Electrochemical Treatment of Jewelry Alloys of Gold in an Acidified

Solution of Thiourea

Sergey Nersisyan, Chemistry Department, Yerevan State University,

Yerevan Factory of Art Watches, Yerevan, Armenia

Etching and polishing of gold alloys is mandatory in the jewelry industry. Both chemical and
electrochemical methods are based on dissolving the surface layer of the alloy with the appropriate
complexing agent to form a brilliant surface. Commonly, a cyanide process has been used for
chemical etching and polishing. However, it is untenable from a health and safety perspective. The
purpose of this work is to study the operation of an anodic electrochemical treatment of jewelry
alloys of gold in an acidified solution of thiourea. Using voltammetry, the ideal concentration ranges
of thiourea and sulfuric acid were determined for etching, polishing and oxidizing. A functioning
prototype is described which is used in the production of gold watches with great success.

For More Information Contact:

Sergey Nersisyan, Ph.D
1 Alek Manookian str,
Yerevan 375025, Armenia
Phone: (3749) 330-231
Fax: (3741) 570-663
E-mail: [email protected]

2005 SUR/FIN Proceedings 626 ©2005 SFIC

 Etching of gold alloys is a mandatory operation after casting. It is realized for dissolving
the surface layer of the alloy, in which during the casting irreversible changes of the quantitative
composition have occurred, connected with oxidation of copper and other active components of
the alloy. Etching is also necessary for removing traces of the material of the casting form from the
surface of the alloy. Chemical and electrochemical methods of etching of gold alloys are known.
Polishing of jewelry alloys of gold is usually realized by mechanical, chemical or electro-
chemical methods. In the cases mechanical polishing cannot give proper results when products
have recesses or uneven relief. Chemical or electrochemical methods are used in such cases.
Both chemical and electrochemical methods of etching and polishing are based on dissolving
the surface layer of the alloy in the appropriate complexing agent that brings to the formation of a
more or less brilliant surface under certain conditions.
The mixture of warm water solutions of potassium cyanide and hydrogen peroxide is used
as an agent for chemical etching and polishing. The mixture is prepared right before carrying out
the process and can be used one time only. When mixing the above mentioned solutions a rapid
reaction with gassing of extremely toxic dicyan takes place. The solution contains cyanides and
alkali. The process is too dangerous from ecological perspective. Its realization by unskilled
personnel is unacceptable. Despite this fact this method of etching is widely spread because of
simplicity of its application.
Chemical methods of etching and polishing are widely spread all over the world, e.g. USA,
Arabic countries, Indo-China. In many countries, for example USA, these methods are forbidden
because of intensification of environmental control. Gold and silverware producers who based
on the technology have to conduct processing of the surface incurs huge penalties imposed
by controlling organizations. Many of them transfer their businesses to Asian countries where
requirements are not so strict.

Essence of the electrochemical method is anodic oxidation of the alloy components in the
presence of a complexing agent. At the same time in micro ledges, where the current density and
diffusion rate are higher dissolving happens faster than in cavities, and as a result the surface
smoothes out. It is possible to use solutions of potassium cyanide, thiourea, etc. as complexing
agents. At present mainly the solution of thiourea, acidified by sulfuric acid is used, considering
extraordinary toxicity of cyanides.
Realization of electropolishing requires high professionalism. The solution often requires
adjustment both by thiourea, and by sulphuric acid; the necessary temperature and voltage need to
be selected. If an incorrect mode is selected non-repeatability of results is observed, outgassing of
hydrogen sulphide takes place on the cathode, and these circumstances prevent this undoubtedly
progressive method from being widely spread.
To solve this problem we have set the task to develop an automatic computer-aided system
that will be able to control the process independently. For that purpose we have started to
investigate anodic dissolving of alloys of gold in acidic solutions of thiourea.

2005 SUR/FIN Proceedings 627 ©2005 SFIC

 Experimental

The first patent for the solution for electrochemical polishing of alloys of gold containing
50g/L of thiourea and sulphuric acid belongs to the company Degussa. All the further proposed
non-cyanide electrolytes also contain thiourea, only its concentration differs. For example,
according to the USSR Standard a solution containing 90g/L of thiourea and 40g/L of sulphuric
acid was suggested for electropolishing. By the same Standard a solution containing 120g/L of
thiourea and 60g/L of sulphuric acid was suggested for electroetching.
Because the data on the composition of electrolytes differs greatly we have conducted
experiments with different solutions for electroetching and electropolishing in the Yerevan
Factory of Art Watches.
We have studied the solutions with the following composition:
I. Thiourea 76g/L , Sulfuric acid 49g/L
II. Thiourea 90g/L , Sulfuric acid 49g/L
III. Thiourea 90g/L , Sulfuric acid 60g/L
IV. Thiourea 100g/L , Sulfuric acid 60g/L
All experiments have been conducted in stationary conditions with fixed electrodes and
without stirring. Plates, frames of watches, bracelets as well as other jewelry made of an alloy of
gold containing 58,5% Au, 33,5% Cu and 8,0% Ag have been used as an anode.

Results and Discussion

It is known that the first rectilinear portion of the anodic polarization curve corresponds
with even dissolving of the metal. In the “wave” section electropolishing takes place and at higher
voltage values oxidizing of the surface of the metal occurs [1].
The anodic polarization of the gold alloy in acidic solution of thiourea depends on the
concentration of thiourea and sulphuric acid, as well as on the temperature of the solution (Fig. 1,
3, 6, 8).

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 Fig.1. Dependence of anodic polarization on the temperature
(solution I) .

Fig.2. Current-Time dependence during the process of electrotreatment

(solution I, 33oC).

Dissolving of the anode can be simplifiedly divided into the following stages:

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 In the first stage oxidation of the metal atoms takes place.
Au - e Au+
Cu - e Cu+
Ag - e Ag+

In the second stage complex forming with two molecules of thiourea occurs
Me+ + 2 SC(NH2)2 Me[(SC(NH2)2]
In the third stage complexes are hydrating and diffusing into the solution
Me[(SC(NH2)2] + n OH2 Me[(SC(NH2)2] (aqua)
A limiting stage is the diffusion of complexes from the surface into the solution and reverse
diffusion of free ligands molecules. The diffusion rate greatly depends on the temperature, naturally
the temperature must strongly influence the course of the process. It can be seen on Fig. 1. For
example increasing the temperature above 37oC results in disappearing of the “wave” at voltage
of about 3V.

Fig.3. Anodic polarization curves at 33OC and 40OC,( solution II).

Increasing the concentration of thiourea from 76g/L to 90g/L doesn’t essentially affect the
shape of the curve (Fig. 3), but at 33oC a clearly expressed periodic process is observed at the range
of 1.6-1.8V (Fig. 4).
This can be explained by periodic formation and dissolution of the oxide film on the anode
[2,3] when the rate of formation of oxides is approximately equal or a bit more than the rate of
diffusion of ligands to anode.

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 When increasing the temperature the rate of diffusion increases so much that even increasing
the voltage up to 3.6V results in a stationary process after only 15-20 sec (Fig. 5).

Fig.4. Current-Time dependence during the process of electrotreatment

(solution II, 33oC).

Fig.5. Current-Ttime dependence during the process of electrotreatment

( solution II, 40OC).

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 The data for solution III is shown in Fig 6 and 7.

Fig.6. Anodic polarization curve at 40OC (solution III).

Fig.7. Current-Time dependence during the process of electrotreatment

( solution III, 40OC ).

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 On Fig 8 and 9 a specific example of electropolishing of a bracelet in solution IV is
illustrated.
At the temperature 25oC a wave is observed at voltage 3V.

Fig.8. Anodic polarization curves at 25OC ( solution IV).

2 minutes after starting electropolishing the periodic process starts. In three minutes only
the product is polished so well that there is no need for mechanical polishing.

Fig.9. Current-Time dependence during electropolishing of bracelet

( solution IV).

2005 SUR/FIN Proceedings 633 ©2005 SFIC

 Summary and conclusions

Studies of the electrochemical dissolution of jewelry alloys of gold in thiourea-sulfuric

acid solution show that the best results are obtained in case of the following composition of the
solution: thiourea - 100 g/L and sulfuric acid – 60 g/L. This is a universal solution that can be
used for all the processes - electroetching, electropolishing and oxidizing only by changing the
conditions of electrochemical treatment (temperature, voltage, etc.).
Investigation of electrochemical dissolving patterns of gold alloys in the solutions of
thiourea and sulphuric acid has shown that it is possible to create a device for electroetching,
eletropolishing and oxidizing which will be able to independently, without intervention determine
the optimal mode for conducting the process and automatically realize the process under the most
appropriate conditions. So the advantages of chemical and electrochemical methods are combined
in one device – simplicity, quality and repeatability.
Such a device will give the opportunity to obtain the maximum possible results with 100%
repeatability.
− No expensive professional executers will be necessary.
− Isolation of gold from the electrolyte will take place on the cathode simultaneously as the
process proceeds. And a separate operation for regeneration of gold from the solution won’t be
required.
− It will be possible to eliminate the emission of poisonous and harmful gases into the
atmosphere.
− Neutralization of the electrolyte won’t be needed because the electrolyte will work for an
unrestrictedly long time. It will be a great achievement from the environmental protection
perspective.
− The device will be of great demand at jewelry firms, because it will improve the quality of
produced products; direct costs of etching and electro polishing operations will decrease;
irretrievable losses of gold will reduce. A great progress in protecting the environment will be
achieved.
Presently we have created a functioning prototype which is used in the production of gold
watches with great success. This automatic device for electrochemical etching and polishing
will allow all jewelry producers to realize the necessary operations without problems and large
expenses.
Our approach will give the opportunity to design and develop similar automatic devices for
electrochemical etching, polishing and oxidizing of practically all metals and alloys.

2005 SUR/FIN Proceedings 634 ©2005 SFIC

 REFERENCES

1. Galvanicheskiye pokritya v mashinostroenii. Hand-book, Editor M.A.Shluger, v1, pp. 82-86

2. E. P. Grishina, S. I. Galanin, & O. A. Ivanova, Russian Journal of Applied Chemistry, Vol. 77,
No. 8, 2004, pp. 1283-1286.
3. Sugun Zhang & M.J.Nicol, Journal of Applied Electrochemistry 33: 767–775, 2003.

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