CN106119906A - The high anti-corrosion trivalent chromium plating chromium of environment-friendly type and chromium phosphorus alloy solution for magnesium alloy - Google Patents
The high anti-corrosion trivalent chromium plating chromium of environment-friendly type and chromium phosphorus alloy solution for magnesium alloy Download PDFInfo
- Publication number
- CN106119906A CN106119906A CN201610567400.XA CN201610567400A CN106119906A CN 106119906 A CN106119906 A CN 106119906A CN 201610567400 A CN201610567400 A CN 201610567400A CN 106119906 A CN106119906 A CN 106119906A
- Authority
- CN
- China
- Prior art keywords
- chromium
- solution
- environment
- friendly type
- high anti
- 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
Classifications
-
- 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
-
- 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
- C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses the high anti-corrosion trivalent chromium plating chromium of a kind of environment-friendly type and chromium phosphorus alloy solution for magnesium alloy, comprise chromic salt, conducting salt, main chelating agent, auxiliary complex-former, reducing agent, slow releasing agent, codeposition derivant and aqueous solvent；Wherein, chromic salt is potassium trioxalatochromate(III).The present invention is in chloride type trivalent chromium plating solution, the chromium phosphorus alloy that induction sodium hypophosphite reduction generates is co-precipitated with chromium, obtain chromium and chromium phosphor alloy coating that total phosphorus content is not more than 0.2%, there is higher corrosion resistance, and, the material that the present invention provides trivalent chromic ion to originate is potassium trioxalatochromate(III), both can provide the trivalent chromic ion of electro-deposition；The reducible solution of oxalate as hexavalent chrome reduction agent, can also be electrolysed the hexavalent chromium of generation；Simultaneously also can be as conducting salt, the potassium ion ionized out in solution has good electric conductivity.
Description
Technical field
The invention belongs to electrodeposited chromium technical field, be specifically related to the high anti-corrosion trivalent chromium plating chromium of a kind of environment-friendly type and chromium-phosphorus
Alloy solution.
Background technology
Trivalent chromium plating has been widely used for five metals, plastic electroplating product, the raising required along with properties of product, trivalent
Chromium electrodeposited chromium does not often reach requirement when " automobile ABS electroplates the mud test of accessory Russia ".
Russia's mud is made up of with filling sand calcium chloride (CaCl2), and calcium chloride (CaCl2) is conventional desiccant and snow melt
Agent, water absorption is strong, and Russia's mud can be kept to moisten, and the corrosion to electrodeposited coating is bigger." automobile ABS electroplates accessory Russia mud
Test " be that the automobile ABS proposed in recent years electroplates the method that accessory corrosion resistance of coating checks: 25g calcium chloride adds 30ml water
In, after dissolving, it is slowly added into 18g kaolin powder, stirs into pasty state standby；Uniformly coat in detected specimen surface, be placed in
In constant temperature humidity chamber, 60 ± 3 DEG C, its corrosion resistance of timing test under 23 ± 2% relative humiditys.
Common trivalent chromium plating sample only 10h, does not reaches far away the requirement of 96h, and therefore, existing trivalent chromium plating chromium is molten
Liquid, requires further improvement.
Summary of the invention
The present invention is the problem overcoming prior art to exist, it is provided that the high anti-corrosion trivalent chromium plating chromium of a kind of environment-friendly type and chromium-
Phosphorus alloy solution for magnesium alloy.
Technical scheme is as follows:
The high anti-corrosion trivalent chromium plating chromium of a kind of environment-friendly type and chromium-phosphorus alloy solution for magnesium alloy, comprise chromic salt, conducting salt, main network
Mixture, auxiliary complex-former, reducing agent, slow releasing agent, codeposition derivant and aqueous solvent；Wherein, chromic salt is potassium trioxalatochromate(III),
Corresponding mass/volume concentration is as follows:
In the present invention
(1), conducting salt: be used for reducing solution resistance, increase electrodeposited coating covering power, preferably ammonium chloride；
(2), main chelating agent: preferably ammonium formate, formate generates stable comple with trivalent chromic ion, stabilizing trivalent chromium from
Son；
(3), auxiliary complex-former: one or more in glycine, glycolic, succinic acid, constitute combinedization
Learning plating auxiliary complex-former, effect has two aspect: a, reduces free trivalent chromic ion concentration further, prevents metallic hydrogen in coating
Being mingled with of oxide；B, serve as the accelerator of chemical deposition chromium-phosphorus alloy；Conventional salt acid type, sulfuric acid type do not use this
Measure.
(4), reducing agent: preferably sodium hypophosphite, constitute combined chemical plating auxiliary with glycine, glycolic, succinic acid
Chelating agent synergism, in electrolytic process, electronation trivalent chromic ion simultaneously, generate in chromium-phosphorus alloy, with electroplating process
The chromium generated forms chromium and chromium-phosphor alloy coating, is the source of phosphorus in coating；
(5), buffer agent: preferred boric acid, act the effect stablizing solution ph；
(6), codeposition derivant: preferably sulfuric acid is ferrous, makes codeposition occur in the high and low district of electric current density.
In the present invention, chemical composition and the mass/volume concentration thereof of preferably one formula are as follows:
The present invention, in chloride type trivalent chromium plating solution, induces chromium-phosphorus alloy and the chromium of sodium hypophosphite reduction generation
Co-precipitation, obtains chromium and chromium-phosphor alloy coating that total phosphorus content is not more than 0.2%, has higher corrosion resistance, and, this
The material in bright offer trivalent chromic ion source is potassium trioxalatochromate(III), both can provide the trivalent chromic ion of electro-deposition；Can also make
For hexavalent chrome reduction agent, the reducible solution of oxalate is electrolysed the hexavalent chromium of generation；Simultaneously also can be as conducting salt, solution
The middle potassium ion ionized out has good electric conductivity；Rear two select be other main salt (such as: chromium trichloride, chromium sulfate basic, oxalic acid
Chromium) do not have；Using potassium trioxalatochromate(III), reduce the total concentration of solute in solution, Chlorine in Solution ion concentration reduces, and subtracts
Lacked solution to parent metal or the corrosivity of basis coating, this corrosion be the impurity of trivalent chromium plating solution main come
Source, impurity source controls, and advantageously reduces owing to impurity causes Troubles of Electroplating.
About hexavalent chrome reduction agent: owing to trivalent chromium is middle valence state, in electroplating process, negative electrode produces crome metal, anode
Producing Cr VI, Cr VI is extremely harmful to, it is necessary to suppress it to produce.Using a to divide groove isolation method, b covers precious metal anode method,
C adds reducing agent method etc., wherein, adds reducing agent method and is applied, and most commonly used is to add bromide ion, bromide ion and six
The reaction of valency chromium generates bromine and trivalent chromium, and bromine and the water in solution react generation bromide ion, and benefit is to be continuously added into reducing agent,
But shortcoming is the current efficiency greatly reducing electrodeposited chromium.In the present invention, hexavalent chrome reduction agent is simultaneously introduced with trivalent chromic ion
And synchronous consumption, also supplement hexavalent chrome reduction agent while of persistently supplementing chromic and do not reduce current efficiency.
Accompanying drawing explanation
Fig. 1 is Bright Nickel Electroplating and chromium and the SEM test figure of chromium-phosphor alloy coating in Copper base material；
Fig. 2 is the EDS energy spectrogram in Fig. 1 at A.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, invention is described in detail.
Embodiment 1
Trivalent chromium plating chromium consists of with chromium-phosphorus alloy solution for magnesium alloy: potassium trioxalatochromate(III) 100g/L, ammonium chloride 50g/L, ammonium formate
40g/L, glycine 5g/L, glycolic 2g/L, succinic acid 2g/L, sodium hypophosphite 5g/L, boric acid 60g/L, ferrous sulfate 20mg/
L, solvent are water.
Using the formula solution of above-mentioned composition, solution ph is adjusted to 3～4, room temperature electroplates trivalent chromium plating chromium solution, with
Pre-plating piece is negative electrode, with graphite electrode as anode, under electric current density is 25A/dm2, and electrodeposited chromium 8min, obtain on pre-plating piece surface
To electrodeposited chromium layers.
With reference to Fig. 1 and Fig. 2, in the present embodiment, pre-plating piece chooses Copper base material, upper Copper base material Bright Nickel Electroplating and chromium with
Chromium-phosphor alloy coating, through SEM sem test, it can be seen that Deposit appearance uniform and delicate, and surface smoothness quality is good；Again
The most optional a little carries out EDS power spectrum test, it is thus achieved that the compositional data shown in table 1:
As it can be seen from table 1 containing phosphorus in chrome plating, therefore, define the multiple structure of chromium and chromium-phosphorus alloy, this
Owing to there is nonmetalloid phosphorus in structure, it is strong, according to " automobile ABS electroplates accessory Russia that its corrosion resistance can compare pure evanohm
Ross mud is tested ", it is anti-corrosion, and duration is up to more than 100h, relatively common chrome plating, and its corrosion resistance is greatly improved.
Embodiment 2
Trivalent chromium plating chromium consists of with chromium-phosphorus alloy solution for magnesium alloy: potassium trioxalatochromate(III) 70g/L, ammonium chloride 35g/L, ammonium formate
30g/L, glycine 3g/L, glycolic 1g/L, succinic acid 1g/L, sodium hypophosphite 3g/L, boric acid 30g/L, ferrous sulfate 15mg/
L, solvent are water.
With reference to embodiment 1 being carried out electroplate and carry out dependence test, obtain Deposit appearance uniform and delicate, surface smoothness quality
Good；It is anti-corrosion, and duration is shown in Table 2.
Table 1 EDS power spectrum micro-area composition table
The mud test of table 2 Russia
Embodiment 3
Trivalent chromium plating chromium, the consisting of of chromium-phosphorus alloy solution for magnesium alloy: potassium trioxalatochromate(III) 120g/L, ammonium chloride 60g/L, ammonium formate
50g/L, glycine 8g/L, glycolic 4g/L, succinic acid 3g/L, sodium hypophosphite 10g/L, boric acid 80g/L, ferrous sulfate
40mg/L, solvent are water.
With reference to embodiment 1 being carried out electroplate and carry out dependence test, obtain Deposit appearance uniform and delicate, surface smoothness quality
Good；It is anti-corrosion, and duration is shown in Table 2.
Comparative example 1
Consisting of of trivalent chromium plating solution: chromic sulfate 100g/L, ammonium chloride 50g/L, ammonium formate 40g/L, glycine
5g/L, glycolic 2g/L, succinic acid 2g/L, ammonium bromide 5g/L, boric acid 60g/L, ferrous sulfate 20mg/L, solvent are water.
With reference to embodiment 1 being carried out electroplate and carry out dependence test, obtain Deposit appearance uniform and delicate, surface smoothness quality
Good；It is anti-corrosion, and duration is shown in Table 2.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto,
Any those familiar with the art in the technical scope of present disclosure, according to technical scheme and
Inventive concept equivalent or change in addition, all should contain within protection scope of the present invention.
Claims (8)
1. the high anti-corrosion trivalent chromium plating chromium of environment-friendly type and chromium-phosphorus alloy solution for magnesium alloy, it is characterised in that comprise chromic salt, lead
Electricity salt, main chelating agent, auxiliary complex-former, reducing agent, slow releasing agent, codeposition derivant and aqueous solvent；Wherein, chromic salt is
Potassium trioxalatochromate(III), corresponding mass/volume concentration is as follows:
The high anti-corrosion trivalent chromium plating chromium of environment-friendly type the most according to claim 1 and chromium-phosphorus alloy solution for magnesium alloy, it is characterised in that
Described conducting salt is ammonium chloride.
The high anti-corrosion trivalent chromium plating chromium of environment-friendly type the most according to claim 2 and chromium-phosphorus alloy solution for magnesium alloy, it is characterised in that
Described main chelating agent is ammonium formate.
The high anti-corrosion trivalent chromium plating chromium of environment-friendly type the most according to claim 3 and chromium-phosphorus alloy solution for magnesium alloy, it is characterised in that
One or more in glycine, glycolic, succinic acid of described auxiliary complex-former.
The high anti-corrosion trivalent chromium plating chromium of environment-friendly type the most according to claim 4 and chromium-phosphorus alloy solution for magnesium alloy, it is characterised in that
Described reducing agent is sodium hypophosphite.
The high anti-corrosion trivalent chromium plating chromium of environment-friendly type the most according to claim 5 and chromium-phosphorus alloy solution for magnesium alloy, it is characterised in that
Described buffer agent is boric acid.
The high anti-corrosion trivalent chromium plating chromium of environment-friendly type the most according to claim 6 and chromium-phosphorus alloy solution for magnesium alloy, it is characterised in that
Described codeposition derivant is ferrous sulfate.
The high anti-corrosion trivalent chromium plating chromium of environment-friendly type the most according to claim 7 and chromium-phosphorus alloy solution for magnesium alloy, it is characterised in that
This trivalent chromium plating chromium is as follows with chromium-phosphorus alloy solution for magnesium alloy chemical composition:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610567400.XA CN106119906B (en) | 2016-07-18 | 2016-07-18 | The high anti-corrosion trivalent chromium plating chromium of environment-friendly type and chromium-phosphorus alloy solution for magnesium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610567400.XA CN106119906B (en) | 2016-07-18 | 2016-07-18 | The high anti-corrosion trivalent chromium plating chromium of environment-friendly type and chromium-phosphorus alloy solution for magnesium alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106119906A true CN106119906A (en) | 2016-11-16 |
| CN106119906B CN106119906B (en) | 2018-10-02 |
Family
ID=57289016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610567400.XA Active CN106119906B (en) | 2016-07-18 | 2016-07-18 | The high anti-corrosion trivalent chromium plating chromium of environment-friendly type and chromium-phosphorus alloy solution for magnesium alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106119906B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108866586A (en) * | 2018-07-05 | 2018-11-23 | 厦门大学 | A kind of electroplate liquid and preparation method thereof of trivalent chromium system electrodeposited chromium ferroalloy |
| CN113445049A (en) * | 2021-06-23 | 2021-09-28 | 九牧厨卫股份有限公司 | Method for electroplating environment-friendly chromium on aluminum and aluminum alloy parts |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4196063A (en) * | 1978-06-02 | 1980-04-01 | International Lead Zinc Research Organization, Inc. | Electrodeposition of black chromium |
| JPS6237391A (en) * | 1985-08-12 | 1987-02-18 | Sumitomo Metal Ind Ltd | Electrolytic coating method with amorphous cr alloy |
| CN1993500A (en) * | 2004-06-24 | 2007-07-04 | 利奥尼德·库兹明 | Chromium plating method |
| CN101469435A (en) * | 2007-12-25 | 2009-07-01 | 中国科学院兰州化学物理研究所 | Method for electrodeposition of chromium-phosphor alloy coating in environment protection type trivalent chromium plating bath |
| CN101665960A (en) * | 2009-09-04 | 2010-03-10 | 厦门大学 | Trivalent chromium sulfate plating solution and preparation method thereof |
-
2016
- 2016-07-18 CN CN201610567400.XA patent/CN106119906B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4196063A (en) * | 1978-06-02 | 1980-04-01 | International Lead Zinc Research Organization, Inc. | Electrodeposition of black chromium |
| JPS6237391A (en) * | 1985-08-12 | 1987-02-18 | Sumitomo Metal Ind Ltd | Electrolytic coating method with amorphous cr alloy |
| CN1993500A (en) * | 2004-06-24 | 2007-07-04 | 利奥尼德·库兹明 | Chromium plating method |
| CN101469435A (en) * | 2007-12-25 | 2009-07-01 | 中国科学院兰州化学物理研究所 | Method for electrodeposition of chromium-phosphor alloy coating in environment protection type trivalent chromium plating bath |
| CN101665960A (en) * | 2009-09-04 | 2010-03-10 | 厦门大学 | Trivalent chromium sulfate plating solution and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 郝照辉等: "硫酸盐三价铬电沉积铬-磷合金工艺的研究", 《电镀与环保》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108866586A (en) * | 2018-07-05 | 2018-11-23 | 厦门大学 | A kind of electroplate liquid and preparation method thereof of trivalent chromium system electrodeposited chromium ferroalloy |
| CN113445049A (en) * | 2021-06-23 | 2021-09-28 | 九牧厨卫股份有限公司 | Method for electroplating environment-friendly chromium on aluminum and aluminum alloy parts |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106119906B (en) | 2018-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fratesi et al. | Electrodeposition of zinc-nickel alloy coatings from a chloride bath containing NH4Cl | |
| JP2017503926A (en) | Electroplating bath containing trivalent chromium and method for depositing chromium | |
| CN106661753A (en) | Ionic liquid electrolyte and method to electrodeposit metals | |
| CN105088287A (en) | Electrolyte prepared based on deep eutetic ion liquid and water and electroplating method thereof | |
| US4161432A (en) | Electroplating chromium and its alloys | |
| CN107829116A (en) | Cyanide-free alkaline copper plating electroplate liquid | |
| Wu et al. | Electrochemical studies of zinc—nickel codeposition in chloride baths | |
| Tu et al. | Electrodeposition of aluminium foils on carbon electrodes in low temperature ionic liquid | |
| US3634211A (en) | Process for electroplating chromium and electrolytes therefor | |
| CN103806044B (en) | The method of electrolytic preparation iridium coating layer in chloro-iridic acid caesium-Chlorides molten salts | |
| CN106119906B (en) | The high anti-corrosion trivalent chromium plating chromium of environment-friendly type and chromium-phosphorus alloy solution for magnesium alloy | |
| US2990343A (en) | Chromium alloy plating | |
| Yin et al. | Current pulse plating of nickel-iron alloys on rotating disk electrodes | |
| Zeng et al. | A review of recent patents on trivalent chromium plating | |
| US4076597A (en) | Method of forming iron foil at high current densities | |
| Takeda et al. | Zirconium metal production by electrorefining of Zr oxycarbide | |
| US2766196A (en) | Process for the electrodeposition of iron-chromium alloys | |
| Jaén et al. | Structural studies of electrodeposited tin—cobalt alloys | |
| Bratoeva et al. | Effect of sulfamate-citrate electrolyte pH on the Ni-W alloy electrodeposition | |
| CN109487309A (en) | A kind of new non-cyanide bright alkaline copper plating complexing agent | |
| Bieliński et al. | Selected problems in the continuous electrodeposition of Ni-Fe alloys | |
| CN108842172A (en) | A kind of method that eutectic solvent electro-deposition prepares stainless steel coating | |
| US4447299A (en) | Use of alcohol for increasing the current efficiency of chromium plating | |
| CN110184631B (en) | Cyanide-free gold plating electroplating solution and preparation method and electroplating process thereof | |
| IE47088B1 (en) | Electroplating chromium and its alloys |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180813 Address after: 314506 Zhejiang Tongxiang city Jiaxing City Tu Dian town Textile Industrial Park Applicant after: Zhejiang ensoo Chemical Technology Co., Ltd. Address before: 318000 1 Sanjiang Road, light industry investment zone, Huangyan Economic Development Zone, Taizhou, Zhejiang Applicant before: Nson (Taizhou) Chemical Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |