc liquid, improves the galvanizing speed, increases the yield, reduces the consumption of zinc ammonium chloride in the plating assistant agent, and can obviously reduce the carrying amount of iron ions; still shorten plating agent drying time, improve production efficiency, effectively clear away and plate the remaining oil stain in piece surface, isolated air alleviates the secondary that the oxidation arouses and rusts, obviously reduces the short circuit and plates, weakens zinc liquid and explodes splash intensity, reduces accident risks such as scald, and the smoke abatement environmental protection simultaneously.

Description

Deep eutectic solvent hot galvanizing additive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of plating assistants, and relates to a hot galvanizing additive, in particular to a deep eutectic solvent hot galvanizing additive, and a preparation method and application thereof.
Background
With the rapid development of economy, the demand for steel is increasing, but steel products are also subject to corrosion to various degrees when used in environmental conditions such as seawater and soil, in addition to exposure to the atmosphere. In order to ensure normal use and prolong the service life of steel products, the corrosion prevention technology of steel has been paid attention by people. Hot galvanizing is one of the most effective means for delaying corrosion of steel materials, and compared with other metal protection methods, the hot galvanizing process can form double protection of electrochemical and physical barriers on a plating layer, and the plating layer has the advantages of high bonding strength with a matrix, compactness, corrosion resistance, no maintenance, low cost and the like.
With the increasing demand of people for high-quality corrosion-resistant hot-galvanized plates, the current research on improving the coating effect is still the key point. The solvent assistant plating is an important processing procedure in the hot galvanizing process, can not only make up the defects in the previous procedures, but also further activate the surface of steel and improve the hot plating effect. The hot galvanizing additive used as the plating assistant additive can ensure that the plating assistant has better interface wettability and compatibility with a workpiece, improve the activity and the utilization rate of the plating assistant, improve the plating assistant effect, prevent plating leakage of the plated workpiece and reduce zinc slag.
The Chinese invention patent applications CN1036411A (named as water-soluble plating assistant agent for hot dip aluminum plating), CN1356404A (named as water-soluble plating assistant agent for hot dip galvanized aluminum alloy of steel), CN101126142A (named as additive for hot dip galvanized plating assistant agent) and the like all provide improvements on the plating assistant agent, strengthen the plating assistant effect, but neglect the problems of economy, environmental protection and the like, and have no strong guarantee on safety.
The deep eutectic solvent is a uniform transparent liquid formed by mixing two or more different hydrogen bond acceptors and hydrogen bond donors at a certain molar ratio and a certain temperature, is widely considered as a novel ionic liquid analogue, but actually, the chemical characteristics of the deep eutectic solvent and the ionic liquid are obviously different, and no report of applying the deep eutectic solvent to the field of hot galvanizing exists at present.
Disclosure of Invention
The invention aims to provide a deep eutectic solvent type hot galvanizing additive, which achieves the purposes of preventing plating leakage, preventing liquid metal from splashing, shortening drying time, reducing the using amount of a plating assistant agent, improving the nonuniformity of the thickness of a plating layer, reducing zinc consumption, and being economical, environment-friendly, safe and reusable in a hot galvanizing process by adding a deep eutectic solvent, a nonionic surfactant, an inorganic salt and deionized water;
the invention also aims to provide a preparation method of the deep eutectic solvent type hot galvanizing additive;
the invention also aims to provide application of the deep eutectic solvent type hot galvanizing additive.
In order to achieve the purpose, the invention adopts the technical scheme that:
the deep eutectic solvent hot galvanizing additive comprises the following raw materials of active ingredients in a weight ratio of 30-70:1-20:3-8:1-10 parts of deep eutectic solvent, nonionic surfactant, inorganic salt and deionized water.
As one definition, the deep eutectic solvent comprises a molar ratio of 1-2:1 and hydrogen bond donor and hydrogen bond acceptor.
As another limitation, the hydrogen bond donor is at least one of urea, thiourea, carboxylic acids, polyols, saccharides, and trifluoroacetamide;
the carboxylic acid-based substance is a compound having a carboxyl group; the polyol is a compound having at least one hydroxyl group; the carbohydrate is polyhydroxy aldehyde, polyhydroxy ketone or an organic compound which is hydrolyzed to generate polyhydroxy aldehyde and/or polyhydroxy ketone;
the hydrogen bond acceptor is at least one of quaternary ammonium salt, quaternary phosphonium salt, sulfonium salt and zwitterion;
wherein the carboxylic acid may be malonic acid, benzoic acid, phenylacetic acid, malic acid, adipic acid, oxalic acid, succinic acid, citric acid, phenylacetic acid, phenylpropionic acid, tricarballylic acid, levulinic acid, itaconic acid, tartaric acid, 4-hydroxybenzoic acid, caffeic acid, coumaric acid, cinnamic acid, suberic acid, or gallic acid;
the polyalcohol can be ethylene glycol, glycerol, butanediol, pentaerythritol, neopentyl glycol, hexanediol, dipropylene glycol, diethylene glycol, xylitol, sorbitol or isosorbide.
As a further limitation, the chemical structure general formula of the quaternary ammonium salt is as follows:
Figure BDA0003000728480000031
in the formula I, R 1 、R 2 、R 3 And R 4 All are alkyl, alkenyl, alcohol or halogenated alkyl with any integer of 1-20 carbon atoms; x 1 - Is F - 、Cl - 、Br - 、HSO 4 - Or RCOO - ；
The chemical structural general formula of the quaternary phosphonium salt is as follows:
Figure BDA0003000728480000032
in the formula II, R 5 、R 6 、R 7 And R 8 All are alkyl or aryl radicals having 1-20 carbon atoms, X 2 - Is F - 、Cl - 、Br - 、HSO 4 - Or RCOO - ；
The general chemical structure formula of the sulfonium salt is as follows:
Figure BDA0003000728480000033
in the formula III, R 9 、R 10 And R 11 All are alkyl or aryl radicals having 1-20 carbon atoms, X 3 - Is F - 、Cl - 、Br - 、HSO 4 - Or RCOO - ；
Wherein the quaternary ammonium salt may be choline chloride, tetraethylammonium chloride, N-ethyl-2-hydroxy-N, N-dimethylethylammonium chloride, 2- (chlorocarbonyloxy) -N, N, N-trimethylethylammonium chloride, N-benzyl-2-hydroxy-N, N-dimethylethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, 2-hydroxy-N, N-diethylethylammonium chloride, 2-chloro-N, N, N-trimethylethylammonium chloride, or choline chloride;
the quaternary phosphonium salt can be tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, methyltriphenylphosphonium bromide, methyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, propyltriphenylphosphonium bromide, propyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, dodecyltriphenylphosphonium bromide, tetradecyltriphenylphosphonium bromide or hexadecyltriphenylphosphonium bromide;
the sulfonium salt may be trimethylsulfonium bromide, dimethyl (4-vinylbenzyl) sulfonium chloride, triphenylsulfonium perfluorobutylsulfonate or (1-) [ [ (chlorophenyl) thio ] phenyl ] diphenylsulfonium hexafluorophosphate.
As a further limitation, the zwitterion is an amino acid type zwitterion, a betaine type zwitterion or an imidazoline type zwitterion;
wherein the zwitterion may be coconut oil fatty acid diethanolamide, dodecyl ethoxy sulfobetaine, dodecyl hydroxypropyl sulfobetaine, dodecyl dimethyl sulfopropyl betaine, lauryl amidopropyl betaine, cocamidopropyl betaine, stearyl amidopropyl betaine, tetradecyl amidopropyl hydroxypropyl sulfobetaine, decyl dimethyl hydroxypropyl sulfobetaine, octadecyl dimethyl sulfopropyl betaine, dodecyl dimethyl hydroxypropyl phosphate betaine, or tetradecyl dimethyl hydroxypropyl phosphate betaine.
As a further limitation, the nonionic surfactant is at least one of the compounds having the following general chemical structures IV-V:
Figure BDA0003000728480000051
in the formula IV, R 12 Is an alkylphenol having 1 to 20 carbon atoms, n 1 Is any integer of 2-80;
Figure BDA0003000728480000052
in the formula V, R 13 Is a long chain alkyl group having 1 to 20 carbon atoms, n 2 Is any integer of 2-80;
wherein, in the formula IV, R 12 Can be alkylphenol ethoxylates with any integer of 8-20 carbon atoms, n 1 Is any integer of 6-80; in the formula V, R 13 Can be alkylamide polyoxyethylene ether with any integer of 8-20 carbon atoms, n 2 Is any integer of 6-80;
preferably, the nonionic surfactant is coconut oil fatty acid diethanolamide;
preferably, the chemical structure of the nonionic surfactant is general formula IV, and R 12 Is alkylphenol polyoxyethylene ether with 11 carbon atoms, n 1 Is 2;
preferably, the chemical structure of the nonionic surfactant is general formula V, and R is 13 Is C11 alkylamide polyoxyethylene ether, n 2 Is 2.
As another limitation, the inorganic salt is at least one of a chloride salt, a fluoride salt, and a fluoride salt;
wherein the chloride salt can be ammonium chloride, sodium chloride, potassium chloride, barium chloride, zinc chloride, aluminum chloride or lithium chloride; the fluoride salt can be sodium fluoride, potassium fluoride, aluminum fluoride, ammonium fluoride or magnesium fluoride; the fluosilicate may be sodium fluorozirconate, potassium fluorozirconate, sodium fluorosilicate, potassium fluorosilicate, sodium fluoroborate, or potassium fluoroborate.
The invention also provides a preparation method of the deep eutectic solvent hot galvanizing additive, which comprises the steps of heating the raw materials, uniformly mixing and standing to obtain the deep eutectic solvent hot galvanizing additive.
As a limitation, the heating is raising the temperature to 40-70 ℃; the standing time is 9-12h.
The invention also provides an application of the deep eutectic solvent hot galvanizing additive, which is to add the deep eutectic solvent hot galvanizing additive into a plating assistant and mix the mixture uniformly for a hot galvanizing process; the dosage of the deep eutectic solvent hot galvanizing additive is 0.8-1% of the dosage of the plating assistant.
Wherein, the same effect can be achieved when the dosage of the deep eutectic solvent hot galvanizing additive is more than 1 percent, but the resource waste is caused.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
(1) The deep eutectic solvent hot galvanizing additive can prevent plating leakage, prevent liquid metal from splashing, shorten drying time, reduce the using amount of a plating assistant agent, improve the nonuniformity of the thickness of a plating layer, reduce zinc consumption, and is economical, environment-friendly, safe and reusable in a hot galvanizing process; the method has great significance for promoting the sustainable development of the metal coating industry;
(2) The deep eutectic solvent hot galvanizing additive is added with the deep eutectic solvent, the deep eutectic solvent is simple and convenient to synthesize, only a hydrogen bond donor and a hydrogen bond acceptor are required to be uniformly mixed, and particularly, the used hydrogen bond donor and the hydrogen bond acceptor are low in price and low in toxicity, most of the hydrogen bond donor and the hydrogen bond acceptor are biodegradable and do not need to be purified; the deep eutectic solvent can also generate chemical inertia with water and is easy to store;
(3) The deep eutectic solvent in the deep eutectic solvent hot galvanizing additive can be combined with ammonium chloride and zinc chloride in the plating assistant agent to form a continuous and uniform compact thin layer on the surface of a plated part, so that the surface tension of the plating assistant agent is greatly reduced, the moisture on a workpiece can be quickly separated from the surface of the workpiece, and the wettability of the plating assistant agent and the surface of the plated part is greatly improved;
(4) The nonionic surfactant in the deep eutectic solvent hot galvanizing additive has multiple functions of wetting, emulsifying, solubilizing, dispersing, permeating, cleaning and the like, can shorten the drying time of a workpiece, and improves the production efficiency; the consumption of ammonium chloride and zinc chloride is saved; the zinc liquid splashing strength is weakened, the zinc explosion amount is reduced by over 75 percent, and accidents such as scalding are reduced; the zinc ash amount is reduced, and the ash discharging speed is improved; the reducing gas can be decomposed to protect the plated part; the surface of the plated part is brighter and smoother; the residual oil stain on the surface of the plated part can be removed, air is isolated, secondary rusting caused by oxidation is reduced, and plating leakage is obviously reduced; smoke is effectively reduced, and the environment is protected;
(5) The deep eutectic solvent in the deep eutectic solvent hot galvanizing additive provided by the invention has a synergistic effect with a nonionic surfactant, so that the wettability of a plated part and a plating assistant is further increased, the surface tension of the plated part is reduced, and the immersion plating time of a workpiece is shortened.
(6) The inorganic salt in the deep eutectic solvent hot galvanizing additive can keep the pH value of the plating assistant agent between 4 and 5, so that the plating assistant effect is better, and the production cost can be reduced;
the preparation method of the invention is simple and rapid, has low cost, low toxicity, is not easy to volatilize, is not decomposed during hot-dip coating, is harmless to human body and is suitable for industrial production, and the prepared deep eutectic solvent hot-dip galvanizing additive is suitable for being used as a plating assistant to be applied to a hot-dip galvanizing process.
Detailed Description
The present invention is further illustrated by the following specific examples, which are to be construed as merely illustrative, and not limitative, of the remainder of the disclosure.
If the experimental conditions not specified in the examples are specified, the conditions are generally conventional or recommended by the reagent company; reagents, consumables and the like used in the following examples are commercially available unless otherwise specified, and all processes used therein are conventional in the art unless otherwise specified.
EXAMPLES 1-28 METHOD FOR PREPARING DEEP eutectic SOLVENT-BASED HOT DIP GALVANIZING ADDITIVE
Examples 1 to 28 are methods for preparing a deep eutectic solvent based hot dip galvanizing additive, respectively, by mixing, by weight, 30 to 70:1-20:3-8:1-10 parts of deep eutectic solvent, nonionic surfactant, inorganic salt and deionized water are heated to 40-70 ℃, mixed uniformly and kept stand for 9-12 hours to obtain corresponding deep eutectic solvent hot galvanizing additives, which are sequentially marked as J1-J28;
wherein the deep eutectic solvent is prepared from the following components in a molar ratio of 1-2:1 and hydrogen bond donor and hydrogen bond acceptor (structure and mark code are shown in table 1-2) are mixed uniformly; the structure and the labeling code of the nonionic surfactant are shown in Table 3;
the preparation of examples 1-28 is essentially the same, except for the choice of starting materials and the adjustment of other process parameters, as detailed in tables 4-7.
TABLE 1 Hydrogen bond acceptor Structure and marker codes
Figure BDA0003000728480000081
TABLE 2 Hydrogen bond acceptor structures and marker codes
Figure BDA0003000728480000091
TABLE 3 Structure of nonionic surfactant and Mark code
Figure BDA0003000728480000101
Table 4 examples 1-7 process parameters
Figure BDA0003000728480000102
Figure BDA0003000728480000111
TABLE 5 examples 8-15 Process parameters
Figure BDA0003000728480000112
Figure BDA0003000728480000121
TABLE 6 EXAMPLES 16-23 Process parameters
Figure BDA0003000728480000122
Figure BDA0003000728480000131
TABLE 7 EXAMPLES 24-31 Process parameters
Figure BDA0003000728480000132
EXAMPLE 29 application of deep eutectic solvent based Hot Dip additive
Preparation of comparative hot galvanizing additive
The comparative hot galvanizing additives CJ1 to CJ5 were prepared respectively in the following manners:
(1) comparative hot dip galvanizing additive CJ1:
the plating assistant additive is prepared according to the method in patent document CN 101126142A: putting 6.3kg of tetradecyl dimethyl benzyl ammonium chloride, 1.2kg of isopropanol, 0.9kg of alkylphenol polyoxyethylene (12) ether, 0.1kg of potassium fluocomplex and 3kg of deionized water into a reaction vessel with a heating device, preserving heat and stirring for two hours at 50 ℃, cooling to room temperature, diluting to 10 liters of constant volume with the deionized water, and stirring uniformly to obtain the comparative hot galvanizing additive CJ1.
(2) Comparative hot dip galvanizing additive CJ2:
according to the weight ratio of choline chloride: the molar ratio of ethylene glycol is 1:2 preparing a deep eutectic solvent at 60 ℃, and weighing 60kg; adding 5kg of zinc chloride, and shaking up; and adding 10kg of deionized water, shaking uniformly, and standing for 12 hours to obtain the comparative hot galvanizing additive CJ2.
(3) Comparative hot dip galvanizing additive CJ3:
according to the weight ratio of dodecyl dimethyl betaine: the molar ratio of ethylene glycol is 1:2 preparing a deep eutectic solvent at 60 ℃, and weighing 68kg; adding 7kg of zinc chloride, and shaking up; 5kg of deionized water is added, shaken uniformly and kept stand for 12 hours, and the comparative hot galvanizing additive CJ3 is obtained.
(4) Comparative hot galvanizing additive CJ4:
according to the weight ratio of choline chloride: the molar ratio of glycerol is 1:2 preparing a deep eutectic solvent at 60 ℃, and weighing 65kg; adding 8kg of zinc chloride, and shaking up; adding 9kg of deionized water, shaking uniformly and standing for 12 hours to obtain the comparative hot galvanizing additive CJ4.
(5) Comparative hot galvanizing additive CJ5:
according to the proportion of tetraethylammonium chloride: the molar ratio of the butanediol is 1:2 preparing a deep eutectic solvent at 60 ℃, and weighing 70kg; adding 7kg of zinc chloride, and shaking up; 5kg of deionized water is added, shaken uniformly and kept stand for 12 hours, thus obtaining the comparative hot galvanizing additive CJ5.
II) application of hot galvanizing additive
Respectively carrying out plating-assisting tests by using the deep eutectic solvent hot galvanizing additives J1-J28 and the comparative hot galvanizing additives CJ1-CJ5, wherein the tests are carried out in 34 groups, wherein 28 groups of the test groups are formed, and the deep eutectic solvent hot galvanizing additives J1-J28 are correspondingly adopted one by one; the control groups are 5 groups, and comparative hot galvanizing additives CJ1-CJ5 are adopted in a one-to-one correspondence mode; the blank control group is 1 group in total, only the plating assistant is used, and no hot galvanizing additive is added;
in the plating assistant test, the average value of each group is taken for 5 times, the conventional hot galvanizing process is adopted, the plating assistant agent additive is changed only in the plating assistant process, and the plating assistant effect is observed.
The application method of each group of hot galvanizing additive comprises the following steps: adding corresponding hot galvanizing additives into the plating assistant agent, uniformly mixing, and using the hot galvanizing additives in the hot galvanizing process instead of the plating assistant agent, wherein the hot galvanizing additives and the using amounts corresponding to each group are shown in a table 8;
wherein, the plating assistant agent is normal ammonium chloride and zinc chloride plating assistant agent, and the plating assistant agent contains 45wt% of ammonium chloride, 30wt% of zinc chloride and 25wt% of deionized water.
Table 8 shows the hot-dip galvanizing additives and the amounts thereof
Group of Types of hot-dip galvanizing additives Amount (kg) of hot galvanizing additive Amount (kg) of plating assistant agent
Test groups 1 to 3 J1-J3 8 1000
Test groups 4 to 5 J4-J5 10 1000
Test groups 6 to 7 J6-J7 9 1000
Test groups 8 to 28 J8-J28 8 1000
Control group 1 CJ1 8 1000
Control group 2 CJ2 8 1000
Control group 3 CJ3 8 1000
Control group 4 CJ4 8 1000
Control group 5 CJ5 8 1000
Blank control group - - 1000
Observing or recording the indexes in the plating assistant test process, and judging the application effect of the invention (see table 9); the observed or recorded indexes are as follows:
surface tension: measuring the contact angle by a contact angle measuring instrument to measure the surface tension;
drying time: the drying time is calculated by taking the drying time of a blank control group as 100%, the shorter the drying time is, the faster the processing speed is, and the larger the yield is;
zinc cascade situation: according to the result obtained by visual observation, the zinc waterfall condition of a blank control group is taken as 'strong', and the comparison record is carried out;
smoke size: comparing and recording the smoke size of a blank control group which is obtained by visual observation and is 'very large';
thickness of zinc layer: measuring the thickness of the base body before assistant plating, and measuring the thickness of the base body after assistant plating, wherein the plating thickness = (the thickness of the base body after assistant plating-the thickness of the base body before assistant plating)/2;
and (3) plating assisting condition: and judging whether plating leakage exists or not according to the smoothness of the surface of the workpiece after plating assistance.
TABLE 9 plating assistant effect of each group
Figure BDA0003000728480000161
Figure BDA0003000728480000171
The results in table 9 show that the deep eutectic solvent hot dip galvanizing additive of the invention achieves the following effects:
the drying time of the workpiece can be shortened, and the production efficiency is improved;
the consumption of ammonium chloride and zinc chloride is saved: after the additive is added, when the effect is reduced, the plating assistant solution is not required to be replaced, only the usage amount of the plating assistant solution is required to be added, and the plating assistant solution can be repeatedly used, so that the usage amounts of ammonium chloride and zinc chloride are reduced compared with the replacement of the plating assistant solution;
the zinc liquid splashing strength is weakened, the zinc explosion amount is reduced by over 75 percent, and accidents such as scalding are reduced; the zinc ash amount is reduced, and the ash discharging speed is improved; the reducing gas can be decomposed to protect the plated part; the surface of the plated part is brighter and smoother; the residual oil stain on the surface of the plated part can be removed, air is isolated, secondary rusting caused by oxidation is reduced, and plating leakage is obviously reduced; effectively reduces smoke and protects environment.
The preparation and use methods of the deep eutectic solvent type hot galvanizing additive are simple, do not cause damage to the environment and related operators, and are suitable for hot galvanizing and hot galvanizing aluminum alloy and hot aluminizing processes based on hot galvanizing processes.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in other forms, and any person skilled in the art may use the above-mentioned technical content as a teaching to make changes or modifications to the equivalent embodiments with equivalent changes, but all those simple changes, equivalent changes and modifications made to the above-mentioned embodiments without departing from the technical spirit of the present invention, and still all those embodiments are within the scope of the present invention as claimed in the claims.

Claims (8)

1. The deep eutectic solvent hot galvanizing additive is characterized in that raw materials for preparing active ingredients of the deep eutectic solvent hot galvanizing additive comprise, by weight, 30-70:1-20:3-8:1-10 parts of deep eutectic solvent, nonionic surfactant, inorganic salt and deionized water;
wherein the deep eutectic solvent comprises the following components in a molar ratio of 1-2:1 hydrogen bond donor and hydrogen bond acceptor; the hydrogen bond donor is at least one of urea, thiourea, carboxylic acid substances, polyalcohol substances, saccharides and trifluoroacetamide;
the carboxylic acid-based substance is a compound having a carboxyl group; the polyol is a compound having at least one hydroxyl group; the carbohydrate is polyhydroxy aldehyde, polyhydroxy ketone or an organic compound which is hydrolyzed to generate polyhydroxy aldehyde and/or polyhydroxy ketone;
the hydrogen bond acceptor is at least one of quaternary ammonium salt, quaternary phosphonium salt, sulfonium salt and zwitterion.
2. The deep eutectic solvent hot dip galvanizing additive according to claim 1, wherein the chemical structural general formula of the quaternary ammonium salt is:
Figure FDA0003867444490000011
in the formula I, R 1 、R 2 、R 3 And R 4 All are alkyl, alkenyl, alcohol with carbon number of 1-20A group or a haloalkyl group; x 1 - Is F - 、Cl - 、Br - 、HSO 4 - Or RCOO - ；
The chemical structural general formula of the quaternary phosphonium salt is as follows:
Figure FDA0003867444490000012
in the formula II, R 5 、R 6 、R 7 And R 8 All are alkyl or aryl radicals having 1-20 carbon atoms, X 2 - Is F - 、Cl - 、Br - 、HSO 4 - Or RCOO - ；
The general chemical structure formula of the sulfonium salt is as follows:
Figure FDA0003867444490000021
in the formula III, R 9 、R 10 And R 11 All are alkyl or aryl radicals having 1-20 carbon atoms, X 3 - Is F - 、Cl - 、Br - 、HSO 4 - Or RCOO - 。
3. The deep eutectic solvent based hot dip galvanizing additive as claimed in claim 1, wherein the zwitterion is an amino acid based zwitterion, a betaine based zwitterion, or an imidazoline based zwitterion.
4. The deep eutectic solvent based hot dip galvanizing additive of claim 1, wherein the non-ionic surfactant is at least one of compounds having the following general chemical structures IV-V:
Figure FDA0003867444490000022
in the formula IV, R 12 Is an alkylphenol having 1 to 20 carbon atoms, n 1 Is any integer of 2-80;
Figure FDA0003867444490000023
in the formula V, R 13 Is a long chain alkyl group having 1 to 20 carbon atoms, n 2 Is any integer of 2-80.
5. The deep eutectic solvent based hot dip galvanizing additive of claim 1, wherein the inorganic salt is at least one of a chloride salt, a fluoride salt, and a fluoride salt.
6. The method for preparing the deep eutectic solvent type hot galvanizing additive according to any one of claims 1 to 5, wherein the deep eutectic solvent type hot galvanizing additive is obtained by heating, uniformly mixing and standing the raw materials.
7. The method of preparing a deep eutectic solvent based hot dip galvanizing additive of claim 6, wherein the heating is to raise the temperature to 40-70 ℃; the standing time is 9-12h.
8. The application of the deep eutectic solvent type hot galvanizing additive as claimed in any one of claims 1 to 5, wherein the deep eutectic solvent type hot galvanizing additive is added into a plating assistant and uniformly mixed for a hot galvanizing process; the dosage of the deep eutectic solvent hot galvanizing additive is 0.8-1% of the dosage of the plating assistant.
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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3230615A (en) * 1962-11-23 1966-01-25 Allied Tube & Conduit Corp Continuous tube forming and galvanizing
AT321056B (en) * 1971-10-21 1975-03-10 Bekaert Sa Nv Coating process
JPS5348030A (en) * 1976-10-14 1978-05-01 Nippon Paint Co Ltd Nonnplating treating agent and method of partial molten metal plating using said nonnplating treating agent
CA1151586A (en) * 1979-11-23 1983-08-09 Alain Palsky Continuous galvanizing and drawing process
JPH0910988A (en) * 1995-06-28 1997-01-14 Sony Corp Flux
KR20030031635A (en) * 2001-10-15 2003-04-23 박준하 Flux compositions for hot dip galvanizing
CN101328568A (en) * 2008-06-23 2008-12-24 南通飞拓生物科技有限公司 Multifunctional assistant plating additive for hot dip plating process, preparation and use method thereof
CN101555576A (en) * 2009-05-22 2009-10-14 昆明理工大学 Plating assistant agent addition agent for immersion plating
CN105256343A (en) * 2015-11-23 2016-01-20 安徽工业大学 Electrogalvanizing method based on choline chloride-xylitol deep eutectic solvent
CN106498452A (en) * 2016-10-27 2017-03-15 安徽工业大学 A kind of electrogalvanizing method based on glycine betaine urea water eutectic solvent
CN107699833A (en) * 2017-08-16 2018-02-16 江苏飞拓界面工程科技有限公司 Help plating additive, quickening liquid and hot dip coating method
CN108707934A (en) * 2018-06-28 2018-10-26 南京信息工程大学 A kind of method of fast-growth thickness spelter coating on Copper substrate
CN109536993A (en) * 2019-01-23 2019-03-29 东北大学 A kind of method of electrodeposit metals zinc in eutectic solvent

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070128246A1 (en) * 2005-12-06 2007-06-07 Hossainy Syed F A Solventless method for forming a coating

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3230615A (en) * 1962-11-23 1966-01-25 Allied Tube & Conduit Corp Continuous tube forming and galvanizing
AT321056B (en) * 1971-10-21 1975-03-10 Bekaert Sa Nv Coating process
JPS5348030A (en) * 1976-10-14 1978-05-01 Nippon Paint Co Ltd Nonnplating treating agent and method of partial molten metal plating using said nonnplating treating agent
CA1151586A (en) * 1979-11-23 1983-08-09 Alain Palsky Continuous galvanizing and drawing process
JPH0910988A (en) * 1995-06-28 1997-01-14 Sony Corp Flux
KR20030031635A (en) * 2001-10-15 2003-04-23 박준하 Flux compositions for hot dip galvanizing
CN101328568A (en) * 2008-06-23 2008-12-24 南通飞拓生物科技有限公司 Multifunctional assistant plating additive for hot dip plating process, preparation and use method thereof
CN101555576A (en) * 2009-05-22 2009-10-14 昆明理工大学 Plating assistant agent addition agent for immersion plating
CN105256343A (en) * 2015-11-23 2016-01-20 安徽工业大学 Electrogalvanizing method based on choline chloride-xylitol deep eutectic solvent
CN106498452A (en) * 2016-10-27 2017-03-15 安徽工业大学 A kind of electrogalvanizing method based on glycine betaine urea water eutectic solvent
CN107699833A (en) * 2017-08-16 2018-02-16 江苏飞拓界面工程科技有限公司 Help plating additive, quickening liquid and hot dip coating method
CN108707934A (en) * 2018-06-28 2018-10-26 南京信息工程大学 A kind of method of fast-growth thickness spelter coating on Copper substrate
CN109536993A (en) * 2019-01-23 2019-03-29 东北大学 A kind of method of electrodeposit metals zinc in eutectic solvent

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Deep Eutectic Solvents (DESs) and Their Applications;Emma L. Smith等;《CHEMICAL REVIEWS》;20141010;第11060-11082页 *
低共熔溶剂处理含锌烟尘;雷震;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》;20180115(第1期);第B027-962页 *
锌在新型低温熔盐中的绿色电沉积;郑勇等;《有色金属（冶炼部分）》;20160512(第5期);第5-9页 *

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