CN109295480A - A kind of acid zinc plating electroplate liquid - Google Patents
A kind of acid zinc plating electroplate liquid Download PDFInfo
- Publication number
- CN109295480A CN109295480A CN201811329666.6A CN201811329666A CN109295480A CN 109295480 A CN109295480 A CN 109295480A CN 201811329666 A CN201811329666 A CN 201811329666A CN 109295480 A CN109295480 A CN 109295480A
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- China
- Prior art keywords
- electroplate liquid
- brightening
- leveling agent
- zinc plating
- acid zinc
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
Abstract
The invention discloses a kind of acid zinc plating electroplate liquids, the acid zinc plating electroplate liquid includes brightening and leveling agent, the brightening and leveling agent includes brightening and leveling agent I and/or brightening and leveling agent II, the brightening and leveling agent I is the mixture of fatty acid methyl ester ethoxylate or its sulfonate sodium and natural alcohol polyoxy alkenyl salt, the brightening and leveling agent II is 2,4,7,9- tetramethyl -5- decine -4,7- glycol salt.The present invention is compared with traditional acid zinc plating electroplate liquid, and the electroplate liquid is nontoxic, pollution-free, exhausted water is easily processed, and meets environmentally protective requirement；Plating solution performance is stablized, the binding force jail of coating and matrix, and low temperature resistant dispersion performance and heat-resisting quantity are preferable；And acid zinc plating electroplate liquid provided by the invention has good low bubble property and foam inhibition effect.
Description
Technical field
The present invention relates to electroplating technologies, and in particular to a kind of acid zinc plating electroplate liquid.
Background technique
In order to provide a corrosion resistant protective layer to steel piece, then it must be deoiled, be removed on steel piece surface
The cleaning process and then utilization electrochemical deposition principle of embroidery, plate one layer of metal layer to achieve the goal.In China or even the world
In range, using it is most be one layer of metal zinc layers of plating.Because zinc is resourceful, cheap；Secondly as the electricity of zinc
Electrode potential is more negative than iron, and for steel substrate, zinc coat belongs to anodic coating, and when corroding, zinc coating is first
It dissolves, sacrifice oneself itself to protect steel substrate.Therefore, the zinc-plated application amount in plating total amount is maximum, reaches 60% or more,
It is the first big plating.
In the technique of electrogalvanizing, mainly there are acid zinc plating technique and alkaline galvanizing technology.During acid zinc plating technique is incoming
More than 40 years history of state, before this, alkaline zinc plating dominates market, since the cyanide in alkali zinc has severe toxicity, to human body,
Water source, soil and environment can all cause biggish harm；Compared with alkaline zinc plating toxicity technique, sour zinc environmental-friendly aspect more
Be conducive to the development of zincincation, current efficiency height (up to 95%), deposition velocity is fast, and dispersibility is good, plates layer porosity phase
To lower, there is higher toughness.
Acid zinc plating is also known as chloride galvanizing, and China's chloride galvanizing technique has been developed as the mainstream work of non-cyanogen galvanization
Skill, however current acid chloride is zinc-plated is primarily present following problem: in order to brightener ingredient such as aromatic aldehyde, aromatic ketone with
And heterocyclic aldehydes and heterocyclic ketone etc. have collaboration compatibility well, acid chloride is zinc-plated would generally to use phenolic compound, this
A little substances can will cause very big harm to human body, water source, soil, environment；Since low bubble plating solution will not influence in electroplating process
Subsequent technique and using more convenient, low bubble plating solution is the development trend of zincincation, but domestic at present manufactures low bubble softness
The chemical raw material less varieties and valuableness of agent, some need import are zinc-plated at high cost.
Summary of the invention
It is an object of the invention to overcome above-mentioned technical deficiency, a kind of acid zinc plating electroplate liquid is proposed, the electroplate liquid is nontoxic,
Pollution-free, low bubble, plating solution performance are stablized, and environmental requirement is met.
To reach above-mentioned technical purpose, technical solution of the present invention provides a kind of acid zinc plating electroplate liquid, the acid plating
Zinc electroplate liquid includes brightening and leveling agent, and the brightening and leveling agent includes brightening and leveling agent I and/or brightening and leveling agent II, the light
Bright leveling agent I is the mixing of fatty acid methyl ester ethoxylate or its sulfonate sodium and natural alcohol polyoxy alkenyl salt
Object, the brightening and leveling agent II are 2,4,7,9- tetramethyl -5- decine -4,7- glycol salts.
Compared with prior art, the beneficial effect comprise that
1, in acid zinc plating electroplate liquid provided by the invention with fatty acid methyl ester ethoxylate or its sulfonate sodium and
In the mixture of natural alcohol polyoxy alkenyl salt, 2,4,7,9- tetramethyl -5- decine -4,7- glycol salt
The mixture of one or both is as brightener, compared with traditional acid zinc plating electroplate liquid, the electroplate liquid is nontoxic, it is pollution-free,
Exhausted water is easily processed, and meets environmentally protective requirement；
2, acid zinc plating electroplate liquid provided by the invention, plating solution performance are stablized, the binding force jail of coating and matrix, and resistance to low
Warm dispersion performance and heat-resisting quantity are preferable；
3, compared with traditional acid zinc plating electroplate liquid, acid zinc plating electroplate liquid provided by the invention has good low bubble
Property and foam inhibition effect.
Detailed description of the invention
Fig. 1 is effect picture of the electroplate liquid of the embodiment of the present invention 4 under cold galvanising test；
Fig. 2 is effect picture of the electroplate liquid of the embodiment of the present invention 4 under room temperature plating test；
Fig. 3 is effect picture of the electroplate liquid of the embodiment of the present invention 4 under high temperature plating test；
Fig. 4 is the foam performance test result figure of electroplate liquid of the invention.
Specific embodiment
Present embodiments provide a kind of acid zinc plating electroplate liquid comprising brightening and leveling agent, brightening and leveling agent include light
Leveling agent I and/or brightening and leveling agent II, brightening and leveling agent I are fatty acid methyl ester ethoxylate or its sulfonate sodium and day
The mixture of right alcohol polyoxy alkenyl salt, brightening and leveling agent II are 2,4,7,9- tetramethyl -5- decine -4,7- glycol ethers
Sulfonate sodium.
In some preferred embodiments, the structural formula of fatty acid methyl ester ethoxylate are as follows:
The structural formula of fatty acid methyl ester ethoxylate sulfonate sodium are as follows:
Wherein, n=0~7.
In some preferred embodiments, fatty acid methyl ester ethoxylate FMEE, fatty acid methyl ester ethoxylate
Sulfonate sodium is FMES.
In some preferred embodiments, natural alcohol polyoxy alkenyl salt is Natural Alcohol Polyoxyethylene Ether sodium sulfonate
Salt or natural alcohol polyoxyethylene-propylene are copolymerized salt, natural alcohol polyoxy alkenyl salt structural formula are as follows:
Wherein, n=0~7；M=7~20；
R is C8、C10、C12、C14、C16、C18、C8-10、C12-14、C16-18；That is R be followed successively by eight alcohol of natural carbon, ten alcohol of natural carbon,
Natural carbon lauryl alcohol, natural carbon tetradecyl alchohol, natural carbon hexadecanol, natural carbon octadecyl alcolol, 80 alcohol of natural carbon, natural carbon 12
Tetrol, natural carbon cetostearyl alcohol.
N represents propoxyl group quantity, and as n=0, which is Natural Alcohol Polyoxyethylene Ether sulfonate sodium；When n ≠ 0
When, which is natural alcohol polyoxyethylene-propylene copolymerization salt.
In some preferred embodiments, natural alcohol polyoxy alkenyl salt is positive octanol sodium sulfonate of ethoxylated
Any one in salt, n-octyl alcohol polyoxyethylene-propylene salt or succinic acid monoester sodium salt, wherein n-octyl alcohol polyoxy
Ethylene-propylene salt structural formula are as follows:
In some preferred embodiments, brightening and leveling agent is the mixture of brightening and leveling agent I and brightening and leveling agent II, i.e.,
By the mixture of fatty acid methyl ester ethoxylate or its sulfonate sodium and natural alcohol polyoxy alkenyl salt, 2,4,7,
Both 9- tetramethyl -5- decine -4,7- glycol salts compound.
In some preferred embodiments, the mass ratio of brightening and leveling agent I and brightening and leveling agent II are 1:1~2, i.e., fatty
The mixture of sour methyl ester ethoxylates or its sulfonate sodium and natural alcohol polyoxy alkenyl salt and 2,4,7,9- tetra-
Methyl -5- decine -4,7- glycol salt is the mixing of 1:1~2 according to mass ratio.
In some preferred embodiments, if fatty acid methyl ester ethoxylate and natural alcohol polyoxy alkene ether sodium sulfonate
Salt mixing, then the mass ratio of fatty acid methyl ester ethoxylate and natural alcohol polyoxy alkenyl salt is 1:5.
In some preferred embodiments, if fatty acid methyl ester ethoxylate sulfonate sodium and natural alcohol polyoxy alkenyl
Salt mixes, then the quality of fatty acid methyl ester ethoxylate sulfonate sodium and natural alcohol polyoxy alkenyl salt
Than for 2:7.
In some preferred embodiments, the content of fatty acid methyl ester ethoxylate is 95%, and surplus is deionized water；
The content of fatty acid methyl ester ethoxylate sulfonate sodium is 60%, and surplus is deionized water；Natural Alcohol Polyoxyethylene Ether sulfonic acid
Sodium salt and natural alcohol polyoxyethylene-propylene copolymerization salt content are 75%, and surplus is deionized water；2,4,7,9- tetra-
The content of methyl -5- decine -4,7- glycol salt is 75%, and surplus is deionized water.
In some preferred embodiments, acid zinc plating electroplate liquid further includes zinc chloride, potassium chloride, buffer, wherein delaying
Electuary is boric acid；Zinc chloride provides zinc ion for galvanizing flux；Conductive salt of the potassium chloride as plating solution；In order to guarantee anode zine plate
Normal dissolution, boric acid are used to adjust the pH value of plating solution.
In some preferred embodiments, acid zinc plating electroplate liquid includes following component:
Acid zinc plating electroplate liquid of the invention further includes the common additive in electroplate liquid field, including but not limited to fill-in light
Bright dose, the inorganic salts for widening bright range, at least one of the anti-compound burnt.
Auxiliary brightener of the invention can be aromatic aldehyde or aromatic ketone；The inorganic salts for widening bright range can be benzene first
Sour sodium or urea；The anti-compound burnt can be niacin or HS-1000 (originating from German BASF)；And auxiliary brightener, expansion
The inorganic salts of wide bright range and the anti-compound burnt are also an option that the additive of the common the type in electroplate liquid field.
The present embodiment additionally provides a kind of preparation method of acid zinc plating electroplate liquid, includes the following steps:
To deionized water is added in the mixture of zinc chloride and boric acid, after stirring and dissolving is complete, chlorine is added into mixed liquor
Change potassium, after potassium to be chlorinated is completely dissolved, then suitable carbon dust and zinc powder is added into mixed liquor, is sufficiently stirred, after mixing
Filtering, brightening and leveling agent is added into filtrate, after mixing, with deionized water constant volume to get finished product.
Wherein, the content of carbon dust is 1g/L, and the content of zinc powder is 2g/L.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
Acid zinc plating electroplate liquid provided by the invention is further elaborated.Experimental material used in the present invention is such as without special theory
It is bright, it is that market is commercially available；It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and do not have to
It is of the invention in limiting.
Embodiment 1:
The embodiment of the present invention 1 provides a kind of acid zinc plating electroplate liquid, and wherein brightening and leveling agent I is FMEE and n-octyl alcohol
Polyoxyethylene-propylene salt mixture, and FMEE and n-octyl alcohol polyoxyethylene-propylene salt are according to quality
It is mixed than 2:5, which includes following component:
To deionized water is added in the mixture of zinc chloride and boric acid, after stirring and dissolving is complete, chlorine is added into mixed liquor
Change potassium, after potassium to be chlorinated is completely dissolved, then 1g/L carbon dust and 2g/L zinc powder is added into mixed liquor, is sufficiently stirred, be uniformly mixed
After filter, brightening and leveling agent is added into filtrate, after mixing, is settled to 1L with deionized water to get finished product.
Embodiment 2:
The embodiment of the present invention 2 provides a kind of acid zinc plating electroplate liquid, and wherein brightening and leveling agent II is 2,4,7,9- tetra-
Methyl -5- decine -4,7- glycol salt, which includes following component:
Using the preparation method in same embodiment 1,1L acid zinc plating electroplate liquid is prepared.
Embodiment 3:
The embodiment of the present invention 3 provides a kind of acid zinc plating electroplate liquid, and wherein brightening and leveling agent I is FMES and n-octyl alcohol
Polyoxyethylene-propylene salt mixture, and FMES and n-octyl alcohol polyoxyethylene-propylene salt are according to quality
It is mixed than 1:7；Brightening and leveling agent II is 2,4,7,9- tetramethyl -5- decine -4,7- glycol salts, which includes
Following component:
Using the preparation method in same embodiment 1,1L acid zinc plating electroplate liquid is prepared.
Embodiment 4:
The embodiment of the present invention 4 provides a kind of acid zinc plating electroplate liquid, and wherein brightening and leveling agent I is FMES and n-octyl alcohol
Polyoxyethylene-propylene salt mixture, and FMES and n-octyl alcohol polyoxyethylene-propylene salt are according to quality
It is mixed than 2:7；Brightening and leveling agent II is 2,4,7,9- tetramethyl -5- decine -4,7- glycol salts, which includes
Following component:
Using the preparation method in same embodiment 1,1L acid zinc plating electroplate liquid is prepared.
Embodiment 5:
The embodiment of the present invention 5 provides a kind of acid zinc plating electroplate liquid, and wherein brightening and leveling agent I is FMEE and n-octyl alcohol
Polyoxyethylene-propylene salt mixture, and FMEE and n-octyl alcohol polyoxyethylene-propylene salt are according to quality
It is mixed than 1:5, brightening and leveling agent II is 2,4,7,9- tetramethyl -5- decine -4,7- glycol salts, which includes
Following component:
Using the preparation method in same embodiment 1,1L acid zinc plating electroplate liquid is prepared.
Test example 1
The plating performance of acid zinc plating electroplate liquid of the invention is tested
1, sample: acid zinc plating electroplate liquid obtained is as test specimen, the light of simultaneous selection routine in selection example 4
The acidic Bath that bright leveling agent is prepared is as reference substance；
2, test method:
(1) cold galvanising is tested: two kinds of electroplate liquids are carried out to 500mL Hull Cell test at 5~20 DEG C respectively；
(2) two kinds of electroplate liquids room temperature plating test: are carried out to 500mL Hull Cell test at 20~35 DEG C respectively；
(3) two kinds of electroplate liquids high temperature plating test: are carried out to 250mL Hull Cell test at 35~50 DEG C respectively.
3, test result:
Cold galvanising test result is shown in Fig. 1, as seen from Figure 1, using acid zinc plating electroplate liquid of the invention, low temperature electric
Plating test piece ratio, using the high area of conventional brightening and leveling agent to burn range smaller, and test piece bright range in area of senior middle school is wider, and low area walks
It is longer, illustrate that the present invention significantly improves the low temperature resistant dispersion performance of acid chloride electroplate liquid；
Room temperature plating test result is shown in Fig. 2, as seen from Figure 2, using acid zinc plating electroplate liquid of the invention, room temperature electricity
It is wider using conventional brightening and leveling agent bright range to plate test piece ratio, walks longer, hence it is evident that improve the brightening and leveling of plating test piece
Property；
High temperature plating test result is shown in Fig. 3, as seen from Figure 3, using acid zinc plating electroplate liquid of the invention, high-temperature electric
It is wider using the conventional high area's bright range of brightening and leveling agent to plate test piece ratio, and the middle area area that whitens is less, hence it is evident that improve acidity
The heat-resisting quantity of chloride electroplate liquid and the stability of plating solution.
Low temperature resistant dispersion performance, heat-resisting quantity, the plating solution of acid zinc plating electroplate liquid of the invention it can be seen from Fig. 1~3
Stability and the electroplate liquid that conventional brightening and leveling agent is prepared is superior to the improvement result of plating test piece brightening and leveling.
Test example 2
The foam performance of acid zinc plating electroplate liquid of the invention is tested
1, sample: as test specimen, simultaneous selection is conventional for acid zinc plating electroplate liquid obtained in selection example 1~5
Brightening and leveling agent prepare acidic Bath as reference substance；
2, test method: by the Examples 1 to 5 of equivalent test specimen and reference substance be injected separately into tool plug graduated cylinder,
It is tested by the bubble mode of shaking for respectively shaking 30 times up and down, foam of the 6 groups of electroplate liquids of record in 0min, 1min, 3min, 5min is high
Spend situation.
3, test result:
The foam performance test result of acid zinc plating electroplate liquid is shown in Fig. 4, as seen from Figure 4, acid zinc plating of the invention
Electroplate liquid has apparent low bubble, and as seen from Figure 4, in Examples 1 to 5, the foam height of embodiment 4 is minimum,
Lather collapse it is most fast, the foam inhibition effect for illustrating that acid zinc plating is electroplated in embodiment 4 is best.
The above described specific embodiments of the present invention are not intended to limit the scope of the present invention..Any basis
Any other various changes and modifications that technical concept of the invention is made should be included in the guarantor of the claims in the present invention
It protects in range.
Claims (10)
1. a kind of acid zinc plating electroplate liquid, which is characterized in that the acid zinc plating electroplate liquid includes brightening and leveling agent, the light
Leveling agent includes brightening and leveling agent I and/or brightening and leveling agent II, the brightening and leveling agent I are fatty acid methyl ester ethoxylate
Or the mixture of its sulfonate sodium and natural alcohol polyoxy alkenyl salt, the brightening and leveling agent II are 2,4,7,9- tetra-
Methyl -5- decine -4,7- glycol salt.
2. acid zinc plating electroplate liquid according to claim 1, which is characterized in that the fatty acid methyl ester ethoxylate
Structural formula are as follows:
The structural formula of fatty acid methyl ester ethoxylate sulfonate sodium are as follows:
Wherein, n=0~7.
3. acid zinc plating electroplate liquid according to claim 1, which is characterized in that the natural alcohol polyoxy alkene ether sodium sulfonate
Salt is Natural Alcohol Polyoxyethylene Ether sulfonate sodium or natural alcohol polyoxyethylene-propylene is copolymerized salt, and the natural alcohol is poly-
Oxy alkylene salt structural formula are as follows:
Wherein, n=0~7；M=7~20；
R is C8、C10、C12、C14、C16、C18、C8-10、C12-14、C16-18。
4. acid zinc plating electroplate liquid according to claim 1, which is characterized in that the brightening and leveling agent is brightening and leveling agent
The mixture of I and brightening and leveling agent II.
5. acid zinc plating electroplate liquid according to claim 4, which is characterized in that the brightening and leveling agent I and brightening and leveling
Agent II mass ratio is 1:1~2.
6. acid zinc plating electroplate liquid according to claim 1, which is characterized in that the fatty acid methyl ester ethoxylate and
The mass ratio of natural alcohol polyoxy alkenyl salt is 1:5.
7. acid zinc plating electroplate liquid according to claim 1, which is characterized in that fatty acid methyl ester ethoxylate sodium sulfonate
The mass ratio of salt and natural alcohol polyoxy alkenyl salt is 2:7.
8. acid zinc plating electroplate liquid according to claim 3, which is characterized in that the fatty acid methyl ester ethoxylate
Content is 95%, and the content of fatty acid methyl ester ethoxylate sulfonate sodium is 60%, Natural Alcohol Polyoxyethylene Ether sulfonate sodium
It is 75% with natural alcohol polyoxyethylene-propylene copolymerization salt content, 2,4,7,9- tetramethyl -5- decine -4,7- bis-
The content of alcohol salt is 75%.
9. acid zinc plating electroplate liquid according to claim 1, which is characterized in that the acid zinc plating electroplate liquid further includes chlorine
Change zinc, potassium chloride and buffer, the buffer is boric acid.
10. acid zinc plating electroplate liquid according to claim 9, which is characterized in that the acid zinc plating electroplate liquid includes such as
Lower component:
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811329666.6A CN109295480A (en) | 2018-11-09 | 2018-11-09 | A kind of acid zinc plating electroplate liquid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811329666.6A CN109295480A (en) | 2018-11-09 | 2018-11-09 | A kind of acid zinc plating electroplate liquid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110284162A (en) * | 2019-07-22 | 2019-09-27 | 广州三孚新材料科技股份有限公司 | Cyanide-free alkaline copper plating solution for photovoltaic confluence welding strip and preparation method thereof |
| CN110965086A (en) * | 2019-11-21 | 2020-04-07 | 武汉奥邦表面技术有限公司 | Acidic zinc plating impurity removing agent and application thereof |
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|---|---|---|---|---|
| US4170526A (en) * | 1978-01-16 | 1979-10-09 | Oxy Metal Industries Corporation | Electroplating bath and process |
| US4229268A (en) * | 1979-07-09 | 1980-10-21 | Rohco, Inc. | Acid zinc plating baths and methods for electrodepositing bright zinc deposits |
| CN102943288A (en) * | 2012-11-19 | 2013-02-27 | 湖北吉和昌化工科技有限公司 | Carrier brightening agent for potassium chloride galvanization and preparation method thereof |
| CN105483762A (en) * | 2015-11-30 | 2016-04-13 | 武汉奥克特种化学有限公司 | Method for preparing potassium chloride galvanization carrier brightener through block polyether |
-
2018
- 2018-11-09 CN CN201811329666.6A patent/CN109295480A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4170526A (en) * | 1978-01-16 | 1979-10-09 | Oxy Metal Industries Corporation | Electroplating bath and process |
| US4229268A (en) * | 1979-07-09 | 1980-10-21 | Rohco, Inc. | Acid zinc plating baths and methods for electrodepositing bright zinc deposits |
| CN102943288A (en) * | 2012-11-19 | 2013-02-27 | 湖北吉和昌化工科技有限公司 | Carrier brightening agent for potassium chloride galvanization and preparation method thereof |
| CN105483762A (en) * | 2015-11-30 | 2016-04-13 | 武汉奥克特种化学有限公司 | Method for preparing potassium chloride galvanization carrier brightener through block polyether |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110284162A (en) * | 2019-07-22 | 2019-09-27 | 广州三孚新材料科技股份有限公司 | Cyanide-free alkaline copper plating solution for photovoltaic confluence welding strip and preparation method thereof |
| CN110965086A (en) * | 2019-11-21 | 2020-04-07 | 武汉奥邦表面技术有限公司 | Acidic zinc plating impurity removing agent and application thereof |
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