CN108754553B - Trivalent gold cyanogen-less gold plating solution and its application based on the coordination of heterocycle Alkaloid - Google Patents
Trivalent gold cyanogen-less gold plating solution and its application based on the coordination of heterocycle Alkaloid Download PDFInfo
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- CN108754553B CN108754553B CN201810672828.XA CN201810672828A CN108754553B CN 108754553 B CN108754553 B CN 108754553B CN 201810672828 A CN201810672828 A CN 201810672828A CN 108754553 B CN108754553 B CN 108754553B
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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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
Abstract
The invention discloses the trivalent gold cyanogen-less gold plating solution being coordinated based on heterocycle Alkaloid and its application, electroplate liquid includes trivalent gold salt, complexant, pH buffer, mould inhibitor and additive.Wherein, to provide auric gold chloride as main salt, using heterocycle Alkaloid as complexant, using Anhydrous potassium carbonate and dipotassium hydrogen phosphate trihydrate mixture as pH buffer, using sodium tetraborate or sodium benzoate or formaldehyde as mould inhibitor, using the organic matter of sulfur-bearing as additive.Cyanogen-less gold liquid gold salt convenient sources of the invention, comprehensive performance are prominent；Plating solution has preferable covering power；Anti- diadochy is strong, and fresh plating nickel sheet, which is placed in 3min in plating solution, will not occur replacing layer gold phenomenon；In 0.1~1.2A/dm2Under broad current density, obtained Gold plated Layer with nickel, copper substrate caking power is good, brightness is high and color is uniformly golden yellow；In addition, also having plating solution preparation simple, craft of gilding facilitates controllable feature.
Description
Technical field
The present invention is cyanide-free gold electroplating technical field, and in particular to the trivalent gold non-cyanide plating based on the coordination of heterocycle Alkaloid
Gold plating bath and its application.
Background technique
Electroplating gold is widely used in electric appliance, connector, printed circuit board, integrated circuit and furnishing fields.
The common oxidation state of gold is trivalent and monovalence.In trivalent gold reduction process, obtaining two electron reductions first is one
Valence gold, then obtaining an electron reduction is elemental gold.Simply, the tervalence gold ion reduction overpotential without coordination is smaller, gained gold
Sedimentary particle is more coarse and may cause aurous be mingled with.In the aqueous solution without complexant, monovalence gold is easy to
Disproportionated reaction occurs, becomes trivalent gold and elemental gold, it is difficult to be stabilized.
In cyanide gold plating solution, cyanide ion and monovalence gold ion stablize coordination, thus bath stability and coating matter
It measures excellent.Cyanide severe toxicity.No cyanogen monovalence gold gold plating liquid main salt is mostly used gold sodium sulfide solution.Gold sodium sulfide solution is not only steady
It is qualitative poor, it is usually only capable of maintaining to save six months, and gold sodium sulfide sells drug without commodity solid-state, needs voluntarily to make
It is standby.In addition, gold plate is easily mingled with sulphur and stress increases and embrittlement when plating solution sulfite na concn is cumulative too high.
Tervalence gold ion has higher positive charge, combines with the containing N, O, S ligands of lone pair electrons is capable of providing
Together.Due to the addition of complexant, golden reduction overpotential is improved, and can obtain more careful gold plate.
Chinese patent (105420771 A of CN) discloses a kind of using cysteine as golden main ligand, 2- thio -5,
5- dimethyl hydantoin, triethylamine, citric acid, inositol etc. are electroplated as the monovalence gold cyanogen-less gold of auxiliary complexant
Liquid improves the stability of plating solution to a certain extent.In existing research, using cysteine as the non-cyanide plating metal working of complexant
Skill forms stronger coordinate bond between cysteine and monovalence gold, can obtain certain thickness coating.But above-mentioned non-cyanide plating
Gold process is that monovalence gold is gold-plated, and the main salt being added remains as and needs homemade gold sodium sulfide solution.
Chinese patent (105112953 A of CN) discloses a kind of using gold sodium sulfide as main salt, potassium sulfite, burnt sulfurous
One of sour sodium, sodium dithionite, sodium thiosulfate and potassium thiosulfate are a variety of as main complexant, and ethylenediamine has
Machine phosphonic acid, pyridine, pyridine-3-sulphonic acid, aminopyridine, quinoline woods, quinolinic acid, quinoline -2- sulfonic acid, oxyquinoline, three second of ethylenediamine
One of acid, ethylenediamine diacetic acid, nitro triacetic acid and iminodiacetic acid or a variety of non-cyanide platings as auxiliary complexing agent
Golden liquid.Chinese patent (105316718 A of CN) discloses one kind with sulphite for main complexant, with the third sulphur of alkali metal sulfydryl
Hydrochlorate is the pulse plating liquid and electro-plating method of the sulphite cyanogen-less gold of auxiliary complexing agent.Chinese patent (CN
105937028 A) disclose a kind of using gold sodium sulfide as main salt, sodium sulfocyanate, thiosemicarbazides, ethylene thiourea, 2- amino-
5- sulfydryl -1,3, one of 4 thiazoles, 6-MP or any two or more as soft base class complexant, potassium pyrophosphate, trimerization
Cyanamide, sulfamate, iminodiacetic acid, glycine, tetren, uridine, caffeine, ammonium citrate, tartaric acid
One of or a kind of any two or more compounding cyanogen-less gold liquid and preparation method thereof as non-soft base class complexant.It is above-mentioned
In monovalence gold cyanogen-less gold technique, sulfur-bearing in main salt or complexant, and it is larger using total amount, obtained coating is easily mingled with sulphur and may
It can embrittlement.
Further, since monovalence gold stability is insufficient, there is research using gold chloride as main salt source, hypoxanthine is complexant,
Polyethyleneimine is the cyanogen-less gold system of additive, although improving electroplate liquid stability, system pH is higher, easily causes
The corrosion of electroplating device.
In short, cyanogen-less gold technique or electroplate liquid stability deficiency or plating conditions harshness or quality of coating at this stage
Not high, corrosive equipment haves the defects that not to be able to satisfy plating processing needs.Therefore, it is prominent to invent a kind of comprehensive performance
Trivalent gold cyanogen-less gold technique have great practical significance.
Summary of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, provide three based on the coordination of heterocycle Alkaloid
Valence gold cyanogen-less gold plating solution and its application solve the problems in above-mentioned background technique.
The technical solution adopted by the present invention to solve the technical problems is: the trivalent gold nothing based on the coordination of heterocycle Alkaloid
Cyanogen gold plating solution, including trivalent gold salt, complexant, pH buffer, mould inhibitor and additive；
The trivalent gold salt is to contain auric gold chloride；
The complexant includes the first complexant and the second complexant, and first complexant and the second complexant are with quality
Than the ratio mixing for 2~4:1；First complexant includes theobromine, aminophylline, theophylline and its alkali metal salt, in ammonium salt
At least one, second complexant includes that caffeine, 8-anaguanine, xanthine, 2,6- diaminopurine, sulphur bird are fast
At least one of purine, 6-benzyl aminopurine and its alkali metal salt, ammonium salt；
The pH buffer is the mixture of Anhydrous potassium carbonate and dipotassium hydrogen phosphate trihydrate, the Anhydrous potassium carbonate and three
Hypophosphite monohydrate hydrogen dipotassium is mixed with mass ratio for the ratio of 1:3~6；
The mould inhibitor includes one of sodium tetraborate, sodium benzoate, formaldehyde；
The additive includes the first additive and Second addition, and first additive includes pyridine-3-sulphonic acid, 3-
One of mercaptopropionic acid, the Second addition include methionine, thiophene carboxylic acid, dimercaptosuccinic acid, in taurine at least
The mass ratio of one kind, first additive and Second addition is 1~3:1.
In a preferred embodiment of the present invention, mass concentration of the trivalent gold salt in electroplate liquid be 1~8.4g/L, three
The mass concentration of valence gold ion is 0.5~4g/L.
In a preferred embodiment of the present invention, the mass concentration of the complexant is 2~55g/L, with trivalent gold salt concentration
Molar ratio be 4.5~15:1.
In a preferred embodiment of the present invention, the mass concentration of the pH buffer is 20~110g/L.
In a preferred embodiment of the present invention, the mould inhibitor is one of sodium benzoate or formaldehyde, mass concentration
For 0.5~5.5g/L.
In a preferred embodiment of the present invention, the mould inhibitor is sodium tetraborate, and mass concentration is 25~65g/L.
It further include for adjusting the hydrochloric acid of bath pH values, hydroxide in a preferred embodiment of the present invention, in electroplate liquid
Potassium, the bath pH values are 8.4~12.1.
The present invention also provides electro-plating methods, and using such as above-mentioned electroplate liquid, electroplating technological parameter includes current density 0.1
~1.2A/dm2, bath pH value is 8.4~12.1, and bath temperature is 30~70 DEG C, and thickness of coating is 0.1~0.6 μm, and anode is
Platinum plating titanium net, plating solution stirring or circulating filtration when plating.
In a preferred embodiment of the present invention, the pH of electroplate liquid is adjusted with 20% hydrochloric acid or 20% potassium hydroxide aqueous solution
Value.
In a preferred embodiment of the present invention, bath temperature is 35~60 DEG C.
Compared to monovalence gold ion, auric advantage is selected to be: electroplate liquid, will not during prolonged use
Rotten, tervalence gold ion can be stabilized.By Density function theory it is found that under aqueous conditions, trivalent gold with match
Body combines the gross energy of complex generated far below the gross energy of complex made of monovalence gold and ligand binding, and energy is got over
It is low more stable.
Currently, in the market for the main salt of monovalence gold cyanideless electro-plating liquid, from the homemade gold sodium sulfide solution of needs.
During storage, sulphite inevitably contacts with air and aoxidizes or decompose, and causes solution rotten.In addition, preparing sulfurous acid
Golden sodium process exception is cumbersome, easily causes the loss of gold salt.And trivalent gold salt gold chloride property is stable, can directly purchase.
Heterocycle Alkaloid complexant has heteroaromatic structures, and N atomic electronegativity therein is big, and has exposed orphan
It to electronics, can not only be coordinated with trivalent gold, and adsorbable in cathode surface, the auric electroreduction of resistanceization improves trivalent gold
Cathodic reduction overpotential, to refine coating crystal grain and improve quality of coating.When heterocycle Alkaloid complexant mass concentration is low
When 2g/L, easily there is gold hydroxide precipitating in plating solution；When mass concentration is higher than 55g/L, cathode hydrogen evolution reaction aggravation.
The addition of Anhydrous potassium carbonate and dipotassium hydrogen phosphate (three water) mixture enables to pH value steady during electroplating gold
8.4~12.1 are scheduled on, pH value is excessively high, perishable plating instrument and equipment；PH value is too low, and heterocycle Alkaloid can analyse in the solution
Out.
Since heterocycle Alkaloid is organic matter, standing is easily mouldy for a long time for electroplate liquid, can obviously change after mould inhibitor is added
It is kind, and will not influence quality of coating.Sodium tetraborate not only has mildew-proof function, it may have pH buffer function.
Additive can be adsorbed in cathode surface, as electron bridge, be coordinated with trivalent gold, and then induce the reduction of trivalent gold heavy
Product.In addition, additive can also make coating bright, crystal grain is finer and close.
Current density is lower than 0.1A/dm2, coating brightness is low and deposition velocity is slow, and current density is higher than 1.2A/dm2, lead
Coating is caused to burn；Temperature is lower than 35 DEG C, and nucleation rate is slower, and coating brightness is low, and temperature is higher than 60 DEG C, and heterocycle Alkaloid is easy
It decomposes.
The technical program compared with the background art, it has the following advantages:
1. electroplate liquid convenient sources of the present invention, comprehensive performance are prominent, there is preferable covering power, is suitble to thin gold plating, it is thick
Degree is 0.1~0.6 μm；Anti- diadochy is strong, and fresh plating nickel sheet, which is placed in 3min in plating solution, will not occur replacing layer gold phenomenon；
2. heterocycle Alkaloid and tervalence gold ion are coordinated, in conjunction with the pH buffer of specific composition and content, mould inhibitor and
Additive ensure that electroplate liquid is environmentally protective and stability；
3. in 0.1~1.2A/dm2Under broad current density, obtained Gold plated Layer and nickel, copper substrate caking power are good, bright
Degree is high and color is uniformly golden yellow；
4. trivalent gold salt can be purchased directly, electroplate liquid preparation is simple, craft of gilding convenience, controllable feature.
Detailed description of the invention
Fig. 1 is the SEM shape appearance figure (10000 times of amplification) of 1 coating of the embodiment of the present invention；
The EDS spectrogram and element of 1 coating of Fig. 2 embodiment of the present invention form.
Specific embodiment
The present invention is based on heterocycle Alkaloid coordination trivalent gold cyanogen-less gold plating solution, including trivalent gold salt, complexant,
PH buffer, mould inhibitor and additive；It further include for adjusting the hydrochloric acid of bath pH values, potassium hydroxide, the electroplate liquid pH
Value is 8.4~12.1.
The trivalent gold salt is to contain auric gold chloride；Mass concentration of the gold chloride in electroplate liquid be 1~
8.4g/L, the mass concentration of tervalence gold ion are 0.5~4g/L.
The complexant is heterocycle Alkaloid complexant, including the first complexant and the second complexant, and described first matches
Position agent and the second complexant are mixed with the ratio that mass ratio is 2~4:1；The mass concentration of the complexant is 2~55g/L, with
The molar ratio of trivalent gold salt concentration is 4.5~15:1.First complexant includes theobromine, aminophylline, theophylline and its alkali gold
Belong to salt, at least one of ammonium salt, second complexant includes that caffeine, 8-anaguanine, xanthine, 2,6- diamino are fast
At least one of purine, thioguanine, 6-benzyl aminopurine and its alkali metal salt, ammonium salt；
The pH buffer is the mixture of Anhydrous potassium carbonate and dipotassium hydrogen phosphate trihydrate, the Anhydrous potassium carbonate and three
Hypophosphite monohydrate hydrogen dipotassium is mixed with mass ratio for the ratio of 1:3~6；The mass concentration of the pH buffer is 20~110g/L.
The mould inhibitor includes one of sodium tetraborate, sodium benzoate, formaldehyde；One in selection sodium benzoate or formaldehyde
When kind, mass concentration is 0.5~5.5g/L；When selecting sodium tetraborate, mass concentration is 25~65g/L, and sodium tetraborate is not
Only there is mildew-proof function, it may have pH buffer function.
The additive includes the first additive and Second addition, and first additive includes pyridine-3-sulphonic acid, 3-
One of mercaptopropionic acid, the Second addition include methionine, thiophene carboxylic acid, dimercaptosuccinic acid, in taurine at least
The mass ratio of one kind, first additive and Second addition is 1~3:1.
The specific process for preparation of electroplate liquid of the present invention is (for preparing 1000mL):
1. precise quality is the heterocycle Alkaloid complexant of 2~55g, 20% potassium hydroxide aqueous solution is added,
Stirring, dissolution；
2. 1~8.4g of gold chloride containing tervalence gold ion, stirring and dissolving is added to 1. middle, and supplement deionized water extremely
500ml；
3. precise gross mass is the pH buffer of 20~110g, it is added in 1., and adjust pH value 8.4~12.1
In range；
4. mould inhibitor sodium benzoate or 25~65g of 0.5~5.5g of formaldehyde or sodium tetraborate is added to 1. middle, and stir
It is uniformly dissolved；
5. to 25~830mg of additive is continuously added in 1., and stirring and dissolving is uniform；
6. be 20% hydrochloric acid with volumetric concentration or mass concentration be 20% potassium hydroxide aqueous solution adjust pH value 8.4~
In 12.1 ranges, appropriate amount of deionized water is added to 1000ml.
Electro-plating method of the invention, using above-mentioned electroplate liquid, electroplating technological parameter includes 0.1~1.2A/ of current density
dm2, bath pH value is 8.4~12.1, and bath temperature is 30~70 DEG C, and thickness of coating is 0.1~0.6 μm, and anode is platinized titanium
Net, plating solution stirring or circulating filtration when plating.The pH value of electroplate liquid is adjusted with 20% hydrochloric acid or 20% potassium hydroxide aqueous solution.
Using copper sheet as base material, process flow are as follows: ultrasonic oil removal (50~70 DEG C, 3~5min of time) → washing
→ pickling (dilute sulfuric acid of mass concentration 5%, 20~40s) → washing → deionization washing → electronickelling → washing → deionized water
Wash → electroplating gold.
Using electroplate liquid of the present invention and aforesaid operations condition, using platinum plating titanium net as anode, nickel plating copper sheet is cathode,
Plating solution stirs when plating, and three kinds of different electroplate liquid compositions and electroplating technological parameter are respectively adopted, can obtain ideal Gold plated Layer,
Specific implementation condition and the performance for obtaining coating are as shown in the table:
1 different component electroplate liquid of table and its electroplating effect (electroplate liquid 1000mL)
The appearance color of method observation gold plate by visual observation, coating is lemon yellow in technique allowed band；Thickness of coating
It is obtained by X-Ray calibrator；By scanning electron microscope (SEM), the microscopic appearance of coating is observed.
Skilled person will appreciate that when technical parameter of the invention changes in the following range, it is contemplated that obtain
Same as the previously described embodiments or similar technical effect: when substrate is using clean copper, corronil, clean copper electroplating layer,
Electroless nickel layer, or when clean chemical plating copper layer, chemical Ni-plating layer, obtained result is identical as above-described embodiment result.
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to
Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.
Claims (9)
1. the trivalent gold cyanogen-less gold plating solution based on the coordination of heterocycle Alkaloid, it is characterised in that: including trivalent gold salt, coordination
Agent, pH buffer, mould inhibitor and additive；
The trivalent gold salt is to contain auric gold chloride；
The complexant includes the first complexant and the second complexant, and first complexant and the second complexant are with mass ratio
The ratio of 2~4:1 mixes；First complexant include theobromine, aminophylline, theophylline and its alkali metal salt, in ammonium salt extremely
Few one kind, second complexant includes caffeine, 8-anaguanine, xanthine, 2,6- diaminopurine, thioguanine, 6-
At least one of benayl aminopurine and its alkali metal salt, ammonium salt；The mass concentration of the complexant is 2~55g/L, with trivalent
The molar ratio of gold salt concentration is 4.5~15:1；
The pH buffer is the mixture of Anhydrous potassium carbonate and dipotassium hydrogen phosphate trihydrate, the Anhydrous potassium carbonate and three hydrations
Dipotassium hydrogen phosphate is mixed with mass ratio for the ratio of 1:3~6；
The mould inhibitor includes one of sodium tetraborate, sodium benzoate, formaldehyde；
The additive includes the first additive and Second addition, and first additive includes pyridine-3-sulphonic acid, 3- sulfydryl
One of propionic acid, the Second addition include at least one of methionine, thiophene carboxylic acid, dimercaptosuccinic acid, taurine,
The mass ratio of first additive and Second addition is 1~3:1.
2. the trivalent gold cyanogen-less gold plating solution according to claim 1 based on the coordination of heterocycle Alkaloid, feature exist
In: mass concentration of the trivalent gold salt in electroplate liquid is 1~8.4g/L, and the mass concentration of tervalence gold ion is 0.5~4g/
L。
3. the trivalent gold cyanogen-less gold plating solution according to claim 1 based on the coordination of heterocycle Alkaloid, feature exist
In: the mass concentration of the pH buffer is 20~110g/L.
4. the trivalent gold cyanogen-less gold plating solution according to claim 1 based on the coordination of heterocycle Alkaloid, feature exist
In: the mould inhibitor is one of sodium benzoate or formaldehyde, and mass concentration is 0.5~5.5g/L.
5. the trivalent gold cyanogen-less gold plating solution according to claim 1 based on the coordination of heterocycle Alkaloid, feature exist
In: the mould inhibitor is sodium tetraborate, and mass concentration is 25~65g/L.
6. the trivalent gold cyanogen-less gold plating solution according to claim 1 based on the coordination of heterocycle Alkaloid, feature exist
In: it further include for adjusting the hydrochloric acid of bath pH values, potassium hydroxide, the bath pH values are 8.4~12.1.
7. electro-plating method, it is characterised in that: use electroplate liquid as described in any one of claims 1 to 6, electroplating technological parameter packet
Include 0.1~1.2A/dm of current density2, bath pH value be 8.4~9.7, bath temperature be 30~70 DEG C, thickness of coating be 0.1~
0.6 μm, anode is platinum plating titanium net, plating solution stirring or circulating filtration when plating.
8. electro-plating method according to claim 7, it is characterised in that: with 20% hydrochloric acid or 20% potassium hydroxide aqueous solution tune
The pH value of economize on electricity plating solution.
9. electro-plating method according to claim 7, it is characterised in that: bath temperature is 35~60 DEG C.
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