CN106167908A - A kind of grill electric chrome solution and electrodeposited chromium method thereof - Google Patents
A kind of grill electric chrome solution and electrodeposited chromium method thereof Download PDFInfo
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- CN106167908A CN106167908A CN201610769991.9A CN201610769991A CN106167908A CN 106167908 A CN106167908 A CN 106167908A CN 201610769991 A CN201610769991 A CN 201610769991A CN 106167908 A CN106167908 A CN 106167908A
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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
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
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Abstract
The present invention provides a kind of grill electric chrome solution and electrodeposited chromium method thereof, described solution includes the composition of following weight portion: chromic salt: 40 ~ 50 parts, cobaltous sulfate: 20 ~ 30 parts, sodium sulfate: 10 ~ 20 parts, potassium sulfate: 15 ~ 25 parts, magnesium sulfate: 15 ~ 30 parts, sodium lauryl sulphate: 5 ~ 10 parts, nano aluminum nitride: 5 ~ 10 parts, dodecylbenzene sodium sulfonate: 1 ~ 5 part, dibutyltin diacetate: 1 ~ 5 part, chelating agent: 1 ~ 5 part, complexant: 1 ~ 5 part, conducting salt: 1 ~ 5 part, buffer agent: 1 ~ 5 part, organic additive: 1 ~ 5 part, deionized water: 80 ~ 100 parts.Described electric chrome solution uses chromic salt, and environmentally friendly, beneficially producers are healthy, and without poisonous metals such as lead, cadmium, and mercuries, thickness of coating is high, and hardness is strong, and corrosion resistance is strong.
Description
Technical field
The invention belongs to field of metal surface treatment technology, in particular it relates to a kind of grill electric chrome solution and electricity thereof
Chrome-plating method.
Background technology
Chromium is a kind of micro-bluish silvery white metal, relative atomic mass 51.99, density 6.98～7.21g/cm3, molten
Point is 1875～1920 DEG C, and crome metal is the most easily passivated, and surface forms one layer of very thin passivating film, thus demonstrates expensive
The character of metal.
Chromium coating has the highest hardness, different with process conditions according to solution composition, and its hardness can be in very wide range 400
～change in 1200HV.Chromium coating has preferable thermostability, heats below 500 DEG C, and its glossiness, hardness are all without substantially becoming
Changing, temperature starts oxidation stain more than 500 DEG C, starts to reduce more than 700 DEG C of hardness.The friction of chromium coating is decimal, particularly
Dry friction coefficient, is minimum in all of metal.So chromium coating tool has good wearability.
Chrome plating has good chemical stability, does not makees in alkali, sulfide, nitric acid and most of organic acid
With, but can be dissolved in the sulphuric acid of hydrochloric acid (example hydrochloric acid) and heat.
After electroplated chromium processes, mould, workpiece have the following advantages:
1, surfacing, bright and clean, be prone to the demoulding；2, antirust；3, electroplating process Central Plains part deformation is little, can after the chromium plating of top layer
Strengthen hardness (more than HR65), high temperature resistant reach 500 DEG C, corrosion-resistant, acid-proof, wear-resistant.
But, electrodeposited chromium technique is frequently present of current efficiency low, and uses chromic electroplate liquid to human body and ring
There is bigger hazardness in border, and therefore electrodeposited chromium those skilled in the art are attempting the succedaneum of electric chrome solution, such as
Stannum-cobalt or stannum-cobalt-zinc ternary alloy can replace decoration chrome plating, chemical plating nickel-phosphorus or nickel-boron alloy or a kind of ferrous alloy
Wear-resistant chromium plating etc. can be replaced, but layers of chrome is because there being its special advantage and purposes, it is difficult to all replace.
Dividing from quantivalence, Cr-plating Bath can divide Cr VI and trivalent chromium two kinds, and Cr VI venom toxicity is relatively big, Er Qie electricity
Stream efficiency is low, and general standard hexavalent chromium plating liquid current efficiency only has about 13%, and trivalent chromium bath then has current efficiency height, plating
Liquid low toxin, but the more difficulty that controls to get up, and tint is not good enough, therefore, it is difficult to promote.
For rust preventive cutting fluid, the most domestic it is primarily present such as Publication about Document:
Patent publication No.: CN105696028A, discloses a kind of electroplating solution and electricity that can use trivalent chromium plating hard chromium
Electroplating method, efficiently solves the problem that trivalent chromium coating can not thicken.The bath element of this trivalent chromium plating solution is: Chlorizate chromium
0.4～1.2mol/L, complexant 0.5～3.0mol/L, buffer agent 0.1～0.8mol/L, conducting salt 0.5～2.0mol/L, have
Machine additive 3～35g/L, remaining is water.Use chloride plate liquid system and high-density graphite anode, 25～45A/dm2's
Preparing surfacing, compact crystallization under electric current density, good with basal body binding force, thickness reaches the trivalent chromium plating of more than 60 μm
Layer, more than coating hardness HV800.But, though the Chlorizate chromium electroplating liquation employing trivalent that this patent provides, its composition
Simply, electroplating effect is worth discussion, and is not suitable for the electrodeposited chromium of grill.
Summary of the invention
For solving the problem of above-mentioned existence, it is an object of the invention to provide a kind of grill electric chrome solution and plating thereof
Chromium method, described electric chrome solution uses chromic salt, and environmentally friendly, beneficially producers are healthy, the most leaded cadmium
The poisonous metals such as hydrargyrum, thickness of coating is high, and hardness is strong, and corrosion resistance is strong.
For reaching above-mentioned purpose, the technical scheme is that
A kind of grill electric chrome solution, described solution includes the composition of following weight portion: chromic salt: 40～50 parts,
Cobaltous sulfate: 20～30 parts, sodium sulfate: 10～20 parts, potassium sulfate: 15～25 parts, magnesium sulfate: 15～30 parts, lauryl sulphate acid
Sodium: 5～10 parts, nano aluminum nitride: 5～10 parts, dodecylbenzene sodium sulfonate: 1～5 part, dibutyltin diacetate: 1～5 part,
Chelating agent: 1～5 part, complexant: 1～5 part, conducting salt: 1～5 part, buffer agent: 1～5 part, organic additive: 1～5 part, go
Ionized water: 80～100 parts.
Further, described solution includes the composition of following weight portion: chromic salt: 45～50 parts, cobaltous sulfate: 20～25
Part, sodium sulfate: 15～20 parts, potassium sulfate: 20～25 parts, magnesium sulfate: 15～25 parts, sodium lauryl sulphate: 5～8 parts, nanometer
Aluminium nitride: 5～7 parts, dodecylbenzene sodium sulfonate: 1～3 part, dibutyltin diacetate: 2～5 parts, chelating agent: 1～3 part, join
Position agent: 1～4 part, conducting salt: 3～5 parts, buffer agent: 2～5 parts, organic additive: 1～3 part, deionized water: 80～90 parts.
Preferably, described solution includes the composition of following weight portion: chromic salt: 45 parts, cobaltous sulfate: 25 parts, sodium sulfate:
15 parts, potassium sulfate: 20 parts, magnesium sulfate: 23 parts, sodium lauryl sulphate: 7 parts, nano aluminum nitride: 6 parts, DBSA
Sodium: 2 parts, dibutyltin diacetate: 3 parts, chelating agent: 2 parts, complexant: 3 parts, conducting salt: 4 parts, buffer agent: 2 parts, You Jitian
Add agent: 2 parts, deionized water: 90 parts.
Separately, described chromic salt is chromic sulfate, chromium sulfate basic, chromium trichloride, chromium carbonate, chromium acetate, chromic formate or hydrogen
Chromium oxide.
Separately having, described chelating agent is malic acid, tartaric acid, oxalic acid, formic acid, citric acid, 5-sulphosalicylic acid, imino-diacetic
Acetic acid, aspartic acid or acetic acid.
Again, described complexant is glycolic, methanol, carbamide or hydantoin.
Further, described conducting salt is sodium chloride or ammonium chloride.
And, described organic additive is Polyethylene Glycol, polyvinyl alcohol, butynediols, polymine or alkyl phenol polyoxy
Vinyl Ether.
Meanwhile, the present invention also provides for a kind of using grill electric chrome solution that grill carries out electric plating method, described electricity
Electroplating method comprises the steps:
1) configuration electric chrome solution
Nano aluminum nitride is added in dodecylbenzene sodium sulfonate, adds 20～30 parts of deionized waters, 600～800 turns/
The rotating speed down cut divided disperses 15～20 minutes, under the rotating speed of 1000～1200 revs/min, shears 5～10 minutes, according to joining
Ratio, add described chromic salt, cobaltous sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, sodium lauryl sulphate, chelating agent, complexant,
Conducting salt, buffer agent, organic additive and residue deionized water, stir 10～15 minutes under 500～600 revs/min of rotating speeds, mixed
Close uniformly, use ultrasound wave dispersion, disperse power 700～800W, jitter time 10～15 minutes, obtain described electric chrome solution；
2) grill electrodeposited chromium
Take step 1) gained electric chrome solution, stir 2～3 hours at the rotating speeds of 700～800 revs/min, bath pH values is
2～3, grill oil removing to be plated, rust cleaning are cleaned up, polishes smooth, as negative electrode, graphite, as anode, immerses electrodeposited chromium molten
In liquid, solution temperature 40～55 DEG C, cathode-current density: 15～25A/dm2, electroplating time 1～2 hours, electroplating process stirs
Mixing, rotating speed is 150～200 revs/min.
Separately, thickness of coating is 50～80 μm.
The beneficial effects of the present invention is:
Described electric chrome solution uses chromic salt, and environmentally friendly, beneficially producers are healthy, after testing,
Without poisonous metals such as lead, cadmium, and mercuries, add nano aluminum nitride, promote coating activity, add chelating agent, complexant, conducting salt, delay
Electuary, organic additive, strengthen thickness of coating, thickness of coating is up to 50～80 μm, and hardness is up to HV and is up to 1000～1100, resistance to
Corrosive power is strong, salt spray resistance test coating invariant color in 10～15 days.
Detailed description of the invention
Following example are used for illustrating the present invention, but can not be used for limiting the scope of the present invention.The reality used in embodiment
The condition of executing can be for further adjustments according to the condition of producer, and unaccounted implementation condition is usually conventional laboratory conditions.
A kind of grill electric chrome solution provided by the present invention, described solution includes the composition of following weight portion: trivalent
Chromic salts: 40～50 parts, cobaltous sulfate: 20～30 parts, sodium sulfate: 10～20 parts, potassium sulfate: 15～25 parts, magnesium sulfate: 15～30
Part, sodium lauryl sulphate: 5～10 parts, nano aluminum nitride: 5～10 parts, dodecylbenzene sodium sulfonate: 1～5 part, oxalic acid two
Butyl tin: 1～5 part, chelating agent: 1～5 part, complexant: 1～5 part, conducting salt: 1～5 part, buffer agent: 1～5 part, You Jitian
Add agent: 1～5 part, deionized water: 80～100 parts.
Further, described solution includes the composition of following weight portion: chromic salt: 45～50 parts, cobaltous sulfate: 20～25
Part, sodium sulfate: 15～20 parts, potassium sulfate: 20～25 parts, magnesium sulfate: 15～25 parts, sodium lauryl sulphate: 5～8 parts, nanometer
Aluminium nitride: 5～7 parts, dodecylbenzene sodium sulfonate: 1～3 part, dibutyltin diacetate: 2～5 parts, chelating agent: 1～3 part, join
Position agent: 1～4 part, conducting salt: 3～5 parts, buffer agent: 2～5 parts, organic additive: 1～3 part, deionized water: 80～90 parts.
Preferably, described solution includes the composition of following weight portion: chromic salt: 45 parts, cobaltous sulfate: 25 parts, sodium sulfate:
15 parts, potassium sulfate: 20 parts, magnesium sulfate: 23 parts, sodium lauryl sulphate: 7 parts, nano aluminum nitride: 6 parts, DBSA
Sodium: 2 parts, dibutyltin diacetate: 3 parts, chelating agent: 2 parts, complexant: 3 parts, conducting salt: 4 parts, buffer agent: 2 parts, You Jitian
Add agent: 2 parts, deionized water: 90 parts.
Separately, described chromic salt is chromic sulfate, chromium sulfate basic, chromium trichloride, chromium carbonate, chromium acetate, chromic formate or hydrogen
Chromium oxide.
Separately having, described chelating agent is malic acid, tartaric acid, oxalic acid, formic acid, citric acid, 5-sulphosalicylic acid, imino-diacetic
Acetic acid, aspartic acid or acetic acid.
Again, described complexant is glycolic, methanol, carbamide or hydantoin.
Further, described conducting salt is sodium chloride or ammonium chloride.
And, described organic additive is Polyethylene Glycol, polyvinyl alcohol, butynediols, polymine or alkyl phenol polyoxy
Vinyl Ether.
Meanwhile, the present invention also provides for a kind of using grill electric chrome solution that grill carries out electric plating method, described electricity
Electroplating method comprises the steps:
1) configuration electric chrome solution
Nano aluminum nitride is added in dodecylbenzene sodium sulfonate, adds 20～30 parts of deionized waters, 600～800 turns/
The rotating speed down cut divided disperses 15～20 minutes, under the rotating speed of 1000～1200 revs/min, shears 5～10 minutes, according to joining
Ratio, add described chromic salt, cobaltous sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, sodium lauryl sulphate, chelating agent, complexant,
Conducting salt, buffer agent, organic additive and residue deionized water, stir 10～15 minutes under 500～600 revs/min of rotating speeds, mixed
Close uniformly, use ultrasound wave dispersion, disperse power 700～800W, jitter time 10～15 minutes, obtain described electric chrome solution；
2) grill electrodeposited chromium
Take step 1) gained electric chrome solution, stir 2～3 hours at the rotating speeds of 700～800 revs/min, bath pH values is
2～3, grill oil removing to be plated, rust cleaning are cleaned up, polishes smooth, as negative electrode, graphite, as anode, immerses electrodeposited chromium molten
In liquid, solution temperature 40～55 DEG C, cathode-current density: 15～25A/dm2, electroplating time 1～2 hours, electroplating process stirs
Mixing, rotating speed is 150～200 revs/min.
Separately, thickness of coating is 50～80 μm.
Wherein, a kind of grill electric chrome solution ingredient lists that table 1 various embodiments of the present invention are provided.
Table 1 (unit: weight portion)
A kind of grill electric chrome solution provided by the present invention and electrodeposited chromium method thereof, described electric chrome solution uses three
Valency chromic salts, environmentally friendly, beneficially producers are healthy, after testing, without poisonous metals such as lead, cadmium, and mercuries, add nanometer
Aluminium nitride, promotes coating activity, adds chelating agent, complexant, conducting salt, buffer agent, organic additive, strengthens thickness of coating,
Thickness of coating is up to 50～80 μm, and hardness is up to HV and is up to 1000～1100, and corrosion resistance is strong, and salt spray resistance is tested 10～15 days
Coating invariant color.
It should be noted that above example is only in order to illustrate technical scheme and unrestricted.Although with reference to relatively
The present invention has been described in detail by good embodiment, it will be understood by those within the art that, can be to the technology of invention
Scheme is modified or equivalent, and without deviating from the scope of technical solution of the present invention, it all should contain the power in the present invention
In profit claimed range.
Claims (10)
1. a grill electric chrome solution, it is characterised in that described solution includes the composition of following weight portion: chromic salt:
40 ~ 50 parts, cobaltous sulfate: 20 ~ 30 parts, sodium sulfate: 10 ~ 20 parts, potassium sulfate: 15 ~ 25 parts, magnesium sulfate: 15 ~ 30 parts, dodecyl
Sodium sulfate: 5 ~ 10 parts, nano aluminum nitride: 5 ~ 10 parts, dodecylbenzene sodium sulfonate: 1 ~ 5 part, dibutyltin diacetate: 1 ~ 5 part,
Chelating agent: 1 ~ 5 part, complexant: 1 ~ 5 part, conducting salt: 1 ~ 5 part, buffer agent: 1 ~ 5 part, organic additive: 1 ~ 5 part, deionization
Water: 80 ~ 100 parts.
A kind of grill electric chrome solution the most according to claim 1, it is characterised in that described solution includes following weight
The composition of part: chromic salt: 45 ~ 50 parts, cobaltous sulfate: 20 ~ 25 parts, sodium sulfate: 15 ~ 20 parts, potassium sulfate: 20 ~ 25 parts, sulphuric acid
Magnesium: 15 ~ 25 parts, sodium lauryl sulphate: 5 ~ 8 parts, nano aluminum nitride: 5 ~ 7 parts, dodecylbenzene sodium sulfonate: 1 ~ 3 part, diethyl
Acid dibutyl tin: 2 ~ 5 parts, chelating agent: 1 ~ 3 part, complexant: 1 ~ 4 part, conducting salt: 3 ~ 5 parts, buffer agent: 2 ~ 5 parts, organic interpolation
Agent: 1 ~ 3 part, deionized water: 80 ~ 90 parts.
A kind of grill electric chrome solution the most according to claim 1, it is characterised in that described solution includes following weight
The composition of part: chromic salt: 45 parts, cobaltous sulfate: 25 parts, sodium sulfate: 15 parts, potassium sulfate: 20 parts, magnesium sulfate: 23 parts, dodecane
Base sodium sulfate: 7 parts, nano aluminum nitride: 6 parts, dodecylbenzene sodium sulfonate: 2 parts, dibutyltin diacetate: 3 parts, chelating agent: 2
Part, complexant: 3 parts, conducting salt: 4 parts, buffer agent: 2 parts, organic additive: 2 parts, deionized water: 90 parts.
A kind of grill electric chrome solution the most according to claim 1, it is characterised in that described chromic salt is sulphuric acid
Chromium, chromium sulfate basic, chromium trichloride, chromium carbonate, chromium acetate, chromic formate or chromic oxide gel.
A kind of grill electric chrome solution the most according to claim 1, it is characterised in that described chelating agent be malic acid,
Tartaric acid, oxalic acid, formic acid, citric acid, 5-sulphosalicylic acid, iminodiacetic acid, aspartic acid or acetic acid.
A kind of grill electric chrome solution the most according to claim 1, it is characterised in that described complexant be glycolic,
Methanol, carbamide or hydantoin.
A kind of grill electric chrome solution the most according to claim 1, it is characterised in that described conducting salt be sodium chloride or
Ammonium chloride.
A kind of grill electric chrome solution the most according to claim 1, it is characterised in that described organic additive is poly-second
Glycol, polyvinyl alcohol, butynediols, polymine or alkylphenol polyoxyethylene.
9. one kind uses the side that grill is electroplated by a kind of grill electric chrome solution according to any one of claim 1 ~ 8
Method, it is characterised in that described electro-plating method comprises the steps:
1) configuration electric chrome solution
Nano aluminum nitride is added in dodecylbenzene sodium sulfonate, add 20 ~ 30 parts of deionized waters, 600 ~ 800 revs/min turn
Speed down cut disperses 15 ~ 20 minutes, under the rotating speed of 1000 ~ 1200 revs/min, shears 5 ~ 10 minutes, according to proportioning, adds described
Chromic salt, cobaltous sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, sodium lauryl sulphate, chelating agent, complexant, conducting salt, buffering
Agent, organic additive and residue deionized water, stir 10 ~ 15 minutes, mix homogeneously under 500 ~ 600 revs/min of rotating speeds, uses super
Sound wave disperses, and disperses power 700 ~ 800W, jitter time 10 ~ 15 minutes, obtains described electric chrome solution；
2) grill electrodeposited chromium
Take step 1) gained electric chrome solution, stir 2 ~ 3 hours at the rotating speeds of 700 ~ 800 revs/min, bath pH values is 2 ~ 3, will
Grill oil removing to be plated, rust cleaning clean up, and polish smooth, and as negative electrode, graphite, as anode, immerses in electric chrome solution, molten
Liquid temp 40 ~ 55 DEG C, cathode-current density: 15 ~ 25A/dm2, electroplating time 1 ~ 2 hour, electroplating process stirs, rotating speed is
150 ~ 200 revs/min.
A kind of grill electrodeposited chromium method the most according to claim 9, it is characterised in that thickness of coating is 50 ~ 80 μm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107460527A (en) * | 2017-08-24 | 2017-12-12 | 成都圻坊生物科技有限公司 | A kind of nano aluminum nitride composite plating solution and electro-plating method |
| CN111349952A (en) * | 2020-03-06 | 2020-06-30 | 广州三孚新材料科技股份有限公司 | Trivalent black chromium electroplating solution for solar heat collector |
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| CN102154665A (en) * | 2011-03-21 | 2011-08-17 | 济南德锡科技有限公司 | Trivalent chromium plating solution composite, preparation method thereof and chromium plating process |
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| CN104611734A (en) * | 2013-11-05 | 2015-05-13 | 无锡市雪江环境工程设备有限公司 | Nano aluminium nitride composite chromium plating solution and electroplating method |
| CN105696028A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院金属研究所 | Trivalent chromium electroplating solution and electroplating method |
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| US4196063A (en) * | 1978-06-02 | 1980-04-01 | International Lead Zinc Research Organization, Inc. | Electrodeposition of black chromium |
| CN101665960A (en) * | 2009-09-04 | 2010-03-10 | 厦门大学 | Trivalent chromium sulfate plating solution and preparation method thereof |
| CN102154665A (en) * | 2011-03-21 | 2011-08-17 | 济南德锡科技有限公司 | Trivalent chromium plating solution composite, preparation method thereof and chromium plating process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107460527A (en) * | 2017-08-24 | 2017-12-12 | 成都圻坊生物科技有限公司 | A kind of nano aluminum nitride composite plating solution and electro-plating method |
| CN111349952A (en) * | 2020-03-06 | 2020-06-30 | 广州三孚新材料科技股份有限公司 | Trivalent black chromium electroplating solution for solar heat collector |
| CN111349952B (en) * | 2020-03-06 | 2021-06-08 | 广州三孚新材料科技股份有限公司 | Trivalent black chromium electroplating solution for solar heat collector |
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