CN101348926A - Plating solution for electroplating matt zinc and preparation thereof - Google Patents
Plating solution for electroplating matt zinc and preparation thereof Download PDFInfo
- Publication number
- CN101348926A CN101348926A CNA2008102122972A CN200810212297A CN101348926A CN 101348926 A CN101348926 A CN 101348926A CN A2008102122972 A CNA2008102122972 A CN A2008102122972A CN 200810212297 A CN200810212297 A CN 200810212297A CN 101348926 A CN101348926 A CN 101348926A
- Authority
- CN
- China
- Prior art keywords
- additive
- zinc
- matt
- matt zinc
- plating bath
- Prior art date
- 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.)
- Granted
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Plating solution used for electroplating matt zinc and a preparation method thereof relate to a matt zinc electroplating process in the surface treatment of a metallic material. The plating solution is characterized in that the compositions of the plating solution comprise a matt zinc addition agent A and a matt zinc addition agent B, wherein the matt zinc addition agent A is a mixture of methylene dinaphthyl and poly(acrylamide/sodium acrylate/N-octylacrylamide); and the matt zinc addition agent B is 4-(4-hydroxyl) phenyl-3 butylene-2-ketone. When the plating solution is adopted, a matt plating coat with obscure appearance, soft luster, better diffused reflection, fine structure, fewer pores, low internal stress and excellent corrosion resistance can be obtained.
Description
[technical field]
The present invention relates to metal material surface handles.In particular, relate to a kind of plating bath that is used for electroplating matt zinc and preparation method thereof.
[background technology]
Conventional galvanizing flux in the worldwide mainly is divided into now: sulfate zinc plating liquid, chloride galvanizing liquid, zincate galvanizing liquid, ammonium salt galvanizing flux.Sulfate bath zinc current efficient height can use very high current density, can obtain the zinc coating of light at short notice.Chloride galvanizing liquid is a kind of bright plating technology that the eighties grows up, and is characterized in not containing complexing agent, and waste water is handled easily, and the light of coating and leveling property to be better than other routines zinc-plated.The zincate galvanizing bath stability, convenient operating maintenance, but the sedimentation velocity of zinc layer is slow partially.The zinc-plated zinc layer of ammonium salt gloss is attractive in appearance, and dispersive ability and degree of depth ability are good.Though above-mentioned four kinds zinc-platedly have that coating gloss is attractive in appearance, dispersive ability and the good advantage of covering power, the chemical property of zinc is active, zinc layer oxidation deepening easily in atmosphere in zinc-plated back produces white rust corrosion at last.The zinc-plated of above conventional kind all exists a little less than the solidity to corrosion, must will handle by chromic salts, so that cover the inferior position that one deck chemical conversion film prolongs the etching time of zinc layer on the zinc layer.As everyone knows, higher " high chromic acid content passivation " technology of chromic acid concentration in traditional chromic salts passivating solution, it is big to have chromic anhydride consumption, and great majority have increased the burden of wastewater treatment with discharging in the rinse water, and environment is caused very big pollution.And be head it off, now the chromium anhydride concentration that adopts very low " low chromic acid passivation ", significantly reduced content of 6-valence Cr ions in the waste water.But passivating solution will often be adjusted, the chemical rightenning poor-performing.In brief, traditional zincincation does not find balance all the time on coating light and solidity to corrosion.
Though above-mentioned four kinds zinc-platedly have that coating gloss is attractive in appearance, dispersive ability and the good advantage of covering power, the chemical property of zinc is active, zinc layer oxidation deepening easily in atmosphere in zinc-plated back produces white rust corrosion at last.The zinc-plated organism that is mingled with in the coating that all exists of above conventional kind is many, thereby has caused a little less than the solidity to corrosion, must will handle by chromic salts, so that cover the inferior position that one deck chemical conversion film prolongs the etching time of zinc layer on the zinc layer.
[summary of the invention]
At the defective that exists in the common electrical galvanizing technique, promptly big to the conventional additives dependency, degradation production is many, it is many to be mingled with organism in the coating, fragility is big, coating is easy to change, corrosion stability is poor, must advance the shortcoming of phase chromic salts passivation later after having plated, the object of the present invention is to provide a kind of plating bath that is used for electroplating matt zinc and preparation method thereof, not need through containing chromium passivating, directly seal, reduced in traditional zincincation must passivation process, reduced the harm of chromium metal pair environment, it is dim to obtain outward appearance, gloss is soft, it is careful to have better diffuse-reflectance and structure, hole is few, internal stress is low, the mute light coating of good corrosion resistance.
The matt zinc additive can make electrode surface adsorb the molecule or the ion of surfactant in electroplating process, meet with obstruction when being equivalent to the reactant reaction on electrode, thereby reaction is difficult to carry out.If compare their speed of response under same electropotential, then the absorption in the matt zinc additive can make speed of response reduce, and promptly current density reduces.If contrast under same current density, after then electrode adsorbed this additive, polarization should increase, and the matt zinc additive is on electrode surface, and electrochemical polarization increases, and helps the formation of nucleus, might obtain tiny crystal grain.On the other hand, the matt zinc additive it can preferentially to be adsorbed on some activity higher, the speed of growth is faster on the crystal face, making the adatom of metal enter these activity sites has any problem, so the speed of growth of these crystal faces descends, just having had may be even with drawing of the speed of growth of each crystal face, forms compact structure, aligns neat crystal.The matt zinc additive adds, having changed Potential distribution makes negative electrode produce stronger polarization, nucleus is had form speed faster, the addition of the man of change interpolation is simultaneously controlled crystal and is reached speed to obtain a certain size crystal grain, on grain formation coating surface, its roughness equals or is slightly larger than optical wavelength, forms diffuse-reflectance, to obtain mute light.The adding of matt zinc additive reduces the preferred orientation degree of crystal face, and surface energy differential reduces.Additive has quickened the formation of nucleus, and impels the crystal grain that has formed the polycrystalline face, and crystal grain has certain regular shape, and intergranule is in conjunction with tight.According to the lower then surface energy of the relevant crystal indices of the surface chemistry physics little theory that heals, crystal face with identical energy is many more, and surface energy is low more, and then the surface corrosion of coating is also more even, because of crystal face can not wait the corrosion that causes also just few more, solidity to corrosion is also just strong more.
Existing matt zinc additive can make the molecule or the ion of electrode surface adsorption surface active substance in electroplating process, meet with obstruction when being equivalent to the reactant reaction on electrode, thereby reaction is difficult to carry out.If compare their speed of response under same electropotential, then the absorption of matt zinc additive can make speed of response reduce, and promptly current density reduces.If contrast under same current density, then after the electrode adsorption surface promoting agent, polarization should increase, and this matt zinc additive is on electrode surface, and electrochemical polarization increases, and helps the formation of nucleus, might obtain tiny crystal grain.On the other hand, the matt zinc additive it can be adsorbed on preferentially that some activity is higher, the speed of growth is faster on the crystal face, making the adatom of metal enter these activity sites has any problem, so the speed of growth of these crystal faces descends, just may drawing of the speed of growth of each crystal face is even, form compact structure, align neat crystal.
And the matt zinc additive adds, and has changed Potential distribution to make negative electrode produce stronger polarization, nucleus is had form speed faster, and the addition that changes the matt zinc additive is simultaneously controlled the crystal coarsening rate to obtain a certain size crystal grain.On grain formation coating surface, its roughness equals or is slightly larger than optical wavelength, forms diffuse-reflectance, has just obtained mute light.
Particularly, the present invention adopts following technical scheme to realize goal of the invention.
The additive that is used for the electroplating matt zinc plating bath of the present invention, its component comprises additive A and additive B, said matt zinc additive A is the mixture of methylene dinaphthalene and poly-(acrylamide/sodium acrylate/N-octyl acrylamide), the blending ratio of the two is 2: 2-3 (weight), preferably 2: 3, said matt zinc additive B was the mixture of 4-(4-hydroxyl) phenyl-3 butene-2s-ketone or 4-phenyl-3 butene-2s-ketone or its arbitrary proportion.The ratio of additive A and additive B is 1: 1～1.2.
The matt zinc additive A is a colourless transparent liquid, and pH is 6.5～7 proportions 1.139 ± 1; The agent of matt zinc additive B is a colourless transparent liquid, and pH is 5.5～6 proportions 1.160 ± 1.
Above the structural formula of described methylene dinaphthalene is:
Wherein, R
1And R
2Be NaSO
3Or KSO
3, R
3And R
4Alkyl for hydrogen or chain length 1～2.Can adopt naphthalenesulfonate or naphthalene ethoxy compound.Can be used as current density and widen agent,, in the electrode process resistanceization effect can take place because under certain current density.
The structure of above described poly-(acrylamide/sodium acrylate/N-octyl acrylamide) is:
2≤n in the formula≤10.It has the effect of compatibility agent.
The structure of matt zinc additive B is:
R in the formula
1Can be hydroxyl or hydrogen.It has the effect that makes the coating light.
Above-mentioned raw materials all has sale on the market.
This additive is applicable to Repone K, ammonia chloride, zincate, sulfate zinc plating.Additive A and B need add simultaneously in 1: 1～1.2 ratio.
The present invention also provides four groups of matt zinc plating baths, and is as described below:
(1) Repone K plating bath
Repone K 180～230g/L, zinc chloride 50～75g/L, boric acid 25～30g/L, ethoxylated dodecyl alcohol 5～8g/L, matt zinc additive A 20ml/L, matt zinc additive B 20ml/L, the pH value is 5～6
(2) ammonia chloride plating bath
Ammonium chloride 180～230g/L, zinc chloride 60～80g/L, boric acid 25～30g/L, ethoxylated dodecyl alcohol 5～8g/L, matt zinc additive A 20ml/L, matt zinc additive B 20ml/L, the pH value is 6～7;
(3) sulfate bath
Zinc sulfate 200～300g/L, boric acid 25～30g/L, AES 4～6g/L, matt zinc additive A 20～30ml/L, matt zinc additive B 20～30ml/L, the pH value is 4.5～5.5;
(4) zincic acid salt plating liquor
Sodium hydroxide 100～140g/L, zinc oxide 8～12g/L, matt zinc additive A 5～10ml/L.Matt zinc additive B 5～10ml/L, pH value 〉=14.
In Repone K, ammonia chloride, zincate, sulfate bath, add additive of the present invention, can quicken the formation of nucleus, and impel the crystal grain that has formed the polycrystalline face, crystal grain has certain regular shape, and intergranule is in conjunction with tight, but crystallite size is bigger, also just because of the bigger reason of granularity, and formed mute light, and can directly seal zinc coating corrosion resistance of coating is improved greatly, the solidity to corrosion of the Repone K zinc coating under the same terms surpassed.Obtaining the moderate matt zinc coating of grain-size is the synergistic result of each component in the additive, though surface-active substance confrontation grain refining effect is stronger, is not active in the matt zinc combined additive.The adding of matt zinc additive does not change the preferred orientation of coating crystal face, but has influenced the diffraction peak intensity of each crystal face, has changed the texture coefficient of each crystal face.According to the lower then surface energy of the relevant crystal indices of the surface chemistry physics little theory that heals, the degree of selecting the superior of low index crystal face is big, illustrate that then the crystal face with identical energy is many more, surface energy is lower, then the surface corrosion of coating is more even, because of crystal face can not wait the corrosion that causes also just few more, corrosion resisting property is also stronger.
The plating bath that is used for electroplating matt zinc of the present invention can obtain that outward appearance is dim, gloss is soft, have better diffuse-reflectance and structure is careful, hole is few, internal stress is low, the mute light coating of good corrosion resistance.
Matt zinc needn't passivation, can adopt the technical process of direct sealing, can reduce the discharging of pollutent.
In order to improve the corrosion resisting property of coating, reaching the salt-fog test index that needs needs supporting use trivalent chromium, chromic passivation in a large amount of at present potassium chloride zinc plating process of popularizing.Especially sexavalent chrome technology has been that European Union's standard bans use of, reason be exactly the discharging of this technology pollutent well beyond environmental protection requirement, and matt zinc needn't passivation, directly sealing just can reach 96 hours corrosion resisting property index of salt-fog test.Having substantially exceeded needs the Repone K of passivation technology galvanizing production, and the quantity discharged of pollutents such as trivalent chromium, sexavalent chrome is almost nil.
2. not dazzling, the irreflexive characteristics of matt zinc coating have reduced the puzzlement of light pollution to productive life.
The optical effect that utilizes not dazzling, the strong irreflexive optical effect in matt zinc surface to reduce high bright coating emergency light reflex in the plating processing of building decoration, lamp decoration, the vehicles, aerospace, production unit brings people's puzzlement, such as the building decoration field, a large amount of light plating pieces rule all the land, the city light pollution is more and more serious, become source of pollution new after water pollution, atmospheric pollution, noise pollution, and matt zinc will find a feasible mode and approach for building decoration, minimizing city, lamp decoration field light pollution.For another example in the vehicles, production unit field, the soft color and luster of matt zinc has reduced the high light that bright coating before this brings and has stimulated, it is tired to avoid eyes to produce, conscientiously improve the production work condition, reduce this field staff's labour intensity, thereby effectively reduce security incident hidden danger such as traffic that light pollution brings, production.
Composition of the present invention is simple, main salts contg height, and plating solution maintenance replenishes convenient, and coating performance is superior, is fit to suitability for industrialized production.
[embodiment]
By the following examples the present invention is described in further detail.Need to prove that these embodiment are only just in order to illustrate the present invention, and can not be interpreted as any restriction protection domain of the present invention.
The preparation of embodiment 1:[methylene dinaphthalene]
A. methylnaphthalene 9.0-12.8g and sulfuric acid 11.2g-13.8 mixing back adding are equipped with the there-necked flask of thermometer, electronic stirring, reacted under the violent stirring 3～4 hours;
B. the mixed solution normal temperature natural cooling crystallization that a is obtained;
C. the crystallisate adding that b is obtained is equipped with in the condensation reaction jar of 6-9g formaldehyde, and condensation is 2～3 hours under the condition of 168-196kPa;
D. in the condensation reaction jar, add massfraction and be 40% NaOH and transfer pH to 8～10;
E. the mixed solution normal temperature natural cooling crystallization that d is obtained;
F. filter the crystallisate obtain among the e, drying is that 40% solution promptly obtains methylene dinaphthalene with distilled water configuration quality mark then.
The preparation of embodiment 2:[poly-(acrylamide/sodium acrylate N-octyl acrylamide)]
A. triethylamine 0.024-0.028mol and n-octyl amine 0.022-0.024mol are dissolved in the 20-40ml tetrahydrofuran (THF);
B. the mixed solution that a is obtained is poured the four-hole bottle that thermometer, logical nitrogen pipe, electronic stirring are housed into, 0～5 ℃ of temperature control slowly splashes into four-hole bottle with acrylate chloride 0.022-0.023mol, is warming up to 10-15 ℃ after drip finishing, under intense stirring condition, be incubated 2～4 hours;
C. the mixed solution that b is obtained desolvates with vacuum distillation apparatus;
D. the mixed solution crystallization in-5 ℃ acetone after will desolvating, acetone and desolvate after the volume ratio of mixed solution be 2: 1;
E. crystallisate that d is obtained and deionized water 20-30ml, acrylate chloride 0.022-0.0024mol, 0.5-0.8g SDS (Sodium dodecyl sulfate) adding are equipped with electronic stirring, lead in the there-necked flask of nitrogen pipe, and under ice bath, add the 2-4g sodium bicarbonate;
F. under the logical nitrogen condition of normal pressure, vigorous stirring 0.5-1 hour, adding 2-4g ammonium sulfate changed 20-25 ℃ water-bath into as initiator and with ice bath, continues to press nitrogen constant temperature 1～2 hour usually, obtains mother liquor;
G. mother liquor is removed SDS and water, intermediate, and be configured to 40% solution with distilled water and promptly gathered (acrylamide/sodium acrylate/N-octyl acrylamide).
The preparation of embodiment 3:[matt zinc intermediate]
A. get n-Octanol 480-520g and add the there-necked flask that band stirs, add NaOH and the 5-10g water of 5-8g;
B. vigorous stirring heat temperature raising gradually;
C. under the vacuum of-0.05MPa, dewater;
D. be warming up to 110～120 ℃, be warming up to 150-200 ℃ until follow-up fully continuing of dehydration;
E. extract air and feed nitrogen;
F. under agitation add oxyethane, reaction pressure 0.2-0.4MPa, 160～180 ℃ of temperature of reaction;
G. discharging when cloud point is 40～50, the there-necked flask that the band of packing into stirs is warming up to 60-70 ℃;
H. get 200-240g sulfuric acid and splash into, temperature control is at 90～100 ℃, drips to finish after 1 hour, and being cooled to 60-70 ℃, to get massfraction be that 50% NaOH transfers pH to 6.5～7.5, obtains mother liquor;
I. the mother liquor standing demix discards down liquid, gets liquid, promptly obtains the intermediate of matt zinc additive A.
The preparation of embodiment 4:[additive A]
The product of embodiment 1 and 2 ratio with 1: 1 (weight ratio) is mixed, perhaps the product of embodiment 1,2,3 ratio (weight ratio) with 1: 1: 0.8 is mixed, obtain additive A.
The preparation of embodiment 5:[matt zinc additive B]
Adopt following any method preparation.
Preparation method (1):
A. get Yan acid 123g-130 and put into there-necked flask, add 400-440g water and stirring;
B. add massfraction and be 40% NaOH and transfer pH to 5.5～6.5;
C. be warming up to 80～105 ℃, splash into phenmethyl chlorine 126-130g with 2～3 droplets/minute speed; Heat then to reflux temperature, keep refluxing 3 hours;
D. surveying the pH value, if less than 6.5, then is 20% NaOH adjust pH 6.5～7.5 with massfraction, and restir is stabilized in 6.5 until pH half an hour, is cooled to the room temperature discharging, promptly obtains the matt zinc additive B;
Preparation method (2):
A. 71g acetone is added and be equipped with in agitator, thermometer and dropping funnel and the band water-bath there-necked flask, add the NaOH of the mixture of catalytic amount Potassium monofluoride and aluminum oxide as catalyzer and 5-7g, the control bath temperature is 20～25 ℃, under violent stirring, in 30～40 minutes, drip the 106g-112 phenyl aldehyde, drip and finished the back vigorous stirring 30 minutes;
B. be 30% hydrochloric acid neutralization with massfraction, suction filtration adds in the powdered sodium bicarbonate and excess acid in the filtrate, and adds salt and saltout, and tells organic layer, and water layer is with benzene extraction 3 times, and merges organic layer, washes with salt solution;
C. organic layer underpressure distillation under the condition of-0.02MP is gone out benzene, condensation drying then promptly obtains the matt zinc additive B.
Embodiment 6:[zinc chloride plating bath]
The component of zinc chloride plating bath is:
Repone K 180～230g/L, zinc chloride 50～75g/L, boric acid 25～30g/L, ethoxylated dodecyl alcohol 5～8g/L, matt zinc additive A 20ml/L, matt zinc additive B 20ml/L, the pH value is 5～6; Its preparation process is:
A. 80 ℃ of hot water with 1/2 prescribed volume dissolve boric acid,
B. add Repone K and zinc chloride successively, stir up to whole dissolvings,
C. the water that adds other 1/2 prescribed volume,
D. handle with zinc powder, each 1g/L agitation and filtration of gac,
E. add ethoxylated dodecyl alcohol and stir evenly,
F. add the matt zinc additive A, the matt zinc additive B stirs.
In a specific embodiment, the component of zinc chloride plating bath is as follows:
Zinc chloride 75g/L
Repone K 230g/L
Boric acid 30g/L
Ethoxylated dodecyl alcohol 5g/L
Matt zinc additive A 20ml/L
Matt zinc additive B 20ml/L
pH 5.5
Water adds to 1 liter
In the HULL groove, in 20-30 ℃, 2A electric current plating 10 minutes on the steel negative electrode.The gained zinc coating is mute ultrawhite sight.
Embodiment 7:[ammonium chloride plating bath]
The component of ammonium chloride plating bath is:
Ammonium chloride 180～230g/L, zinc chloride 60～80g/L, boric acid 25～30g/L, matt zinc additive A 20ml/L, matt zinc additive B 20ml/L, the pH value is 6～7;
Its preparation process is:
A. 80 ℃ hot water with 1/2 prescribed volume dissolves boric acid,
B. add ammonium chloride and zinc chloride successively, stir up to whole dissolvings,
C. the water that adds other 1/2 prescribed volume,
D. handle with zinc powder, each 1g/L agitation and filtration of gac,
E. add ethoxylated dodecyl alcohol and stir evenly,
F. add the matt zinc additive A, the matt zinc additive B stirs;
In a specific embodiment, the component of zinc chloride plating bath is as follows:
Zinc chloride 80g/L
Ammonium chloride 230g/L
Boric acid 25g/L
Ethoxylated dodecyl alcohol 5g/L
Matt zinc additive A 20ml/L
Matt zinc additive B 20ml/L
pH 6.5
Water adds to 1 liter
In the HULL groove, in 20-30 ℃, 1A electric current plating 5 minutes on the steel negative electrode.The gained zinc coating is mute ultrawhite sight.
Embodiment 8:[zinc sulfate plating bath]
The component of zinc sulfate plating bath is:
Zinc sulfate 200～300g/L, boric acid 25～30g/L, AES 4～6g/L, matt zinc additive A 20～30ml/L, matt zinc additive B 20～30ml/L, the pH value is 4.5～5.5;
Its preparation process is:
A. 80 ℃ hot water with 1/2 prescribed volume dissolves boric acid,
B. add zinc sulfate successively, stir up to whole dissolvings,
C. the water that adds other 1/2 prescribed volume,
D. handle with zinc powder, each 1g/L agitation and filtration of gac,
E. add the matt zinc additive A, the matt zinc additive B stirs;
In a specific embodiment, the component of zinc sulfate plating bath is as follows:
Zinc sulfate 300g/L
Boric acid 30g/L
Polyoxyethylenated alcohol sodium sulfate (AES) 4g/L
Matt zinc additive A 20ml/L
Matt zinc additive B 20ml/L
pH 5.5
Water adds to 1 liter
In the HULL groove, in 20-30 ℃, 2A electric current plating 10 minutes on the steel negative electrode.The gained zinc coating is mute ultrawhite sight.
Embodiment 9:[zincic acid salt plating liquor]
The component of zincic acid salt plating liquor is:
Sodium hydroxide 100～140g/L, zinc oxide 8～12g/L, matt zinc additive A 5～10ml/L.Matt zinc additive B 5～10ml/L; Its preparation process is:
A. zinc oxide and sodium hydroxide are mixed,
B. the water that adds 1/2 prescribed volume is stirred to whole dissolvings,
C. handle with zinc powder, each 1g/L agitation and filtration of gac,
D. add the matt zinc additive A, the matt zinc additive B stirs.
In a specific embodiment, the component of zincic acid salt plating liquor is as follows:
Sodium hydroxide 140g/L
Zinc oxide 8-12g/L
Matt zinc additive A 8ml/L
Matt zinc additive B 10ml/L
pH 5.5
Water adds to 1 liter
In the HULL groove, in 20～30 ℃, 1A electric current plating 5 minutes on the steel negative electrode.The gained zinc coating is mute ultrawhite sight.
Adopt plating bath of the present invention, under corresponding operational condition, can obtain that structure is careful, hole is few, internal stress is low, good corrosion resistance, and anti-touch ability is good, the mute light coating that this gloss is soft, covering power is good, and neutral salt spray test can reach 96 hours.
Through removing the component matt zinc in plating bath after the oil corrosion activation, obtain plating speed in cathode current density during for 2.5A/dm2 and be about 45-50 μ m/h, plating mode is for hanging plating, and power supply is a dc constant current power supply.Should note during plating can not short circuit, open circuit, and the time is decided by desired thickness of coating.Guarantee preferably during plating that negative electrode moves and continuous filtration, and timing analysis solution composition and additional main salt etc.
Carrying out quality index as follows tests.
1. test according to the hull trough test of JB/T7704.1-1995 electroplating solution test method.
In being defined as the Hull groove of 267ml, add the plating bath 250ml to be measured that contains matt zinc additive of the present invention.Anode is a zine plate, and Hull groove test piece is a latten(-tin).Test conditions: 25 ℃, electric current 1A, time 5min, obtain full sheet light do not have burn, no plating leakage district.
2. carry out the covering power test according to JB/T7704.2-1995 electroplating solution test method
Adopt φ 10nm * 500mm to copper pipe in accordance with regulations.Two ends become plumbness with anode in the 1000ml plating bath.25 ℃ of electroplating time 10min, electric current 1A, temperature, the baking of plating after washing is vertically cut sample, observes the coating length that plates in the endoporus.By formula:
The result is: covering power 〉=65%
3. carry out the cathode efficiency test according to JB/T7704.3-1995 electroplating solution test method
Use voltameter to measure cathode efficiency in accordance with regulations,
Formula is:
The result is η
k≤ 95%
η
k--cathode efficiency to be measured
A--surveys the actual weightening finish of A (g) in the negative electrode test piece in the solution tank
The actual weightening finish of negative electrode test piece B (g) on the b--meter
Separate out the electrochemical equivalent (g/Ah) of material in the k-solution tank to be measured on the negative electrode
4. carry out the dispersive ability test according to JB/T7704.4-1995 electroplating solution test method
In accordance with regulations with formula:
The result is T 〉=+1%
K-negative electrode far away is from anodic distance and the ratio of nearly negative electrode from the anodic distance;
M
Closely--the weightening finish (g) after electroplating on the nearly negative electrode
M
Far--the weightening finish (g) after electroplating on the negative electrode far away
5. according to the test of JB/T7704.5-1995 electroplating solution test method leveling property
Measure the microcosmic difference of altitude of sample basic surface before the plating with metaloscope, measure microcosmic difference of altitude after the plating again with a part.Be calculated as follows leveling ability:
The result is: leveling property 〉=0.8%
6. coating performance test:
(1) pliability test
It is in 25 ℃ the matt zinc plating bath that the test specimen of 100 * 20 * 1mm is hung the groove temperature, and electric current 1A electroplates down and takes out oven dry behind the 15min, is clipped in that alternating bending is to fracture on the bench vice then, and incision position does not have coating and comes off.
(2) quenching test
Dozens of is plated the matt zinc oven dry, test specimen is inserted constant temperature 30min in 200 ℃ of Electric heat ovens, take out and drop into the cold water quenching immediately.Test-results, sample coating do not have foaming or come off.
(3) friability test of elastic part
50 of power taking plating matt zinc and 6 spring washers of the Φ after the dehydrogenation Passivation Treatment.Be enclosed within on the screw rod of M5, with spanner with nut tightly till the packing ring opening part flattens, place and unclamp after 24 hours.Test-results, none brittle failure.
(4) drawing test result
Through drawing test (internal mold 17mm drift 14mm thickness of slab 1mm, thickness of coating 15 μ m) test, the compression distance of gained sample is 5mm (recording traditional bright galvanization gained sample compression distance 4.5mm equally) in the matt zinc plating bath, shows that the test-results of mute light galvanizing flux gained sample slightly is better than traditional bright galvanization liquid gained sample.
As everyone knows, in monometallic was electroplated, the particularly organic inclusion of the inclusion of coating mechanical property more at least was good more.The coating section structure that under metaloscope, obtains in the section structure of careful relatively matt zinc coating of the present invention and the traditional bright galvanization liquid, substantially do not contain inclusion in the matt zinc coating of the present invention, and bright Repone K zinc coating has more inclusion, and above-mentioned drawing test etc. also confirm this conclusion.
(5) solidity to corrosion of coating
Adopting surface-area respectively is that 1.0dm2, thickness are the 08F steel plate sample of 2mm, under identical envrionment conditions, electroplated 30 minutes with the 1.0A/dm2 current density, and carry out common silvery white passivation, then carry out neutral salt spray test, the time that occurs red point with the surface is the time of passing through.As a result, red corrosion product promptly appears in the continuous spraying of coating through 12 cycles (288h) of adopting traditional bright galvanization brightening agent to obtain, has just eroded to matrix metal; And the coating of the additive among employing the present invention (LAN-616) gained, red corrosion product just appears in (336h) through 14 cycles, cycle life than traditional bright nanocrystalline zinc deposit prolongs nearly 17%, this shows, adopt the zinc coating that additive obtained among the present invention, because inside does not almost have inclusion, its solidity to corrosion is more better than traditional bright nanocrystalline zinc deposit.
Detected result shows in mechanical industry surface coating product quality supervision inspection center: matt zinc only carries out under the condition of sealing treatment in not passivation, and anti-neutral salt spray test is higher than 96 hours.
Claims (8)
1. additive that is used for the electroplating matt zinc plating bath, described additive is made up of additive A and additive B, said additive A is the mixture of methylene dinaphthalene and poly-(acrylamide/sodium acrylate/N-octyl acrylamide), the blending ratio of the two is 2: 2-3 (weight ratio), said additive B is the mixture of 4-(4-hydroxyl) phenyl-3 butene-2s-ketone or 4-phenyl-3 butene-2s-ketone or its arbitrary proportion, and the ratio of additive A and additive B is 1: 1～1.2.
2. additive according to claim 1, the blending ratio of the mixture of wherein said methylene dinaphthalene and poly-(acrylamide/sodium acrylate/N-octyl acrylamide) is 2: 3 (weight ratio).
3. additive according to claim 1, wherein said matt zinc plating bath are Repone K plating bath, ammonia chloride plating bath, zincic acid salt plating liquor or sulfate bath.
4. Repone K matt zinc plating bath comprises:
Repone K 180～230g/L, zinc chloride 50～75g/L, boric acid 25～30g/L, ethoxylated dodecyl alcohol 5～8g/L, matt zinc additive A 20ml/L, matt zinc additive B 20ml/L;
Wherein said additive A and additive B are according to claim 1.
5. ammonia chloride matt zinc plating bath comprises:
Ammonium chloride 180～230g/L, zinc chloride 60～80g/L, boric acid 25～30g/L, ethoxylated dodecyl alcohol 5～8g/L, matt zinc additive A 20ml/L, matt zinc additive B 20ml/L;
Wherein said additive A and additive B are according to claim 1.
6. vitriol matt zinc plating bath comprises:
Zinc sulfate 200～300g/L, boric acid 25～30g/L, AES 4～6g/L, matt zinc additive A 20～30ml/L, matt zinc additive B 20～30ml/L;
Wherein said additive A and additive B are according to claim 1.
7. zincate matt zinc plating bath comprises:
Sodium hydroxide 100～140g/L, zinc oxide 8～12g/L, matt zinc additive A 5～10ml/L.Matt zinc additive B 5～10ml/L;
Wherein said additive A and additive B are according to claim 1.
8. according to any described matt zinc plating bath among the claim 4-7, the concentration ratio of wherein said additive A and additive B is 1: 1-1.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102122972A CN101348926B (en) | 2008-09-09 | 2008-09-09 | Plating solution for electroplating matt zinc and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102122972A CN101348926B (en) | 2008-09-09 | 2008-09-09 | Plating solution for electroplating matt zinc and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101348926A true CN101348926A (en) | 2009-01-21 |
| CN101348926B CN101348926B (en) | 2011-01-12 |
Family
ID=40267891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102122972A Expired - Fee Related CN101348926B (en) | 2008-09-09 | 2008-09-09 | Plating solution for electroplating matt zinc and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101348926B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103451690A (en) * | 2013-08-13 | 2013-12-18 | 南京飞燕活塞环股份有限公司 | Method for galvanizing treatment of spring lined in piston ring |
| CN108950161A (en) * | 2018-08-13 | 2018-12-07 | 林州凤宝管业有限公司 | A kind of production technology of anticorrosive casing |
-
2008
- 2008-09-09 CN CN2008102122972A patent/CN101348926B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103451690A (en) * | 2013-08-13 | 2013-12-18 | 南京飞燕活塞环股份有限公司 | Method for galvanizing treatment of spring lined in piston ring |
| CN108950161A (en) * | 2018-08-13 | 2018-12-07 | 林州凤宝管业有限公司 | A kind of production technology of anticorrosive casing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101348926B (en) | 2011-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ITTO950840A1 (en) | ELECTROLYTIC ALKALINE BATHS AND PROCEDURES FOR ZINC AND ZINC ALLOYS | |
| CN101922028B (en) | Galvanized iron (vanadium) alloy process of acid system | |
| CN101476099B (en) | Method for steel product batch hot dip galvanizing | |
| CN101348926B (en) | Plating solution for electroplating matt zinc and preparation thereof | |
| Naik et al. | Electrodeposition of zinc from chloride solution | |
| CN104911645A (en) | Alkaline cyanide-free zinc plating agent and application method thereof | |
| CN104164687A (en) | Plating solution for electroplating nanometre pearl zinc and preparation method thereof | |
| RU2437967C1 (en) | Procedure for sedimentation of composite coating nickel-vanadium-phosphorus-boron nitride | |
| CN101063219B (en) | Technique for preparing zinc and Zn-Fe alloy electroplating brightener | |
| CN105648485A (en) | Cyanide-free silver electroplating liquid | |
| SU1581781A1 (en) | Zinc-plating electrolyte | |
| Shivakumara et al. | Effect of condensation product on electrodeposition of zinc on mild steel | |
| CN105063686A (en) | Auxiliary brightening agent for subacidity system electroplated bright zinc-nickel alloy and electroplating technology thereof | |
| RU2169798C1 (en) | Method of production of composite zinc-based coats | |
| CA1050471A (en) | Electroplating of rhodium-ruthenium alloys | |
| Bozzini et al. | Influence of selenium-containing additives on the electrodeposition of zinc-manganese alloys | |
| Kavirajwar et al. | Influence of a New Brightener on Electrodeposition of Zn-Ni Alloy | |
| CN104630845A (en) | Electroplating solution for composite organic phosphonic acid cyanide-free copper plating and electroplating method | |
| CN105316728A (en) | Electroplate liquid and electroplate method for gelatin cyanide-free plated Cu-Sn alloy | |
| CN103726080B (en) | A kind of natrium potassium salt for chloride galvanizing technique and purposes thereof | |
| CN103806045A (en) | Process of mechanically lapping electroplated nickel-phosphorus alloy plating layer by horizontal vibration | |
| CN105316724A (en) | Electroplate liquid and electroplate method for pyrophosphate used for cyanide-free plated Cu-Sn alloy | |
| CN106521579A (en) | Cyanide-free alkaline low-tin copper-tin alloy electroplating liquid | |
| Kavirajwar et al. | Investigation of nucleation mechanism and surface morphology of the crystallites in zinc-cobalt alloy coating. | |
| SU1650785A1 (en) | Electrolyte for precipitation of alloy zinc-boron |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110112 Termination date: 20200909 |