CN1247822C - Non-aqueous solvent cyanogens-free gold plating solution - Google Patents

Non-aqueous solvent cyanogens-free gold plating solution Download PDF

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Publication number
CN1247822C
CN1247822C CN 200310106231 CN200310106231A CN1247822C CN 1247822 C CN1247822 C CN 1247822C CN 200310106231 CN200310106231 CN 200310106231 CN 200310106231 A CN200310106231 A CN 200310106231A CN 1247822 C CN1247822 C CN 1247822C
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China
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gold
aqueous solvent
plating
gold plating
concentration
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CN 200310106231
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CN1542167A (en
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顾建胜
王海霞
童剑英
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Suzhou University
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Suzhou University
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Abstract

The present invention relates to a non-aqueous solvent cyanogen-free gold plating solution which is prepared from the following ingredients of non-aqueous solvents, gold sources and supporting electrolytes. The present invention is characterized in that the non-aqueous solvents are at least one of DMSO, DMF and PC; the gold sources are at least one of AuPPh3X, wherein X represents Cl, Br, I or acac; the supporting electrolytes are inorganic or organic aminium salts which can be dissolved in the non-aqueous solvents; the inorganic aminium salts are NH4X, wherein X represents Cl, Br or I; the organic aminium salts are R4NX, R represents C2H5 or n-C4H9, and X represents Cl, Br or I. The present invention has the characteristics that gold plating liquids belong to environmental protection type plating liquids with small toxicity, and the use of the gold plating liquids is favorable for human bodies' health and environment protection; the non-aqueous solvents are adopted to be used as solvents, the best advantage of enlarging the gold sources is obtained, and more raw materials which comprise gold compounds can be used for plating gold; when the gold plating liquids are adopted, spherical crystal plating structures with favorable properties can be obtained.

Description

Non-aqueous solvent cyanogen-less gold liquid
Technical field
The present invention relates to a kind of gold plating liquid, particularly a kind of cyanogen-less gold liquid of non-aqueous solvent, this gold plating liquid toxicity is very little, and contained golden source concentration is higher, need not additive, no liberation of hydrogen effect, and also coating is the spheroidal with premium properties.
Background technology
Gold is the most corrosion-resistant in metal plating, and conduction, thermal conductivity is good, high temperature resistant, therefore use at aspects such as printed circuit board, integrated circuit, shell, electric contacts in recent years increase very fast.Gold-plated is matrix with Cu, Ni metal usually, adopts electrolysis process to electroplate in gold plating liquid.Modern age, gold-plated technology was mainly used the prussiate plating bath, and wherein solvent is a water, and the fatal shortcoming of this gold plating liquid is a hypertoxicity, not only had been harmful to HUMAN HEALTH but also contaminate environment.Concerning electronic industry, need to carry out selective electroplating, and prussiate has Degradation to it, easily makes its cracking or dissolving with photo-resist; In addition, be difficult to obtain spheroidal coating during plating.The non-prussiate plating bath that adopts, is very limited in the application because of stability is not high as sulfurous acid gold salt at present.Usually make water as the plating solvent, but Jin Yuan that can be water-soluble seldom, also easily produce the liberation of hydrogen effect sometimes, than the difficult gold plate that obtains spheroidal.The bibliographical information of relevant non-aqueous solvent gold plating liquid is less, and is representative, and the one, the Japanology paper of nineteen ninety-five (" Hyomen Gijutsu ", 46 (12), 1182-4 (Japanese) 1995); Two is Japanese Patent JP09031681 (spy opens flat 9-31681, open day on February 4th, 1997) in 1997, though both adopt non-aqueous solvent system, but still carries out the plating of gold with the cyaniding plating bath of severe toxicity and the chlor(o)aurate plating bath of less stable.
For this reason, the invention provides a kind of non-aqueous solvent cyanogen-less gold liquid technical scheme, this scheme use non-aqueous solvent and be simple and easy to, the non-cyanogen gold-containing compound electroplate liquid of good stability, can obtain the gold plate of spheroidal after the plating.
Summary of the invention
For achieving the above object, the technical solution used in the present invention is: a kind of non-aqueous solvent cyanogen-less gold liquid, and its component comprises non-aqueous solvent, Jin Yuan, supporting electrolyte, wherein:
Non-aqueous solvent is at least a among DMSO, DMF, the PC;
Jin Yuan is AuPPh 3At least a among the X, wherein X=Cl, Br, I, acac;
Supporting electrolyte is the inorganic or organic ammonium salt that dissolves in non-aqueous solvent, and inorganic ammonium salt is NH 4X, wherein X=Cl, Br, I; Organic ammonium salt is R 4NX, wherein 4 R groups are at C 2H 5, n-C 4H 9Choose any one kind of them X=Cl, Br, I in two kinds of groups.
Related content and change interpretation are as follows in the technique scheme:
1, the Chinese name of such scheme organic solvent is respectively:
The DMSO dimethyl sulfoxide (DMSO)
DMF N, dinethylformamide
The PC propylene carbonate
2, " Jin Yuan " described in the such scheme is meant the source of gold, refers to specifically among the present invention that chemical formula is AuPPh 3The gold-containing compound that X is represented.AuPPh 3X among the X represents negative ion.The following four kinds of gold-containing compounds of concrete expression:
(1), AuPPh 3Cl chlorinated triphenyl base phosphine alloy (I)
(2), AuPPh 3Br bromination triphenylphosphine alloy (I)
(3), AuPPh 3I iodate triphenylphosphine alloy (I)
(4), AuPPh 3(acac) methyl ethyl diketone triphenylphosphine alloy (I)
Wherein the chemical formula of acac is
3, the inorganic or organic ammonium salt of such scheme select generally speaking with gold-containing compound in the corresponding ammonium salt of negative ion element, can certainly select not corresponding chemical element ammonium salt, as long as it is within above-mentioned scope.
4, the notion of " at least a " described in the such scheme comprise selection wherein a kind of, select wherein two kinds, until full choosing.Here can produce the combination of Dan Xuan and various multiselects.Wherein the scheme of Dan Xuan is more commonly used, and specifically: non-aqueous solvent is a kind of among DMSO, DMF, the PC; Jin Yuan is AuPPh 3A kind of among the X, wherein X=Cl, Br, I, acac; Inorganic or organic ammonium salt also is wherein a kind of.
5, best group becomes in the such scheme: non-aqueous solvent is DMSO; Jin Yuan is AuPPh 3Cl; Supporting electrolyte is NH 4Cl.
6, Jin Yuan and the supporting electrolyte concentration in non-aqueous solvent is respectively in the such scheme:
Maximum range: golden source concentration is 0.005mol/l～saturation concentration, and supporting electrolyte concentration is 0.05mol/l～saturation concentration.
Better scope: golden source concentration is 0.008mol/l～0.03mol/l, and supporting electrolyte concentration is 0.1mol/l～0.3mol/l.
7, explain about the relativity of concentration
For gold plating liquid of the present invention, the concentration of Jin Yuan and supporting electrolyte is influential to gold plating quality, but this influence is along with temperature and gold-plated strength of current change and changes, therefore the concentration of this programme proposition limits and has relativity, the general electroplating temperature condition that adopts 30～70 ℃, strength of current can be with reference to embodiment.
8, the solvent of the present invention's use is all higher to golden source solubleness, and four kinds of gold-containing compounds or its mixing all can be used.The use continuous current is electroplated.Current density is about 0.01A/dm 2～0.2A/dm 2, bath temperature was switched on 1～3 hour about 30～70 ℃, and coating is by the light brown golden yellow that changes into gradually.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1, gold plating liquid toxicity of the present invention is very little, belongs to a kind of environment-friendly type gold plating liquid comparatively speaking, and it is very favourable to HUMAN HEALTH and environment protection to promote the use of this gold plating liquid.
2, the present invention will be originally changes the gold plating liquid of non-aqueous solvent with water into as the gold plating liquid of solvent, and its maximum benefit is to have enlarged Jin Yuan, has more gold-containing compound raw material can be used for gold-plated.
3, the present invention adopts specific DMSO, DMF, PC as non-aqueous solvent, its characteristics: (1), boiling point height; (2), good conductivity; (3), polarity is big, the solute easily ionizable; (4), self be difficult to by electrolysis; (5), the solubleness of each gold-containing compound is bigger in this programme.As when 30 ℃ of the temperature, gold-containing compound solubleness in DMF can reach 40g/l.
4, gold plating liquid of the present invention can reach the gold-plated effect of prussiate gold plating liquid routine in the past, and better effects if on some single index is a spheroidal such as electroplating its Gold plated Layer of back employing ultramicroscopic observation, and mostly is wire greatly in the past.
5, the performance test of coating of the present invention
(1), outward appearance: coating gloss, golden yellow is not peeled, and is non-foaming.
(2), stereoscan photograph
Can find out that from Fig. 1～Fig. 4 coating is spheroidal and distributes.
(3), combining power test
A, use the file cut on coating, coating can not be provoked, and does not peel off;
B, apart from coating 1.6mm with interior punching, coating does not ftracture around the hole;
C, grip coating facing to coarse wheel, make emery wheel be cut to coating in the dancing mode from matrix metal, non-scale does not come off;
(4), porosity:
With the nitric acid vapor test, spot just appears in coating surface after about 1 hour.
(5), simulation salt mist experiment:
Soaked 48 hours in 5% NaCl solution, coating does not corrode.
Description of drawings
Accompanying drawing 1～accompanying drawing 4 is four gold-plated stereoscan photographs of gold plating liquid of the present invention, and coating is spheroidal and distributes, and plating bath consists of: non-aqueous solvent---DMSO (dimethyl sulfoxide (DMSO)); Jin Yuan---AuPPh 3Cl (chlorinated triphenyl base phosphine alloy (I)); Supporting electrolyte---NH 4Cl (ammonium chloride).
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one:
(1), the copper sheet of research electrode: 12mm * 14mm, purity 99.5%, with 500 #, 800 #, 1200 #The import abrasive paper for metallograph grinds off the copper surface film oxide successively, and polishing on the sharpening machine that the fine, soft fur felt-cloth is housed, alkali cleaning, pickling, distillation are washed, dried up.
(2), counter electrode: 10mm * 12mm, purity 99.9% gold plaque.
(3), reference electrode; Saturated Ag/AgCl electrode.
(4), solvent DMSO, Jin Yuan AuPPh 3Cl, supporting electrolyte NH 4Cl.Plating bath is formed and concentration is:
Form peak concentration scope optimum concentration range optimum concn
(mol/l) (mol/l) (mol/l)
DMSO
AuPPh 3Cl 0.005～0.04 0.008～0.03 0.015
NH 4Cl 0.05～0.3 0.1～0.3 0.2
Add AuPPh among the 20ml DMSO 3Cl, NH 4Cl stirs to above-mentioned concentration range, and current density is 0.01A/dm 2～0.2A/dm 2, 60～70 ℃ of bath temperatures, 1～3 hour conduction time.Thickness of coating can reach a few μ m, and coating is spheroidal and distributes.
Embodiment two:
Press embodiment one sample thief electrode, solvent DMSO, Jin Yuan AuPPh 3Br, supporting electrolyte NH 4Br, coating gloss, golden yellow.
Plating bath is formed and concentration is:
Form peak concentration scope optimum concentration range optimum concn
(mol/l) (mol/l) (mol/l)
DMSO
AuPPh 3Br 0.005～0.04 0.008～0.03 0.015
NH 4Br 0.05～2.0 0.1～0.5 0.2
Embodiment three:
Press the plating condition of embodiment one, solvent DMSO, Jin Yuan AuPPh 3I, supporting electrolyte NH 4I, coating gloss, golden yellow.
Plating bath is formed and concentration is:
Form peak concentration scope optimum concentration range optimum concn
(mol/l) (mol/l) (mol/l)
DMSO
AuPPh 3I 0.005～0.04 0.008～0.03 0.015
NH 4I 0.05～1.5 0.1～0.5 0.2
Embodiment four:
The plating condition is with embodiment one, solvent DMF, Jin Yuan AuPPh 3Cl, supporting electrolyte NH 4Cl, coating gloss, golden yellow.
Plating bath is formed and concentration is:
Form peak concentration scope optimum concn
(mol/l) (mol/l)
DMF
AuPPh 3Cl 0.005～0.08 0.02
NH 4Cl 0.05～saturation concentration saturation concentration
Embodiment five:
The plating condition is identical with embodiment one, solvent DMF, Jin Yuan AuPPh 3Br, supporting electrolyte NH 4Br, coating gloss, golden yellow.
Plating bath is formed and concentration is:
Form peak concentration scope optimum concentration range optimum concn
(mol/l) (mol/l) (mol/l)
DMF
AuPPh 3Br 0.005～0.07 0.008～0.03 0.02
NH 4Br 0.05～1 0.1～0.5 0.2
Embodiment six:
The plating condition is with embodiment one, solvent DMF, Jin Yuan AuPPh 3I, supporting electrolyte NH 4I, coating gloss, golden yellow.
Plating bath is formed and concentration is:
Form peak concentration scope optimum concentration range optimum concn
(mol/l) (mol/l) (mol/l)
DMF
AuPPh 3I 0.005～0.06 0.008～0.03 0.02
NH 4I 0.05～2 0.1～0.5 0.2
Embodiment seven:
Sample (electrode) is used the nickel sheet of 10mm * 2mm * 12mm, solvent DMSO, Jin Yuan AuPPh instead 3Cl, supporting electrolyte NH 4Cl, other plating condition is with embodiment one, the careful light of coating.
The plating bath composition is identical with embodiment one with concentration.
Embodiment eight:
The plating condition is with embodiment one, solvent DMF, Jin Yuan AuPPh 3Br, supporting electrolyte n-Bu 4NBr (positive Tetrabutyl amonium bromide), coating gloss golden yellow.
Plating bath is formed and concentration is:
Form peak concentration scope optimum concentration range
(mol/l) (mol/l)
DMF
AuPPh 3Br 0.005～0.04 0.008～0.03
n-Bu 4NBr 0.1～1.5 0.1～0.5

Claims (5)

1, a kind of non-aqueous solvent cyanogen-less gold liquid, its component comprises non-aqueous solvent, Jin Yuan, supporting electrolyte, it is characterized in that:
Non-aqueous solvent is at least a among DMSO, DMF, the PC;
Jin Yuan is AuPPh 3At least a among the X, wherein X=Cl, Br, I, acac;
Supporting electrolyte is the inorganic or organic ammonium salt that dissolves in non-aqueous solvent, and inorganic ammonium salt is NH 4X, wherein X=Cl, Br, I; Organic ammonium salt is R 4NX, wherein 4 R groups are at C 2H 5, n-C 4H 9Choose any one kind of them X=Cl, Br, I in two kinds of groups.
2, gold plating liquid according to claim 1 is characterized in that: described non-aqueous solvent is a kind of among DMSO, DMF, the PC; Jin Yuan is AuPPh 3A kind of among the X, wherein X=Cl, Br, I, acac.
3, gold plating liquid according to claim 1 and 2 is characterized in that: described golden source concentration is 0.005mol/l～saturation concentration, and supporting electrolyte concentration is 0.05mol/l～saturation concentration.
4, gold plating liquid according to claim 3 is characterized in that: described golden source concentration further is 0.008mol/l～0.03mol/l, and supporting electrolyte concentration further is 0.1mol/l～0.3mol/l.
5, gold plating liquid according to claim 1 is characterized in that: described non-aqueous solvent is DMSO; Jin Yuan is AuPPh 3Cl; Supporting electrolyte is NH 4Cl.
CN 200310106231 2003-11-07 2003-11-07 Non-aqueous solvent cyanogens-free gold plating solution Expired - Fee Related CN1247822C (en)

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JP4530111B2 (en) * 2008-10-15 2010-08-25 日立金属株式会社 Electro-aluminum plating solution and method for forming aluminum plating film
CN108441901A (en) * 2018-04-18 2018-08-24 中国工程物理研究院激光聚变研究中心 A kind of gold-plating solution of no cyanogen organic solvent

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