Chemical Papers 66 (6) 617620 (2012)

DOI: 10.2478/s11696-011-0117-z

SHORT COMMUNICATION

Etching and recovery of gold from aluminum substrate

in thiourea solution

a,b
Tom Jindra*, a Zdenk Prokop, b Dalimil nita

a Materion Czech s.r.o., Vclavsk nmst 808/66, 110 00 Prague, Czech Republic

b Department of Chemical Engineering, Faculty of Chemical Engineering, Institute of Chemical Technology,

Technick 5, 166 28 Prague 6, Czech Republic

Received 15 June 2011; Revised 20 October 2011; Accepted 21 October 2011

This paper deals with two (main) problems of specic gold etching from parts of industrial
equipment (e.g., supporting inserts into chambers for physical or chemical vapor deposition). First
part of the paper is focused on selective etching of gold from aluminum substrates. Selectivity of the
reaction, i.e. leaving substrates intact, is crucial. For this reason, the environmentally friendly and
safe method of etching gold in a thiourea solution was tested. This method, while well described
in literature, does not preserve various substrates (e.g., aluminum, stainless steel). The main goal
of this part of the paper was to understand the mechanism of the reaction and to improve the
reaction selectivity towards the aluminum alloy substrate. Thus, dierent acidifying agents were
tested. Second part of the paper is focused on recovery (reduction) of gold from thiourea solutions.
Chemical, electrochemical, and biological reduction were tested for gold recovery.

c 2011 Institute of Chemistry, Slovak Academy of Sciences

Keywords: gold, selective etching, thiourea, electrowinning, Spirulina platensis

Gold and other expensive metals can be obtained,
besides by mining, also as a secondary raw material
from, e.g., semiconductor, photovoltaic, and automo-
tive industry in the form of production scrap or de-
position on various parts of the manufacturing equip-
ment (e.g., supporting inserts into chambers for physi-
cal or chemical vapor deposition). An intercepted layer
of metals is created during the deposition processes
and can cause serious problems in the deposition of
other materials when this layer is too thick. Thus, the
parts with deposited metal layer have to be cleaned.
Also, recycling of the deposits is highly demanded es-
pecially in case of expensive materials (gold, platinum,
indium, etc.).
Gold is chemically etched by various agents,
e.g., iodine in potassium iodide, aqua regia (nitro
hydrochlorid acid, r = 1 : 3), cyanide, amalgam,
etc. (Hilson & Monhemius, 2006; Vukcevic, 1996;
Kuzugudenli & Kantar, 1999). However, none of these
methods is ideal for many industrial applications.
The amalgam method is environmentally harmful, the
cyanide one is very dangerous for humans, iodine in
potassium iodide is uncomfortable for handling, and
aqua regia does not reach sucient selectivity. The
possibility of using a solution of acidic thiourea is well
described in literature (Vodvka, 1987; Ubaldini et
al., 1998) and it is also industrially tested (Ardiwilaga,
1991; Whitehead et al., 2009). This method is su-
ciently selective and does not constitute a risk to the
operator as the above mentioned methods and, more-
over, it seems to be environmentally friendly.
This work deals with the removal of gold deposits
(contaminated with other metals like tantalum and
copper) from aluminum component (standard alu-
minum alloy AlMgx ) for semiconductor manufactur-
ing. The aim of this paper was to nd a practically

*Corresponding author, e-mail: tomas.jindra@materion.cz

Presented at 38th International Conference of the Slovak Society of Chemical Engineering, Tatransk Matliare, 2327
May 2011.

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618 T. Jindra et al./Chemical Papers 66 (6) 617620 (2012)
Fig. 1. Observed corrosion on aluminum substrate.
applicable etching solution for selective removal of the
deposition and subsequent recovery of gold from this
solution.
All chemicals used in the experiments were of an-
alytical grade quality (SigmaAldrich, Seelze, Ger-
many). Industrial quality of chemicals was applied in
the pilot plant scale. An acidic thiourea solution was
used for chemical etching. Standard etching solution
(Ubaldini et al., 1998) consists of thiourea (CS(NH2 )2 ;
the complexing agent), sulfuric acid (acidifying agent),
and iron(III) sulfate (Fe2 (SO4 )3 ; oxidizing agent).
Three dierent acids were tested with respect to
the deposition; sulfuric acid, 2-hydroxypropane-1,2,3-
tricarboxylic acid (citric acid), and ethanedioic acid
(oxalic acid). Most other inorganic acids are not suit-
able for the aluminum substrate as aluminum reacts
with them. Sulfuric acid was used only to test the fea-
sibility of gold etching with acidic thiourea solutions.
Sulfuric acid passivates aluminum but preliminary re-
sults showed that corrosion can occur. At rst, cit-
ric acid seemed to be appropriate for the etching but
small local corrosion also appeared on the aluminum
substrate after some time (so-called galvanic corro-
sion). Corrosion occurs only at locations where pieces
of the deposition (in form of larger akes) touch the
aluminum substrate (Fig. 1).
Another tested acidifying agent was oxalic acid.
No negative eects of this acid on the substrate sur-
face were observed. Oxalic acid was nally used as the
acidifying agent.
Potassium persulfate (K2 S2 O8 ) was also tested as
an oxidizing agent instead of Fe2 (SO4 )3 . Persulfate as
the oxidizing agent does not damage the substrate but
preliminary results show that the etching rate is two
times lower.
Overall reaction of thiourea gold etching is de-
scribed by the equation (Ubaldini et al., 1998):
Au + 2CS(NH2 )2 = Au(CS(NH2 )2 )+
2 +e
(1)
Detailed description of the mechanism of thiourea
gold etching is described below. The rst step of
thiourea gold etching is the oxidation of thiourea and
the formation of formamidine disulde:
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2CS(NH2 )2 = C2 S2 (NH)2 (NH2 )2 + 2H+ + 2e (2)
Formamidine disulde is a very good oxidant for
gold etching. The second step is the reaction between
gold, thiourea, and formamidine disulde:
2Au + 2CS(NH2 )2 + C2 S2 (NH)2 (NH2 )2 + 2H+ =
+ 2Au(CS(NH2 )2 )+ 2 (3)
Composition of the solution was chosen according
to literature (Vodvka, 1987; Ardiwilaga, 1991; Ubal-
dini et al., 1998), where dierent ratios of chemicals
are presented. The amount of chemicals used for one
etching solution batch was: 50 L of deionized water,
2 kg of thiourea, 400 g of Fe2 (SO4 )3 , and 0.5 L of oxalic
acid (10 %). This ratio of chemicals was the same for
all batches. The solution batch was exchanged every
13 days in order to avoid substrate damage. A batch
exchange has to be done when pH decreases, solution
changes its color (gets dark) or noticeable decrease of
the etching rate is observed. In this way, 45 batches
(total volume of about 2500 L) of the solution with
dierent gold content were obtained.
After etching of the deposition, 45 batches of
thiourea solution with the concentration of gold in
the range from 4.5 mg L1 to 250 mg L1 were ob-
tained as mentioned above. The concentration was es-
timated by atomic absorption spectroscopy (AAS; a
model Varian SpectrAA880, Varian, USA). The solu-
tion also contained copper and iron found by X-ray
uorescence analysis (XRF; a model Spectroscan V,
Spectron, Russia). The concentration of copper was
of about 200 mg L1 and that of iron was of about
440 mg L1 . Copper was probably a part of the de-
position but its presence was not known before the
etching. The presence of iron is caused by Fe2 (SO4 )3
used during the etching.
There are many methods for gold recovery from
thiourea solutions. Three of them were tested in this
work: chemical reduction, biological reduction (Sav-
vaidis, 1998), and electrochemical recovery (Urban-
ski et al., 2000; Juarez & Dutra, 2000). Other (not
tested) possibilities for gold recovery are: adsorption
of gold on activated carbon (Soto & Machuca, 1989;
Zhang et al., 2004), application of special ion-exchange
resins (Mensah-Biney, 1997) or other reducing chemi-
cals (Awadalla & Ritcey, 1991).
Ammonia solution was tested for chemical reduc-
tion of the gold complex. The gold complex was re-
duced but it consumed a large amount of the ammonia
solution, which in combination with the low concen-
tration of the gold solution resulted in high possibility
of gold loses during the manipulation with the solu-
tion.
Spirulina platensis (a kind of bluegreen algae)
was used for biological reduction of gold (Savvaidis,
1998). It was observed that Spirulina extracts gold
from thiourea solution in small volumes. Three dier-
 T. Jindra et al./Chemical Papers 66 (6) 617620 (2012) 619

Table 1. Observed corrosion on aluminum substrate

cSP /(g L1 ) cAu /(mg L1 ) cCu /(mg L1 )

0 115 202
10 109 198
30 91 175
60 77 160

cSP Concentration of Spirulina platensis, cAu concentration

of gold, cCu concentration of copper.

Fig. 3. Time dependence of: gold concentration and

iron concentration.

tered through a paper lter and then the lter with the
lter cake was burned at high temperature (1050 C)
in a furnace. Burning in the furnace has to be gradual;
the gold complex is rst reduced by carbon emerging
from burning algae and lter paper and then, gold
is melted into metal state at a higher temperature
(Fig. 2). Preliminary results show that the purity of
gold (after nal melting) was higher than 95 %.
Reaction of electrochemical recovery of gold from
thiourea solution can be described by the equation
(Urbanski et al., 2000):

b
Fig. 2. Burned algae (a) and melted gold from burned algae
(b).
ent concentrations of Spirulina were tested (reaction
time was four days) (Table 1).
The complex of gold was extracted from the so-
lution. Spirulina (with trapped gold complex) was l-
Au(CS(NH2 )2 )+
2 + e = Au + 2CS(NH2 )2 (4)
First, electrowinning was tested in a small volume
of gold solution. Black coating formed on the cathode.
XRF analysis showed that the coating is composed of
gold ( 50 %), iron ( 20 %), and copper ( 30 %).
For larger volumes, a simple electrowinning appara-
tus was designed and tested. The apparatus consists
of two vessels (volume of 70 L and 5 L) separated with
a cation exchange membrane (CEM, a model RALEX
CM-PES, MEGA, Czech Republic). Cathode area is
stirred with modied bench drill. Anode is made from
titanium coated with platinum, cathode is made from
copper plate, power supply is Manson HC-D9106SIM
(Hong Kong, China). Cathode and anode area have
to be separated due to the unwanted formation of sul-
fur in the galvanic bath. For this purpose, the small
vessel containing a CEM was used. This vessel repre-
sents the anode space and during the process it was
lled with sulfuric acid. Kinetics of gold (and iron)
electrodeposition was measured on this apparatus.
Decreasing concentrations of iron and gold are
shown in Fig. 3 (for the voltage of 15 V and the cur-
rent of 1.5 A). The cathode area was approximately
100 cm2 .
However, the gold recovery tests provided incom-
parable results; very important criteria for the tests
are the simplicity and robustness of the recovery

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620 T. Jindra et al./Chemical Papers 66 (6) 617620 (2012)
method. Biological reduction is slower but not de-
manding of service or equipment. Electrochemical re-
duction is faster but it is sensitive to a qualied opera-
tor and suitable equipment. This was the most impor-
tant argument for the selection of biological reduction
for gold recovery.
A method of selective etching of gold (and other
metals) from the aluminum substrate without dam-
aging the substrate was introduced. Thiourea etch-
ing was found a suitable method for gold etching not
only in mining industry but also in other applications.
The original mixture of compounds was successfully
changed and it was shown that an appropriate combi-
nation of compounds can lead to remarkable results.
Not only the acidifying agent was changed (oxalic acid
was used instead of sulfuric acid), also a dierent oxi-
dizing agent (K2 S2 O8 instead of Fe2 (SO4 )3 ) was suc-
cessfully tested.
Finding the optimal composition of the solution is
not (nor could be) the subject of this paper. In com-
mercial operation, a quick decision on the method to
be used is often needed and the chemicals are often
selected on basis of previous experience and visual
observation. Once the method is (at least somewhat)
functional, no changes are made. This paper shows a
possible way of selective etching of gold and eventual
improvement of chemical composition of the etching
solution is left for later studies.
Three dierent methods for recovery of gold from
a thiourea solution were tested. All three methods are
eectual. Biological reduction with Spirulina platensis
was chosen as the most practically applicable (with
regard to technology, simplicity, and complexity of the
process).
Purity of the obtained gold was not the key point
of this work since it can be improved by any standard
rening process (e.g., etching of obtained raw material
in aqua regia).
Despite the successful application of thiourea so-
lution, other possibilities of gold etching from specic
substrates are searched for because other metals, e.g.
copper, are also soluble in acidic thiourea solutions.
Acknowledgements. The work was supported by the Tech-
nology Agency of the Czech Republic (project No. TA01010353).
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