CN107604393B - A kind of no cyanogen alkali copper electroplating composition and preparation method thereof - Google Patents
A kind of no cyanogen alkali copper electroplating composition and preparation method thereof Download PDFInfo
- Publication number
- CN107604393B CN107604393B CN201710963412.9A CN201710963412A CN107604393B CN 107604393 B CN107604393 B CN 107604393B CN 201710963412 A CN201710963412 A CN 201710963412A CN 107604393 B CN107604393 B CN 107604393B
- Authority
- CN
- China
- Prior art keywords
- copper
- electroplating composition
- copper electroplating
- cyanogen alkali
- cyanogen
- 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.)
- Active
Links
Abstract
The present invention relates to field of electroplating, and in particular to arrives a kind of no cyanogen alkali copper electroplating composition and preparation method thereof.A kind of no cyanogen alkali copper electroplating composition, the raw material for preparing without cyanogen alkali copper electroplating composition described in 1L include：Bivalent cupric ion：15~17g；Citric acid：185~195g；Sodium potassium tartrate tetrahydrate：50~60g；Potassium nitrate：5~6.5g；1,2 1,2-diaminocyclohexane tetraacetic acids：0.5~1g；Wetting agent：0.2~0.3g；Brightener：1.2~1.6g；Leveling agent：0.1~0.15g；Deionized water adds to 1L.
Description
Technical field
The present invention relates to field of electroplating, and in particular to arrives a kind of no cyanogen alkali copper electroplating composition and preparation method thereof.
Background technology
Plating be with electrolytic method it is smooth in substrate deposit layer of surface and with the firm metal of basal body structure, conjunction
The technology of gold or composite material.It with electrochemistry, Coordinative Chemistry, organic chemistry, surface chemistry, crystallography, Metal Material Science with
And the subjects such as electromechanical engineering have close relationship.From the formation for being formulated into coating of plating solution, the intermediate shape that pass through complex compound
At the electrode reduction of, complex ion and the processes such as electrocrystallization of metallic atom.Therefore, the composition of electrolyte, such as complexing agent, addition
Agent, other auxiliary reagents and plating conditions (such as temperature, acidity, current density, electrode potential, stirring), all will directly or
The electric discharge for influencing complex ion and electrocrystallization process are connect, to influence the various properties of acquired deposition layer, such as the cause of coating
The bond strength etc. of close degree, reflective property, dispersibility, covering power, leveling ability, coating and parent metal.
Copper is a kind of rich in ductility, is easy to the soft metal of mechanical processing, conductive and thermal conductivity is fabulous.Copper is for water, salt
And acid solution, there is preferable stability in no dissolved oxygen and reducing atmosphere, and copper processing is cheap, with other coating knots
Resultant force is good, and the porosity of copper plate is low, therefore can be as the prime coat or middle layer of steel and other base materials, extensively
It is general to be used in protected decoration coating (such as：On automobile, building materials, daily-use electrical appliance etc.).Based on the good conductive and ductility of copper
Can, copper facing is in plastics metalizing intermediate deposit, printed circuit board (PCB), IC package technology, VLSI chip
There is great application value in technology.In addition to this high-melting-point and carbon for utilizing copper cannot form solid solution and compound with copper
Characteristic, copper plating film also can apply to the anti-carburizi ng field of steel.
Copper plating bath is divided into cyanide electroplating, cyanide-free copper electroplating two major classes.The advantages of cyanide electroplating electrolyte, is dispersibility and covers
Lid ability is good, and bath composition is simple, easy care, is suitable for the bottoming coating etc. of steel and iron parts and zinc, Al-alloy products.The disadvantage is that
Cyanide of the electrolyte containing a large amount of severe toxicity, is electroplated the waste water of generation, exhaust gas endangers operator's health, pollutes environment and is electrolysed
Liquid stability is poor.Cyanide-free copper electroplating is divided into acid copper-plating and alkaline copper plating.Acid copper-plating is mainly to plate thick copper layer on nickel or Copper substrate,
Steel and iron parts and zinc alloy piece all directly cannot carry out copper facing in acid copper electrolyte, generally require through alkaline copper plating in steel and iron parts
Preplating, which is carried out, with zinc alloy surface is convenient for subsequent acid copper-plating, nickel plating to improve the binding force of coating and parent metal
Etc. techniques.
Be widely used that pyrophosphate copper plating in alkaline non-cyanide electro-coppering field, but its there is also some disadvantages, such as
Plating solution is of high cost, and since pyrophosphoric acid is poor to the complexing of copper, and direct copper plating can be due to replacing layers of copper in steel and iron parts
In the presence of satisfactory copper plate cannot be obtained.The fatal defects of pyrophosphate copper plating are that pyrophosphate method of electro-plating liquid stability is poor,
Pyrophosphate therein can be hydrolyzed into orthophosphoric acid root, and with the increase of electroplating time, the content of orthophosphoric acid root is continuously increased, electric current
Density declines, and deposition velocity reduces.And contain a large amount of P elements in pyrophosphate method of electro-plating liquid, waste water treatmentntrol difficult does not meet state
The requirement of family's clean manufacturing.
With citric acid or its salt for main complexing agent, multi-hydroxy carboxy acid's salt prepares copper plating bath as auxiliary complexing agent, can be effective
Inhibit the displacement reaction on iron and Zinc Matrix, the binding force of the copper coating of gained on various matrixes can meet actual requirement.Make
It is high with citric acid or its salt copper plating bath current efficiency, 99.5% is reached as high as, the 60~70% of cyanide electroplating, deposition velocity are higher than
Soon, as intermediate deposit can no longer acid coppering and directly bright nickel plating or other coating, so as to shorten technological process and life
Produce the period.But citric acid or its salt copper plating bath easily mildew, and often need that mould inhibitor, but mould inhibitor meeting in electroplating process is added
Copper plate is mixed into influence binding force of cladding material and make coating embrittlement etc., there is also plating solutions for existing citric acid or its salt copper plating bath
The problems such as Surface flat is bad, stability is bad.
In view of the above-mentioned problems, the present invention provides a kind of no cyanogen alkali copper electroplating composition, it is multiple with citric acid for main complexing agent
It is electroplated with various other complexing agents.The present invention's does not use cyanide and phosphide without cyanogen alkali copper electroplating composition, right
Environmental nonpollution meets the requirement of national clean manufacturing；Use the coating light of the present invention obtained without cyanogen alkali copper electroplating composition
Bright leveling, binding force of cladding material are good, and bath stability is good.
Invention content
In order to solve the above-mentioned technical problem, first part of the invention provides a kind of no cyanogen alkali copper electroplating composition,
The raw material for preparing without cyanogen alkali copper electroplating composition of 1L includes：Bivalent cupric ion：15~17g；Citric acid：185~195g；Winestone
Sour potassium sodium：50~60g；Potassium nitrate：5~6.5g；1,2- 1,2-diaminocyclohexane tetraacetic acids：0.5~1g；Wetting agent：0.2~0.3g；Light
Bright dose：1.2~1.6g；Leveling agent：0.1~0.15g；Deionized water adds to 1L.
As a kind of preferred technical solution of the present invention, the bivalent cupric ion is by basic copper carbonate, copper chloride, bromination
Copper, copper 8-quinolinolate, cupric ethylene diamine tetraacetate, copper citrate, copper sulphate, copper nitrate, copper acetate, copper gluconate, acetyl
Pyruvic acid copper, cupric tartrate, copper diethyl dithiocarbamate, cupric oxalate any one or more of provide.
As a kind of preferred technical solution of the present invention, the wetting agent is selected from cetomacrogol 1000, polyethylene glycol
4000, Macrogol 6000, PEG 8000, myristyl betaine, cetyl betaine, dodecyl weight ratio
Glycine betaine any one or more of.
As a kind of preferred technical solution of the present invention, the brightener is selected from selenium dioxide, ethylenediamine tetra-acetic acid, 1,
4- butynediols, methylene-disulfonic acid, thiocarbamide, potassium rhodanate, triethanolamine, Allyl thiourea, 2-mercaptobenzimidazole, 2- mercaptos
Base benzothiazole, benzotriazole, polyethyleneimine, ethylhexyl sulfate any one or more of.
As a kind of preferred technical solution of the present invention, the leveling agent is (1,2-benzisothiazolin-3-one)-the third
Alkynes.
As a kind of preferred technical solution of the present invention, the leveling agent is quaternized (1,2- benzisothiazole-
3- ketone)-propine, structural formula isX is selected from any one of F, Cl, Br, I.
As a kind of preferred technical solution of the present invention, the raw material for preparing of the no cyanogen alkali copper electroplating composition further includes
Cyclodextrin.
As a kind of preferred technical solution of the present invention, the cyclodextrin is selected from alpha-cyclodextrin, beta-cyclodextrin, γ-ring
Any one of dextrin.
As a kind of preferred technical solution of the present invention, the temperature in use of the no cyanogen alkali copper electroplating composition is 30~
50℃。
The second part of the present invention provides the preparation method without cyanogen alkali copper electroplating composition, include at least with
Lower step：
It takes 700mL deionized waters, is added citric acid, sodium potassium tartrate tetrahydrate, 1,2-cyclohexanediaminetetraacetic acid, after stirring and dissolving,
The salt that bivalent cupric ion is provided is added, 1h is stirred at 50~60 DEG C；Then potassium nitrate is added, stirring and dissolving uses potassium hydroxide
PH to 9.5~10.5 is adjusted with sodium bicarbonate；Then wetting agent, brightener, leveling agent is added, deionization is added in stirring and dissolving
Water is settled to 1L.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to following detailed description.
Advantageous effect：
(1) present invention does not use cyanide and phosphide, environmentally safe, meets the requirement of national clean manufacturing.
(2) good using the coating brightening and leveling obtained without cyanogen alkali copper electroplating composition, the binding force of cladding material of the present invention, plating solution
Stability is good.
Specific implementation mode
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim be closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to the element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end
Value and all integers and score in the range.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " arbitrary
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.
In order to solve the above-mentioned technical problem, first part of the invention provides a kind of no cyanogen alkali copper electroplating composition,
The raw material for preparing without cyanogen alkali copper electroplating composition of 1L includes：Bivalent cupric ion：15~17g；Citric acid：185~195g；Winestone
Sour potassium sodium：50~60g；Potassium nitrate：5~6.5g；1,2- 1,2-diaminocyclohexane tetraacetic acids：0.5~1g；Wetting agent：0.2~0.3g；Light
Bright dose：1.2~1.6g；Leveling agent：0.1~0.15g；Deionized water adds to 1L.
As a kind of preferred technical solution of the present invention, the raw material for preparing without cyanogen alkali copper electroplating composition of 1L includes：Two
Valence copper ion：16g；Citric acid：192g；Sodium potassium tartrate tetrahydrate：56g；Potassium nitrate：6g；1,2- 1,2-diaminocyclohexane tetraacetic acids：0.6g；Profit
Humectant：0.25g；Brightener：1.5g；Leveling agent：0.12g；Deionized water adds to 1L.
As a kind of preferred technical solution of the present invention, the bivalent cupric ion is provided by cupric salt.
The cupric salt is limited there is no other, specifiable to have basic copper carbonate, copper chloride, copper bromide, 8-
Copper quinolinate, cupric ethylene diamine tetraacetate, copper citrate, copper sulphate, copper nitrate, copper acetate, copper gluconate, acetopyruvic acid
Copper, cupric tartrate, copper diethyl dithiocarbamate, cupric oxalate etc..
As a kind of preferred technical solution of the present invention, the bivalent cupric ion is by basic copper carbonate, copper chloride, bromination
Copper, copper 8-quinolinolate, cupric ethylene diamine tetraacetate, copper citrate, copper sulphate, copper nitrate, copper acetate, copper gluconate, acetyl
Pyruvic acid copper, cupric tartrate, copper diethyl dithiocarbamate, cupric oxalate any one or more of provide.
As a kind of preferred technical solution of the present invention, the bivalent cupric ion is by basic copper carbonate, 8-hydroxyquinoline
Copper, copper citrate, cupric tartrate any one or more of provide.
Citric acid
Citric acid also known as citric acid, CAS：77-92-9 is a kind of relatively inexpensive industrial chemicals.Anhydrous citric acid is general
It is indicated with Cit, the structural formula of anhydrous citric acid is as follows：
Citric acid has 4 dentates, energy and Cu2+Form the chelating object of a five-membered ring and a hexatomic ring.Citric acid plates
Copper electroplating liquid main component is citrate and cupric.The complex compound quite stable that they are generated under alkaline condition.Work as lemon
In the case of lemon excessive acid, citrate and Cu2+Complex ion [the Cu (OH) of formation2Cit2]6-KIt is unstable=1.7 × 10-19, and it is same
Complex ion [Cu (the P that the excessive pyrophosphate of sample is formed with copper2O7)2]6-KIt is unstable=1.7 × 10-19, it is seen then that citrate with
Cu2+The complex ion of formation is more more stable than pyrophosphate, and the copper in steel and iron parts can be effectively prevent to replace phenomenon.And use citric acid
The copper plating bath dispersibility and covering power of preparation are very good, and current efficiency is up to 95%.In addition, citric acid also has pH bufferings
Function can stablize the pH value of electroplate liquid, the coating flaw caused by effectively preventing in electroplating process due to bath pH values change
Defect.Again, the anti-impurity pollution of citric acid copper plating bath is very capable, it is ensured that the stability of copper-plating technique production.Citric acid
Copper plating bath is nontoxic, and no poison gas generates, and is not required to set ventilation device.Citric acid is environmentally friendly complexing agent, and waste water is easier to locate
It manages, therefore meets the requirement of national environmental protection using citric acid copper facing.
Stable copper citrate complex compound cannot be formed when citric acid content is relatively low, in plating solution, copper ion is easy to happen
Displacement reaction；Citric acid content is where appropriate, form stable mixed-ligand complex [Cu in plating solution2(OH)2Cit2]4-, enhancing
Cathodic polarization acts on, and the citrate to dissociate in plating solution not only contributes to anodic solution, is also adsorbed on cathode surface, a side
Face inhibits the reduction reaction of copper ion, additionally aids and forms the careful coating of crystallization in wider current density range；Work as citric acid
When too high levels, free citrate ion increases, and current efficiency reduces, and deposition velocity is slack-off, and coating is easy to burn.
Sodium potassium tartrate tetrahydrate
Sodium potassium tartrate tetrahydrate also known as rocchelle's salt, Rochelle salt, CAS：304-59-6, have complexing, can with aluminium, beryllium, cadmium,
The metal ions such as cobalt, molybdenum, niobium, lead, nickel, palladium, platinum, rhodium, antimony, tin, tantalum, tungsten, zinc, copper and selenium, tellurium are formed in alkaline solution can
Solubleness complex.
Two kinds of complexing agents of citric acid and sodium potassium tartrate tetrahydrate cooperate with the coordination for participating in copper ion, increase cathodic polarization energy
Power, copper ion can be stablized at more high current density carries out deposition process, improves the dispersibility of plating solution.But potassium tartrate
Sodium itself is also a kind of strong complex, is easy to compete with citric acid after being added excessively, makes copper ion in the reaction in cathodic region
Become chaotic, cathode efficiency reduces, and occurs that coating color is bad, phenomena such as point occurs.
Potassium nitrate
The effect of potassium nitrate mainly enhances solution conductivity ability, reduces the concentration polarization in electroplating process, is conducive to improve
Current efficiency and raising cathode-current density range.In addition nitrate ion can be reacted with hydrogen ion, reduce evolving hydrogen reaction hair
Raw possibility.
1,2- 1,2-diaminocyclohexane tetraacetic acids
1,2-cyclohexanediaminetetraacetic acid, CAS：482-54-2 crystallizes for white powder, it can be with Fe, Ni, Cu, Zn, Cd
Equal various metals form stable chelate, are generally commonly used for complexing of metal ion agent, screening agent, agriculture chemistry spray, day
Apply some make up additive, blood anticoagulant, dyeing assistant, fibre finish, synthetic rubber polymerization initiator, color sensitive material
Bleach-fixing liquid, stabilizer of washing processing etc..1,2- 1,2-diaminocyclohexane tetraacetic acid properties are stable, complex performance is excellent.The present invention
1,2- 1,2-diaminocyclohexane tetraacetic acids be purchased from Hangzhou Jie Heng Chemical Co., Ltd.s.
Wetting agent
Wetting agent is generally surfactant.Wetting agent is adsorbed on metal surface, inhibits evolving hydrogen reaction and displacement reaction
Generation, be conducive to, to metal surface " cleaning ", improve surface effect and the porosity of coating can be reduced.
The wetting agent is limited there is no other, specifiable to have ether nonionic surfactant, betaines
Amphoteric surfactant etc..
The ether nonionic surfactant is specifiable cetomacrogol 1000, Macrogol 4000, poly- second two
Alcohol 6000, PEG 8000 etc..
The betaines amphoteric surfactant, it is specifiable have myristyl betaine, cetyl betaine,
Dodecyl hydroxyl sulfo betaine etc..
As a kind of preferred technical solution of the present invention, the wetting agent is selected from ether nonionic surfactant, sweet tea
Dish bases amphoteric surfactant any one or more of.
As a kind of preferred technical solution of the present invention, the wetting agent is selected from cetomacrogol 1000, polyethylene glycol
4000, Macrogol 6000, PEG 8000, myristyl betaine, cetyl betaine, dodecyl weight ratio
Glycine betaine any one or more of.
Brightener
Brightener is a kind of electroplating additive, its main function is to be adsorbed on electrode surface, forms one layer of very thin suction
Attached layer improves cathodic polarization while playing retardance to the reduction of metal ion so that the Nucleation of metallic crystal increase and
Growth rate slows down, and in this way refines crystallization and achievees the effect that light.
As a kind of preferred technical solution of the present invention, the brightener is selected from selenium dioxide, ethylenediamine tetra-acetic acid, 1,
4- butynediols, methylene-disulfonic acid, thiocarbamide, potassium rhodanate, triethanolamine, Allyl thiourea, 2-mercaptobenzimidazole, 2- mercaptos
Base benzothiazole, benzotriazole, polyethyleneimine, ethylhexyl sulfate any one or more of.
As a kind of preferred technical solution of the present invention, the brightener is selenium dioxide.
Leveling agent
The covering power reflection of plating solution is its macroscopical dispersibility, and what Surface flat then reflected is its microcosmic dispersion energy
Power.In actual production, piece surface has certain roughness, after plating coats, is generally intended to make piece surface
Roughness reduces, and improves surface brightness, and wishes to be improved or fill and lead up in the place for having hole.Surface flat is also plating
One basic demand of fluidity energy.In general, the Surface flat of plating solution can be improved by the way that leveling agent is added.
For the mechanism of action of leveling agent, Ka Duosi (Kardos) proposes diffusion theory, he thinks in microcosmic bumps
On surface, since effective thickness of diffusion layer of the lowest point is more than the value of summit, leveling agent diffuses into the diffusion of microcosmic the lowest point
Speed is less than the speed into summit, in this way, the concentration of summit leveling agent will be greater than the concentration of the lowest point, as a result leveling agent is to summit
The Inhibition of electrode reaction is greater than the Inhibition to the lowest point, i.e. the deposition velocity of the lowest point will be greater than the deposition speed of summit
Degree, this has just achieved the effect that leveling.
When leveling agent concentration is too low, there is no leveling agent or concentration too low without showing Inhibition in summit, the lowest point, yet
Not aobvious leveling effect；When leveling agent concentration is excessive, summit, the lowest point be not equally also aobvious to flatten effect simultaneously by serious resistanceization,
Just there is leveling effect when only concentration is appropriate.
As a kind of preferred technical solution of the present invention, the leveling agent is (1,2-benzisothiazolin-3-one)-the third
Alkynes.
As a kind of preferred technical solution of the present invention, the preparation of (the 1,2-benzisothiazolin-3-one)-propine
Method at least includes the following steps：
A. o-amino thiophenol and urea are taken, is warming up to 155~165 DEG C, stirring stops reaction after 1 hour, will be obtained with hot water
Product recrystallization obtains 1,2-benzisothiazolin-3-one twice, the molar ratio of the o-amino thiophenol and urea is 1：
1.2；
B. it takes 1,2-benzisothiazolin-3-one dissolving in acetone, is slowly added to potassium carbonate, after stirring 15~30min,
3- propargyl chlorides are added, are heated to reflux 4h, the 1,2-benzisothiazolin-3-one, potassium carbonate, 3- propargyl chlorides and acetone rub
You are than being 1：1：1：3；Then mixture is cooled to 0 DEG C, pours into the mixture of ice and water of 100mL thereto, control temperature 0~
10 DEG C, stir 1h；The precipitation generated is collected, is filtered with deionized water, it is that neutrality obtains (1,2- benzisothiazole-to be washed till pH
3- ketone)-propine.
O-amino thiophenol, CAS：137-07-5 is purchased from the joyful beauty bio tech ltd in Wuhan.
3- propargyl chlorides, CAS：624-65-7 is purchased from Sinopharm Chemical Reagent Co., Ltd..
The structural formula of (1,2- benzisothiazole-3-ketones)-propine is
As a kind of preferred technical solution of the present invention, the leveling agent is quaternized (1,2- benzisothiazole-
3- ketone)-propine, structural formula isX is selected from any one of F, Cl, Br, I.
As a kind of preferred technical solution of the present invention, the leveling agent is quaternized (1,2- benzisothiazole-
3- ketone)-propine, structural formula isX is Cl.
As a kind of preferred technical solution of the present invention, quaternized (1,2-benzisothiazolin-3-one)-the third
The preparation method of alkynes, at least includes the following steps：
It takes (1,2-benzisothiazolin-3-one)-propine to be placed in reaction kettle, is slowly added to concentrated hydrochloric acid, methanol and ion
Liquid, (1,2-benzisothiazolin-3-one)-propine, concentrated hydrochloric acid, methanol and ionic liquid 1- ethyl-3-methylimidazole hydrochloric acid
The mass ratio of salt is 13：8：5：0.016, synthesis under normal pressure under nitrogen atmosphere, 3 hours reaction time are stirred at 55 DEG C；Reaction production
After object vacuum dried (drying temperature is controlled at 80 DEG C), it is added in autoclave, after purging reaction kettle three times with nitrogen,
Be added dimethyl carbonate and methanol, (1,2-benzisothiazolin-3-one)-propine, dimethyl carbonate, methanol mass ratio be
4.2：2.4：1, confined reaction, 175 DEG C, reaction pressure 1.7MPa of reaction temperature stirs lower reaction 12 hours；Reaction product is through true
Quaternized (1,2- benzisothiazole-3-ketones)-propine is made in sky dry (drying temperature is controlled at 80 DEG C) afterwards.
1- ethyl-3-methylimidazole hydrochlorides, CAS：65039-09-0 is purchased from Wuhu Hua Ren Science and Technology Ltd.s.
As a kind of preferred technical solution of the present invention, the raw material for preparing of the no cyanogen alkali copper electroplating composition further includes
Cyclodextrin.
Cyclodextrin
Cyclodextrin is one that amylose generates under the cyclodextrin glycosyltransferase effect generated by bacillus
The general name of series of annular oligosaccharide usually contains 6~12 D- glucopyranose units.Form each glucose unit of cyclodextrin
Cyclization is combined with 1,4- glycosidic bonds.Since the glycosidic bond of connection glucose unit cannot rotate freely, cyclodextrin is not cylinder
Shape molecule but the annulus tapered slightly.
As a kind of preferred technical solution of the present invention, the cyclodextrin is selected from alpha-cyclodextrin, beta-cyclodextrin, γ-ring
Any one of dextrin.
As a kind of preferred technical solution of the present invention, the temperature in use of the no cyanogen alkali copper electroplating composition is 30~
50℃。
As a kind of preferred technical solution of the present invention, the temperature in use of the no cyanogen alkali copper electroplating composition is 35~
45℃。
The second part of the present invention provides the preparation method without cyanogen alkali copper electroplating composition, include at least with
Lower step：
It takes 700mL deionized waters, is added citric acid, sodium potassium tartrate tetrahydrate, 1,2-cyclohexanediaminetetraacetic acid, after stirring and dissolving,
The salt that bivalent cupric ion is provided is added, 1h is stirred at 50~60 DEG C；Then potassium nitrate is added, stirring and dissolving uses potassium hydroxide
PH to 9.5~10.5 is adjusted with sodium bicarbonate；Then wetting agent, brightener, leveling agent is added, deionization is added in stirring and dissolving
Water is settled to 1L.
It is worth noting that, the superposition of single additive component effect and the effect not equal to additive package, sometimes very
Effect to one-component is opposite with multicomponent synergistic effect.Therefore the selection of each component is not in the additive of electro-coppering
Conventional selection, inventor is a large amount of it was found that, the change of some parameters and component can cause larger variation, even
Opposite has to make the creative labor as a result, to obtain suitably being formulated.
During completing the present invention, the present inventor is found surprisingly that use (1,2-benzisothiazolin-3-one)-the third
This leveling agent of alkynes can effectively increase the use temperature range of plating solution, and can improve binding force of cladding material, enhancing plating solution leveling
Property and stability.There is preferably leveling effect using quaternized (1,2- benzisothiazole-3-ketones)-propine.It is possible
The reason is that (1,2- benzisothiazole-3-ketones)-propine contain the big atomic energy of S, O, N isopolarity be complexed well cupric from
Son, the presence of the triple carbon-carbon bonds of reproducibility enhances the Surface flat of plating solution, while bivalent cupric ion being inhibited to be reduced into monovalence copper
Ion improves the stability of plating solution.S-N keys in quaternized (1,2-benzisothiazolin-3-one)-propine are weaker, when it
When being contacted with fungal cell, it is prone to be broken, to form S -- S with the protein of sulfur-bearing in recipient cell, destroy cell
Normal function, to make electroplating composition have extraordinary anti-mold effect.Quaternized (1,2- benzisothiazoles -3-
Ketone)-propine and potassium nitrate, wetting agent can act as hole sealing agent, and plating layer porosity is reduced, quality of coating is improved.
Present invention uses this complexing agents of 1,2- 1,2-diaminocyclohexane tetraacetic acids to assist chela of the citric acid to bivalent cupric ion
Cooperation is used, and can effectively improve electroplating velocity, and do not influence quality of coating.
The present invention is also added into cyclodextrin, and cyclodextrin can be stabilized under strongly alkaline conditions, and multiple hydroxyls thereon are
Excellent cationic binding site, to various metals ion all have it is good coordinating, also have hydrophobic cavity, cyclodextrin
Addition effectively enhance tolerance of the no cyanogen alkali copper electroplating composition to foreign metal ion, and cyclodextrin can be inhaled
The surface for being attached to stainless steel substrate inhibits the generation of displacement reaction, improves binding force of cladding material.
The present invention's contains micro chlorion without cyanogen alkali copper electroplating composition, in electroplating process, wetting agent energy and chlorine
Ion is completely covered on layers of copper surface by bridge linking effect, is hindered jointly with the other components of the no cyanogen alkali copper electroplating composition
The migration for hindering polluted by copper state atom or ion, is conducive to obtain that binding force is good, coating of brightening and leveling.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available.
Embodiment 1：
Embodiment 1 provides a kind of no cyanogen alkali copper electroplating composition, and 1L's prepares raw material without cyanogen alkali copper electroplating composition
Including：Bivalent cupric ion：15g；Citric acid：185g；Sodium potassium tartrate tetrahydrate：50g；Potassium nitrate：5g；1,2- 1,2-diaminocyclohexane tetraacetic acids：
0.5g；Wetting agent：0.2g；Brightener：1.2g；Leveling agent：0.1g；Deionized water adds to 1L.
The bivalent cupric ion is provided by basic copper carbonate；
The wetting agent is cetomacrogol 1000；
The brightener is 1,4- butynediols；
The leveling agent is (1,2- benzisothiazole-3-ketones)-propine.
The preparation method of (the 1,2-benzisothiazolin-3-one)-propine, at least includes the following steps：
A. o-amino thiophenol and urea are taken, is warming up to 160 DEG C, stirring stops reaction after 1 hour, and product will be obtained with hot water
It recrystallizes and obtains 1,2-benzisothiazolin-3-one twice, the molar ratio of the o-amino thiophenol and urea is 1：1.2；
B. it takes 1,2-benzisothiazolin-3-one dissolving in acetone, is slowly added to potassium carbonate, after stirring 20min, be added
3- propargyl chlorides are heated to reflux 4h, the 1,2-benzisothiazolin-3-one, the molar ratio of potassium carbonate, 3- propargyl chlorides and acetone
It is 1：1：1：3；Then mixture is cooled to 0 DEG C, pours into the mixture of ice and water of 100mL thereto, control temperature is stirred at 5 DEG C
Mix 1h；The precipitation generated is collected, is filtered with deionized water, it is that neutrality obtains (1,2-benzisothiazolin-3-one)-the third to be washed till pH
Alkynes.
O-amino thiophenol, CAS：137-07-5 is purchased from the joyful beauty bio tech ltd in Wuhan.
3- propargyl chlorides, CAS：624-65-7 is purchased from Sinopharm Chemical Reagent Co., Ltd..
The preparation method without cyanogen alkali copper electroplating composition, includes the following steps：
It takes 700mL deionized waters, is added citric acid, sodium potassium tartrate tetrahydrate, 1,2-cyclohexanediaminetetraacetic acid, after stirring and dissolving,
The salt that bivalent cupric ion is provided is added, 1h is stirred at 50 DEG C；Then potassium nitrate, stirring and dissolving, with potassium hydroxide and carbon is added
Sour hydrogen sodium adjusts pH to 10；Then wetting agent, brightener, leveling agent is added, stirring and dissolving is added deionized water and is settled to 1L.
Embodiment 2：
Embodiment 2 provides a kind of no cyanogen alkali copper electroplating composition, and 1L's prepares raw material without cyanogen alkali copper electroplating composition
Including：Bivalent cupric ion：17g；Citric acid：195g；Sodium potassium tartrate tetrahydrate：60g；Potassium nitrate：6.5g；1,2- cyclohexanediamine tetrems
Acid：1g；Wetting agent：0.3g；Brightener：1.6g；Leveling agent：0.15g；Deionized water adds to 1L.
The bivalent cupric ion is provided by copper citrate；
The wetting agent is myristyl betaine；
The brightener is thiocarbamide；
The leveling agent is (1,2- benzisothiazole-3-ketones)-propine.
The preparation method is the same as that of Example 1 for-propine for (the 1,2- benzisothiazole-3-ketones).
It is described that without cyanogen alkali copper electroplating composition, the preparation method is the same as that of Example 1.
Embodiment 3：
Embodiment 3 provides a kind of no cyanogen alkali copper electroplating composition, and 1L's prepares raw material without cyanogen alkali copper electroplating composition
Including：Bivalent cupric ion：16g；Citric acid：192g；Sodium potassium tartrate tetrahydrate：56g；Potassium nitrate：6g；1,2- 1,2-diaminocyclohexane tetraacetic acids：
0.6g；Wetting agent：0.25g；Brightener：1.5g；Leveling agent：0.12g；Deionized water adds to 1L.
The bivalent cupric ion is provided by cupric tartrate；
The wetting agent is dodecyl hydroxyl sulfo betaine；
The brightener is 2-mercaptobenzimidazole；
The leveling agent is (1,2- benzisothiazole-3-ketones)-propine.
The preparation method is the same as that of Example 1 for-propine for (the 1,2- benzisothiazole-3-ketones).
It is described that without cyanogen alkali copper electroplating composition, the preparation method is the same as that of Example 1.
Embodiment 4：
Embodiment 4 provides a kind of no cyanogen alkali copper electroplating composition, and 1L's prepares raw material without cyanogen alkali copper electroplating composition
Including：Bivalent cupric ion：16g；Citric acid：192g；Sodium potassium tartrate tetrahydrate：56g；Potassium nitrate：6g；1,2- 1,2-diaminocyclohexane tetraacetic acids：
0.6g；Wetting agent：0.25g；Brightener：1.5g；Leveling agent：0.12g；Deionized water adds to 1L.
The bivalent cupric ion is provided by basic copper carbonate；
The wetting agent is cetomacrogol 1000；
The brightener is selenium dioxide；
The leveling agent is quaternized (1,2- benzisothiazole-3-ketones)-propine.
The preparation method is the same as that of Example 1 for-propine for (the 1,2- benzisothiazole-3-ketones).
The preparation method of quaternized (the 1,2-benzisothiazolin-3-one)-propine includes at least following step
Suddenly：
It takes (1,2-benzisothiazolin-3-one)-propine to be placed in reaction kettle, is slowly added to concentrated hydrochloric acid, methanol and ion
Liquid, (1,2-benzisothiazolin-3-one)-propine, concentrated hydrochloric acid, methanol and ionic liquid 1- ethyl-3-methylimidazole hydrochloric acid
The mass ratio of salt is 13：8：5：0.016, synthesis under normal pressure under nitrogen atmosphere, 3 hours reaction time are stirred at 55 DEG C；Reaction production
After object vacuum dried (drying temperature is controlled at 80 DEG C), it is added in autoclave, after purging reaction kettle three times with nitrogen,
Be added dimethyl carbonate and methanol, (1,2-benzisothiazolin-3-one)-propine, dimethyl carbonate, methanol mass ratio be
4.2：2.4：1, confined reaction, 175 DEG C, reaction pressure 1.7MPa of reaction temperature stirs lower reaction 12 hours；Reaction product is through true
Quaternized (1,2- benzisothiazole-3-ketones)-propine is made in sky dry (drying temperature is controlled at 80 DEG C) afterwards.
1- ethyl-3-methylimidazole hydrochlorides, CAS：65039-09-0 is purchased from Wuhu Hua Ren Science and Technology Ltd.s.
It is described that without cyanogen alkali copper electroplating composition, the preparation method is the same as that of Example 1.
Embodiment 5：
Embodiment 5 provides a kind of no cyanogen alkali copper electroplating composition, and 1L's prepares raw material without cyanogen alkali copper electroplating composition
Including：Bivalent cupric ion：16g；Citric acid：192g；Sodium potassium tartrate tetrahydrate：56g；Potassium nitrate：6g；1,2- 1,2-diaminocyclohexane tetraacetic acids：
0.6g；Wetting agent：0.25g；Brightener：1.5g；Leveling agent：0.12g；Deionized water adds to 1L.
The bivalent cupric ion is provided by copper 8-quinolinolate；
The wetting agent is cetomacrogol 1000；
The brightener is selenium dioxide；
The leveling agent is quaternized (1,2- benzisothiazole-3-ketones)-propine.
The preparation method is the same as that of Example 1 for-propine for (the 1,2- benzisothiazole-3-ketones).
The preparation method of described quaternized (1,2- the benzisothiazole-3-ketones)-propine is the same as embodiment 4.
It is described that without cyanogen alkali copper electroplating composition, the preparation method is the same as that of Example 1.
Embodiment 6：
The specific implementation mode of embodiment 6 with embodiment 5, the difference is that, the no cyanogen alkali copper electroplating composition
The raw material for preparing further include cyclodextrin, the cyclodextrin is beta-cyclodextrin, and 1L's includes without cyanogen alkali copper electroplating composition
0.05g cyclodextrin.
Comparative example 1：
The specific implementation mode of comparative example 1 with embodiment 6, the difference is that, the no cyanogen alkali copper electroplating composition
Prepare raw material not include leveling agent.
Comparative example 2：
The specific implementation mode of comparative example 2 with embodiment 6, the difference is that, by (1, the 2- benzisothiazole
Quinoline -3- ketone)-propine (the 1,2- benzisothiazole-3-ketones) of quality and the mixture of propine chlorine such as is changed to.Comparative example 3：
The specific implementation mode of comparative example 3 with embodiment 6, the difference is that, by quaternized (1, the 2- benzo
Isothiazoline -3- ketone)-propine the mixing of (the 1,2- benzisothiazole-3-ketones), propine chlorine and hydrochloric acid of quality such as is changed to
Object.
Comparative example 4：
The specific implementation mode of comparative example 4 with embodiment 6, the difference is that, the no cyanogen alkali copper electroplating composition
Prepare raw material not include 1,2- 1,2-diaminocyclohexane tetraacetic acids.
Comparative example 5：
The specific implementation mode of comparative example 5 with embodiment 6, the difference is that, by quaternized (1, the 2- benzo
Isothiazoline -3- ketone)-propine the common mould inhibitor NaF of quality such as is changed to.
Performance evaluation：
The present invention carries out electroplating experiments using the Hulls 250mL slot, and cathode used is stainless steel plate, cathode size 100
×70×0.5mm3, anode used is phosphorous copper coin, and anode dimension is 100 × 70 × 5mm3.It is needed before plating stainless to cathode
Steel plate carries out pre-electroplating treatment, including derusting, ultrasonic oil removal, electrolytic degreasing, acid-wash activation, is both needed to use after the completion of each step
Deionized water rinses stainless steel plate, and fine cloth is used in combination to scrub stainless steel plate, cold wind drying, finally stainless by what is cleaned up
Interal fixation is electroplated in the slot of Hull.
Air is persistently blasted in electroplating process below cathode sample to be plated to be stirred.It powers off, takes out after plating
Cathode stainless steel plate, with a large amount of distilled water flushings, coating performance is tested in cold wind drying.All plating tests respectively 30~
It carries out at 50 DEG C, electroplating time 5min, current density 1.5A, is stirred using compressed air in test process.
1. binding force
The bond strength that binding force of cladding material refers to coating with matrix or intermediate deposit, the i.e. coating of per surface area are from matrix
Required power is removed on metal.As intermediate deposit, the quality of the bond strength of copper coating is directly related to final coating
Quality.So the binding force of copper coating is an important indicator of coating performance.
This experiment tests binding force of cladding material using bend test, and crooked experiment refers to being specimen holder after plating in bench vice
On, it bends repeatedly, until fracture, is qualification if coating phenomena such as peeling, fall off does not occur, is otherwise unqualified.
2. leveling ability
The leveling ability of plating solution refers to that coating fills and leads up the metal surface with micro-rough (roughness is less than 0.5mm)
Ability fills and leads up degree and depends on distribution of the coating on micro-rough metal surface.The present invention is using the test leveling of contourgraph method
Ability.With sandblasting or grinding wheel, sand paper polishing cathode stainless steel plate, surface roughness R is madeaFor 3 μm of test piece, place it in
In Hull slot equipped with plating solution, it is electroplated.The test piece after plating is measured with contourgraph, according to test piece table before and after plating
The respective change of surface roughness value calculates plating solution leveling ability, formulaIn formula, R is leveling ability,
RaFor strip mean roughness before plating, μm；R＇ aFor strip roughness after plating, μm.
3. bath stability
Citrate copper-plating electroplate liquid is prepared by Examples 1 to 6 and comparative example 1~5, places one at a constant temperature
Month, whether observation plating solution is muddy and whether has Signs of Mould.
1 performance characterization of table is tested
As can be seen from Table 1, carrying out plating without cyanogen alkali copper electroplating composition using the present invention can be in wider work
Temperature range can obtain the coating of binding force qualification, and plating solution leveling ability is excellent, stablizes.
Example above-mentioned is merely illustrative, some features for explaining the method for the invention.Appended right is wanted
The range as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible implementation
The explanation of the embodiment of the selection of the combination of example.Therefore, the purpose of applicant is that the attached claims are not illustrated this hair
The exemplary selectional restriction of bright feature.Some numberical ranges used also include sub- model in the claims
It encloses, the variation in these ranges should also be construed to be covered by the attached claims in the conceived case.
Claims (9)
1. a kind of no cyanogen alkali copper electroplating composition, which is characterized in that prepare raw material without cyanogen alkali copper electroplating composition described in 1L
Including：Bivalent cupric ion：15~17g；Citric acid：185~195g；Sodium potassium tartrate tetrahydrate：50~60g；Potassium nitrate：5~6.5g；1,
2- 1,2-diaminocyclohexane tetraacetic acids：0.5~1g；Wetting agent：0.2~0.3g；Brightener：1.2~1.6g；Leveling agent：0.1~0.15g；
Deionized water adds to 1L；The leveling agent is (1,2- benzisothiazole-3-ketones)-propine.
2. as described in claim 1 without cyanogen alkali copper electroplating composition, which is characterized in that the bivalent cupric ion is by alkali formula carbon
Sour copper, copper chloride, copper bromide, copper 8-quinolinolate, cupric ethylene diamine tetraacetate, copper citrate, copper sulphate, copper nitrate, copper acetate,
Any one of copper gluconate, cupric acetylacetonate, cupric tartrate, copper diethyl dithiocarbamate, cupric oxalate are more
Kind provides.
3. as described in claim 1 without cyanogen alkali copper electroplating composition, which is characterized in that the wetting agent is selected from polyethylene glycol
1000, Macrogol 4000, Macrogol 6000, PEG 8000, myristyl betaine, cetyl betaine, ten
Dialkyl group hydroxyl sulfo betaine any one or more of.
4. as described in claim 1 without cyanogen alkali copper electroplating composition, which is characterized in that the brightener is selected from titanium dioxide
Selenium, ethylenediamine tetra-acetic acid, 1,4- butynediols, methylene-disulfonic acid, thiocarbamide, potassium rhodanate, triethanolamine, Allyl thiourea,
Any one of 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, benzotriazole, polyethyleneimine, ethylhexyl sulfate
Or it is a variety of.
5. as described in claim 1 without cyanogen alkali copper electroplating composition, which is characterized in that the leveling agent is quaternized
(1,2-benzisothiazolin-3-one)-propine, structural formula areX appointing in F, Cl, Br, I
It is a kind of.
6. as described in claim 1 without cyanogen alkali copper electroplating composition, which is characterized in that the no cyanogen alkali copper electroplating composition
The raw material for preparing further include cyclodextrin.
7. as claimed in claim 6 without cyanogen alkali copper electroplating composition, which is characterized in that the cyclodextrin is selected from α-ring paste
Any one of essence, beta-cyclodextrin, gamma-cyclodextrin.
8. as described in claim 1 without cyanogen alkali copper electroplating composition, which is characterized in that its temperature in use is 30~50 DEG C.
9. such as preparation method of claim 1~8 any one of them without cyanogen alkali copper electroplating composition, which is characterized in that at least
Include the following steps：
It takes 700mL deionized waters, is added citric acid, sodium potassium tartrate tetrahydrate, 1,2-cyclohexanediaminetetraacetic acid, after stirring and dissolving, be added
The salt for providing bivalent cupric ion, 1h is stirred at 50~60 DEG C；Then potassium nitrate, stirring and dissolving, with potassium hydroxide and carbon is added
Sour hydrogen sodium adjusts pH to 9.5~10.5；Then wetting agent, brightener, leveling agent is added, it is fixed that deionized water is added in stirring and dissolving
Hold to 1L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710963412.9A CN107604393B (en) | 2017-10-17 | 2017-10-17 | A kind of no cyanogen alkali copper electroplating composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710963412.9A CN107604393B (en) | 2017-10-17 | 2017-10-17 | A kind of no cyanogen alkali copper electroplating composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107604393A CN107604393A (en) | 2018-01-19 |
| CN107604393B true CN107604393B (en) | 2018-07-13 |
Family
ID=61078492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710963412.9A Active CN107604393B (en) | 2017-10-17 | 2017-10-17 | A kind of no cyanogen alkali copper electroplating composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107604393B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109868492A (en) * | 2018-05-18 | 2019-06-11 | 临海市伟星电镀有限公司 | A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof |
| CN108677227A (en) * | 2018-08-27 | 2018-10-19 | 重庆立道新材料科技有限公司 | A kind of cyanide-free copper electroplating brightener and its electroplate liquid |
| CN109112509A (en) * | 2018-10-29 | 2019-01-01 | 重庆立道新材料科技有限公司 | A kind of high corrosion-resistant chemical nickel-plating liquid and preparation method thereof |
| CN109440144B (en) * | 2018-12-19 | 2021-10-12 | 长安大学 | Method for preparing conductive anticorrosive copper coating on aluminum alloy |
| CN109457272A (en) * | 2018-12-26 | 2019-03-12 | 深圳市祺鑫天正环保科技有限公司 | The stabilizer and electrolyte of alkali etching regeneration cathode copper |
| CN109825861A (en) * | 2019-03-18 | 2019-05-31 | 辽宁科技大学 | A kind of pure iron base basic plating copper coating technique |
| CN110306215B (en) * | 2019-07-30 | 2024-02-13 | 东光运城制版有限公司 | Nickel-removing and bottom-copper-changing plating solution and method for plate roller and production line |
| CN110484941A (en) * | 2019-08-29 | 2019-11-22 | 深圳市崇辉表面技术开发有限公司 | A kind of LED support electroplating solution and preparation method thereof |
| CN110424030B (en) * | 2019-08-30 | 2020-06-30 | 广州三孚新材料科技股份有限公司 | Cyanide-free alkaline copper electroplating solution, preparation thereof and application thereof in flexible printed circuit board |
| CN110438535A (en) * | 2019-09-03 | 2019-11-12 | 四川省蜀爱新材料有限公司 | A kind of plating solution for copper-plating used and its application method |
| CN111058065A (en) * | 2020-01-17 | 2020-04-24 | 浙江金欣新材料科技股份有限公司 | Composite electroplating brightener and preparation method thereof |
| CN113909605A (en) * | 2021-10-25 | 2022-01-11 | 北京嘉洁能科技股份有限公司 | Carbon fiber wire and metal wire connecting joint and connecting method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665962A (en) * | 2009-09-04 | 2010-03-10 | 厦门大学 | Alkaline non-cyanide plating solution for copper-plating used on iron and steel base and preparation method thereof |
| CN103469261A (en) * | 2013-09-16 | 2013-12-25 | 杭州和韵科技有限公司 | Cyanide-free silver plating solution additive |
| CN105154928A (en) * | 2015-09-07 | 2015-12-16 | 湖州方明环保科技有限公司 | Novel cyanide-free alkaline copper plating solution and preparation method thereof |
| CN106065486A (en) * | 2016-06-10 | 2016-11-02 | 太原工业学院 | A kind of non-cyanide copper electroplating compound additive and production technology thereof |
-
2017
- 2017-10-17 CN CN201710963412.9A patent/CN107604393B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665962A (en) * | 2009-09-04 | 2010-03-10 | 厦门大学 | Alkaline non-cyanide plating solution for copper-plating used on iron and steel base and preparation method thereof |
| CN103469261A (en) * | 2013-09-16 | 2013-12-25 | 杭州和韵科技有限公司 | Cyanide-free silver plating solution additive |
| CN105154928A (en) * | 2015-09-07 | 2015-12-16 | 湖州方明环保科技有限公司 | Novel cyanide-free alkaline copper plating solution and preparation method thereof |
| CN106065486A (en) * | 2016-06-10 | 2016-11-02 | 太原工业学院 | A kind of non-cyanide copper electroplating compound additive and production technology thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107604393A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107604393B (en) | A kind of no cyanogen alkali copper electroplating composition and preparation method thereof | |
| JP2859316B2 (en) | Platinum or platinum alloy electroplating bath and electroplating method | |
| Dimitrijević et al. | Non-cyanide electrolytes for gold plating–a review | |
| JP4832962B2 (en) | Improved gold alloy electrolyte | |
| Carbajal et al. | Electrochemical production and corrosion testing of amorphous Ni‐P | |
| Sharma et al. | Influence of current density on microstructure of pulse electrodeposited tin coatings | |
| TWI675129B (en) | Environmentally friendly nickel electroplating compositions and methods | |
| AT514818A1 (en) | Deposition of Cu, Sn, Zn coatings on metallic substrates | |
| Satpathy et al. | A comparative study of electrodeposition routes for obtaining silver coatings from a novel and environment-friendly thiosulphate-based cyanide-free electroplating bath | |
| TWI674341B (en) | Environmentally friendly nickel electroplating compositions and methods | |
| Christophe et al. | Cyanide-free silver electrochemical deposition on copper and nickel | |
| CA1129805A (en) | Electrodeposition of ruthenium-iridium alloy | |
| CN117071015A (en) | Forward and reverse pulse electrolytic silver alloy solution, preparation method, electroplating method and silver alloy coating | |
| Selvam | Electroless silver deposition on ABS plastic using Co (II) as reducing agent | |
| CN109023461A (en) | Form zinc-iron laminated coating of modulation | |
| Nineva et al. | Electrodeposition of Silver-Cobalt Coatings. Electrolytes. | |
| CN101392395B (en) | Environmental friendly chemical plating nickel plating brightener and use thereof | |
| CN108754553A (en) | Trivalent gold cyanogen-less gold plating solution based on the coordination of heterocycle Alkaloid and its application | |
| Qadr et al. | Nickel electrodeposition from deep eutectic solvents containing copper ions at a high temperature | |
| CN104611742A (en) | Cr-Ni alloy plating solution and electroplate method | |
| Kamel et al. | Brass Alloy Coatings Electrodeposited from an Environmentally Friendly Alkaline Lactate Bath under Different Operating Conditions | |
| TW546418B (en) | Method of producing AuCuGa alloy coating using electrolysis, and alloys produced by such a method | |
| JPS6029483A (en) | Pure gold plating liquid | |
| Sharma et al. | Effect of current density and alkaline pH on morphology and properties of electroplated Sn | |
| JP2009280867A (en) | Electrolytic alloy plating solution, and plating method using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |