CN103882484A - Plating solution for high-speed electrotinning - Google Patents

Abstract

The invention discloses a plating solution for high-speed tin plating. The plating solution comprises the following components: 5-100g/L tin methanesulfonate, 10-100mL/L methanesulfonic acid, 0.1-20ml/L sulfuric acid, 0.1 -200mg/L defoamer, 0.1-50g/L fine crystal agent, 0.01-20g/L walking agent, 0.1-40g/L antioxidant. The plating solution of the present invention has excellent dispersion and deep plating ability, can meet various technical requirements of a high-speed tin plating production line, and can further reduce the amount of tin plating (≈0.7g/m ² ) to save resources. In addition, iron ions and chlorine in the plating solution The highest ion tolerance limits can reach 20g/L and 1000ppm respectively. The plating solution obtained by the invention is more stable than the plating solution without crystal finer agent added, and a good plating layer can still be obtained after the plating solution is used and placed for several weeks.

Description

High-speed tin plating plating solution

Technical field

The invention belongs to the technical field of electrochemical deposition of metal and alloy, relate to a kind of high-speed tin plating plating solution.

Background technology

High-speed tin plating is widely used in sheet material, wire rod and electronics are electroplated, with regard to electrolytic tinplate (being commonly called as tinplate), it is a kind of functional material, have that intensity is high, weldability good, the feature such as corrosion-resistant and nontoxicity, the long-term main wrapping material as foodstuffs industry, and be widely used in medicine, light industry, automobile and other industries, be one of most popular steel product.

It is the main smooth electroplating technology of fluorine Loews that existing eleetrotinplate technique adopts sulfocarbolic acid (PSA) mostly, the plating line of this technique accounts for 65.7% of world's electrotinned wire, but in PSA, contain the very large phenolic compound of toxicity, and the treatment cost of waste liquor producing is also higher.This plating solution limit current density is low, and consequently domestic unit actual motion speed is in 175m/min left and right (be generally～600m/min of unit design linear velocity), and production efficiency also has the very large rising space.High-speed tin plating is high to additive and plating solution performance requirement thereof, and plated material will overcome parallel electric field, gas field, temperature field, flow field and concentration field effect, obtains high quality coating in 10s.In addition, domestic zinc-plated unit adopts block tin as soluble anode greatly, needs regularly to shut down and change anode, and production efficiency is low, and tin mud volume production goes out many, and labor strength is large; The insoluble anode such as iridium dioxide and platinum plating is following application tendency.In production process, insoluble anode is separated out active oxygen in a large number, and some zinc-plated additives are very easily aging.Therefore the additive to high speed tin plating and plating solution thereof just seem particularly urgent.

It is sub-matte pure tin electroplating additive and plating solution thereof that CN101922026A discloses a kind of methylsulphonic acid, its additive contains the disagreeableness heterocyclic compound of environment and aminated compounds, in addition this plating solution also contains the organic solvent of 100-150g/L, in high-speed motion strong convection, organic solvent volatilizees rapidly, the control of tin mud amount is not good, plating solution very easily lost efficacy, and improved production cost, also to production plant environment.CN1570219 discloses electroplating composition and electro-plating method, and its composition contains thiocarbamide and aminated compounds, and decomposes is emitted nitrogen, sulfur oxide, is unfavorable for that operator's is healthy.CN1733977A discloses a kind of zinc-plated additive and preparation method thereof, and its additive contains polyoxyethylene aniline ether, naphthene sulfonic acid etc. to the disagreeableness chemical substance of environment.

US7517443B2 discloses a kind of eleetrotinplate plating solution, and main component is thionamic acid tin, sulfuric acid and contains the oxyethane of N and the additive of propylene oxide block copolymer; Consider that conduct hydrolysis and the stannous ion of oxygen base sulfonic acid stablize required strong acid condition, also need further checking for high-speed tin plating.US RE39476E discloses a kind of tin bath solution composition, wherein contains polyoxyalkylene alcohol homopolymer and oxyethane and epoxy propane copolymer composition, and plating solution also needs to optimize in foaming and froth breaking ability; In this patent, oxidation inhibitor only has one or more of pyrocatechol, Resorcinol and Resorcinol simultaneously, can not effectively suppress the grey black that soft-melting process brings to tin-plated product.

Summary of the invention

Main purpose of the present invention is to provide one to can be used for high-speed tin plating plating solution, is mainly used in improving plating solution performance, improves quality of coating, and meets high speed electrodeposition requirement; And optimize High Speed Tin Plating Technology by this approach, and reduce original product consumption, reduce production costs, and realize the production domesticization of high-speed tin plating additive and plating solution thereof simultaneously.Chlorine

The object of the invention is to be achieved through the following technical solutions: chlorine

A kind of for high-speed tin plating plating solution, comprise following composition: tin methane sulfonate 5-100g/L, methylsulphonic acid 10-100mL/L, sulfuric acid 0.1-20ml/L, additive: 0.1-200mg/L defoamer, the thin brilliant agent of 0.1-50g/L, 0.01-20g/L walk agent, 0.1-40g/L oxidation inhibitor.

In the present invention, described defoamer is a compounds of polyoxyethylene oxypropylene glycerine, and molecular weight is at 500-15000.

In the present invention, described thin brilliant agent is one or more mixture of formaldehyde, oxyethane and epoxy propane copolymer.Be preferably the segmented copolymer of formaldehyde, oxyethane and propylene oxide and random copolymers is a kind of, the mixture of two or three arbitrary proportion.

In the present invention, described thin brilliant agent block polymer is MO _x-EO _y, PO _x-EO _y, MO _x-EO _y-MO _z, EO _x-MO _y-EO _z, MO _x-EO _y-PO _z, EO _x-MO _y-PO _z, EO _x-PO _y-MO _z, PO _x-EO _y-PO _z, EO _x-PO _y-EO _zand random copolymers is MO _meO _npO _t.Wherein, MO is that methoxyl group, EO are that oxyethyl group, PO are propoxy-; X, y, z is MO, the EO of segmented copolymer, the polymerization degree of PO, and the scope of x, y, z, m, n and t is 1-60.

In the present invention, described thin brilliant agent EO mass content is at 5-90%, and polymericular weight is between 2000-10000, and density is at 1.10 ± 0.10g/cm ³, cloud point is at 55-95 ℃.

In the present invention, the described agent that walks is a kind of alkyl alcohol Soxylat A 25-7, can increase plating solution limit current density value.Its structural formula is R-O-(CH ₂cH ₂o) n-H, the branched hydrocarbyl that R is unsaturated C7～13, n is in 60-280.

In the present invention, described oxidation inhibitor is any two kinds in Resorcinol, pyrocatechol, Resorcinol, xitix, oxysuccinic acid, citric acid, tartrate, with 1:0.1-5 mixed in molar ratio.

The present invention, than prior art, has following features:

1, high-speed tin plating provided by the invention does not contain homopolymer, aldehydes, heterocyclic compound, aminated compounds, polyamino carboxylic acid, sulphur amino acid and any organic solvent of yin, yang ion and amphoterics, polyoxymethylene and polyethylene oxide and poly(propylene oxide) with additive.

2, the present invention configures additive concentrating liquid and plating solution institute water is deionized water, specific conductivity <20 μ S/cm; Gained coating is the sub-light coating of canescence.

3, the plating solution working temperature interval of additive composition of the present invention is at 10-70 ℃; Under high-speed condition, can reach 60-120A/dm containing the plating solution limit current density of additive of the present invention ².

4, plating solution dispersion and the covering power of additive composition of the present invention are good, can meet every technical requirements of high speed tin plating production line, can further reduce zinc-plated amount (≈ 0.7g/m simultaneously ²) to economize on resources, plating solution iron ion and chlorion tolerance limit content best result Bie Keda 20g/L, 1000ppm in addition.

5, the plating solution energy on-line velocity of additive composition of the present invention is under 0-800m/min condition, obtains crystallization careful, covers uniform coating.

6, the plating solution of additive of the present invention and composition thereof does not contain nonbiodegradable substance and to the disagreeableness chemical of environment, sewage disposal is simple, meets environmental requirement, is worth promoting the use of in high speed tin plating industry.

7, the not bath stability of the brilliant agent of refinement of the plating solution ratio that the present invention obtains, plating solution uses, placement still can obtain good coating after several weeks.

Accompanying drawing explanation

Fig. 1 is embodiment 1 Hull Cell sample photo, and experiment condition is 45 ℃, 2A, and 2min, without convection agitation;

Fig. 2 is embodiment 2 Hull Cell sample photos, and experiment condition is 45 ℃, 2A, and 2min, without convection agitation;

Fig. 3 is embodiment 3 Hull Cell sample photos, and experiment condition is 45 ℃, 2A, and 2min, without convection agitation;

Fig. 4 is that embodiment 1 is at 15.0A/dm ²the 0.7g/m obtaining under different current density conditions ²tin plate SEM photo;

Fig. 5 is that embodiment 1 is at 15.0A/dm ²the 0.7g/m obtaining ²the local energy spectrum analysis of coating tin plate SEM photo (spectrogram 2);

Fig. 6 is that embodiment 1 is at 15.0A/dm ²the 0.7g/m obtaining ²the local energy spectrum analysis of coating tin plate SEM photo (spectrogram 3);

Fig. 7 is that embodiment 1 is at 6.75A/dm ²the 1.1g/m obtaining under condition ²tin plate SEM photo;

Fig. 8 is that embodiment 1 is at 15.0A/dm ²the 1.1g/m obtaining under condition ²tin plate SEM photo;

Fig. 9 is that embodiment 1 is at 24.75A/dm ²the 1.1g/m obtaining under condition ²tin plate SEM photo;

Figure 10 is that embodiment 1 is at 15.0A/dm ²the 1.1g/m obtaining ²the local energy spectrum analysis of coating tin plate SEM photo (spectrogram 3);

Figure 11 is that embodiment 1 is at 15.0A/dm ²the 1.1g/m obtaining ²the local energy spectrum analysis of coating tin plate SEM photo (spectrogram 4);

Figure 12 is that embodiment 1 is at 15.0A/dm ²the 1.1g/m obtaining under condition ²6000 times of SEM photos of tin plate;

Figure 13 is that embodiment 2 is at 15.0A/dm ²the 1.1g/m obtaining under condition ²6000 times of SEM photos of tin plate;

Figure 14 is that embodiment 3 is at 15.0A/dm ²the 1.1g/m obtaining under condition ²6000 times of SEM photos of tin plate.

Embodiment

Below in conjunction with embodiment, technical scheme of the present invention is further described, plating solution composition and processing condition can be adjusted according to product demand.Every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.

Embodiment 1

Embodiment 2

Embodiment 3

Plating solution performance test

1) Hull groove test piece test.Test with 267mL plating solution, test piece adopts the long 100mm of cold-rolled steel sheet, is highly 70mm.Experiment condition is 45 ℃, 2A, and 2min, without convection agitation.Sample is electroplated clean the drying up of rear taking-up deionized water, measures coating scorch region width, and embodiment 1,2,3 formula Hull test piece photos are referring to Fig. 1-3, and this plating solution is under static conditions, and limit current density is up to 8.5A/dm ², and occur without defective coating in whole current density district, can meet existing tin plating technique.

2) covering power test.Use endoporus method, it is 10mm that test specimen adopts internal diameter, and the long copper pipe for 50mm uses the pore vertical surface pole plate that faces south when plating, and the mouth of pipe is apart from anode 100mm, with 0.5A/dm ²cathode current density electroplate after 5min pipe negative electrode taken out, clean and dry up, cut vertically, measure pore coating and plate into the degree of depth, evaluate covering power.

The copper pipe that the plating solution that uses embodiment 1 additive of filling a prescription to be made into is plated to is cut rear discovery open, and copper pipe endoporus is all gone up tin metal, illustrates that the plating solution covering power that additive formulations that embodiment 1 provides is made into is good.

3) dispersive ability test.By far and near cathode method mensuration, transparent organic glass rectangular tank for coating bath (inner cavity size is 150mm × 50mm × 70mm), open uniformly five sulculuses in the both sides of groove and be used for inserting negative electrode, negative electrode adopts the cold-rolled steel sheet that thickness is 0.17mm, be of a size of 5.5mm × 110mm, inoperative surface seals with insulation tape, and the orificed anode of use and negative electrode same size, is convenient to plating solution flow of the electrolyte.Test current density is 1.0A/dm ², in the middle of two negative electrode test pieces, put into anode, negative electrode far away with the distance ratio of nearly negative electrode and positive electrode be 2: 1, take out negative electrode electroplate 10min at 45 ℃ after to clean up, weigh the increment of metal refining on far away, nearly negative electrode, be calculated as follows the dispersive ability of plating solution.

$T=\frac{K-\mathrm{<figure-callout\; id="1"\; label="m"\; filenames="HDA0000487512220000021.png,HDA0000487512220000061.png"\; state="\{\{state\}\}">m</figure-callout>}1/m2}{K-1}*100\%,$

In formula: T---dispersive ability, %;

K---the distance ratio of negative electrode far away and nearly negative electrode and positive electrode;

M1---the metal quality depositing on nearly negative electrode, g;

M2---the metal quality depositing on negative electrode far away, g.

3 covering powers of additive that embodiment 1 provides test, data are as table 1:

Parallel 3 the dispersive ability test results of table 1 embodiment 1

Project	Example 1	Example 2	Example 3
				1	37.6%	55.3%	78.1%
2	36.62%	54.8%	79.4%
				3	36.83%	54.7%	78.0%

Coating performance test

Adopting the cold-rolled steel sheet of temper rolling technology is research object, and its surface not only exists rolling lines, but also has rolling pit, and this requires high to high-speed tin plating with additive and plating solution performance thereof.Fig. 4-6th, embodiment 1 is at 15.0A/dm ²the 0.7g/m obtaining under current density condition ²the local energy spectrum analysis data of tin plate SEM photo and SEM photo.Found that: plating solution is at 15.0A/dm ²under condition, 0.7g/m ²thin tin amount tin plate sheet tin rolling direction and pit portion tin atom per-cent are respectively 25.44%, 35.88%, and the zinc-plated amount of pit will be higher than rolling line place, and plating solution has certain leveling ability, is conducive to the zinc-plated amount of further attenuate, save tin resource.

Fig. 8-11 are respectively the 1.1g/m that embodiment 1 obtains under different current density conditions ²tin plate SEM photo and at 15.0A/dm ²the 1.1g/m obtaining ²the local energy spectrum analysis data of coating tin plate SEM photo.Found that: under three kinds of current density conditions, coating uniform and delicate, without revealing plating, tin crystal grain is careful.15.0A/dm ²the 1.1g/m obtaining under condition ²tin plate sheet tin rolling direction and pit portion tin atom per-cent are respectively 62.25%, Sn62.17%, compared with 0.7g/m ²coating content has obvious rising, and the tin atom percentage difference at pit and rolling lines place further reduces, even thickness.Can draw thus, the plating solution performance that embodiment 1 provides is good, and coating uniform and delicate is suitable for high speed electrodeposition process of tin.

Figure 12-14th, embodiment 1,2,3 is at 15.0A/dm ²the 1.1g/m obtaining under condition ²6000 times of SEM photos of tin plate; Can find out according to electromicroscopic photograph, plated crystal tactical rule is even, zero defect.

Claims (9)

1. for a high-speed tin plating plating solution, it is characterized in that described plating solution comprises following composition: 5-100g/L tin methane sulfonate, 10-100mL/L methylsulphonic acid, 0.1-20ml/L sulfuric acid, 0.1-200mg/L defoamer, the thin brilliant agent of 0.1-50g/L, 0.01-20g/L walk agent, 0.1-40g/L oxidation inhibitor.

2. according to claim 1 for high-speed tin plating plating solution, it is characterized in that described defoamer is polyoxyethylene oxypropylene glycerine.

3. according to claim 2 for high-speed tin plating plating solution, the molecular weight that it is characterized in that described polyoxyethylene oxypropylene glycerine is 500-15000.

4. according to claim 1 for high-speed tin plating plating solution, it is characterized in that one or more mixtures that described thin brilliant agent is formaldehyde, oxyethane and epoxy propane copolymer.

5. according to claim 4 for high-speed tin plating plating solution, it is characterized in that described thin brilliant agent is MO _x-EO _y, PO _x-EO _y, MO _x-EO _y-MO _z, EO _x-MO _y-EO _z, MO _x-EO _y-PO _z, EO _x-MO _y-PO _z, EO _x-PO _y-MO _z, PO _x-EO _y-PO _zor EO _x-PO _y-EO _zblock polymer, wherein MO is that methoxyl group, EO are that oxyethyl group, PO are propoxy-; X, y, z is MO, the EO of segmented copolymer, the polymerization degree of PO; The scope of x, y, z is 1-60.

6. according to claim 4 for high-speed tin plating plating solution, it is characterized in that described thin brilliant agent is MO _meO _npO _trandom copolymers, wherein MO is that methoxyl group, EO are that oxyethyl group, PO are propoxy-, MO, the EO that m, n, t are random copolymers, the unit number of PO, the scope of m, n and t is 1-60.

According to described in claim 5 or 6 for high-speed tin plating plating solution, it is characterized in that described thin brilliant agent EO mass content is at 5-90%, polymericular weight is between 2000-10000, density is at 1.10 ± 0.10g/cm ³, cloud point is at 55-95 ℃.

8. according to claim 1 for high-speed tin plating plating solution, the agent that walks described in it is characterized in that is alkyl alcohol Soxylat A 25-7, and its structural formula is R-O-(CH ₂cH ₂o) n-H, the branched hydrocarbyl that R is unsaturated C7～13, n is in 60-280.

9. according to claim 1 for high-speed tin plating plating solution, it is characterized in that described oxidation inhibitor is any two kinds in Resorcinol, pyrocatechol, Resorcinol, xitix, oxysuccinic acid, citric acid, tartrate.

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