Materials Science Forum Submitted: 2018-01-12

ISSN: 1662-9752, Vol. 930, pp 541-545 Accepted: 2018-01-24

doi:10.4028/www.scientific.net/MSF.930.541 Online: 2018-09-14
© 2018 Trans Tech Publications, Switzerland

Characterization of Galvanic Sludges Waste Derived of the Metal Plating

Industry from Cariri Region, Northeastern of Brazil
Cícero Lucas Martins de Oliveira1,a*, Francisco José de Paula Filho1,b,
João Victor Barbosa Moura1,c, Daniel Muller G. Freitas1,d
and Marcelo Oliveira Santiago1,e
1
Federal University of Cariri, Science and Technology Center, 63.048-080,
Juazeiro do Norte, CE, Brazil
a
cicero.lucas122@gmail.com, bfrancisco.filho@ufca.edu.br, cvictor.moura@ufca.edu.br

Keywords: Galvanic sludge waste; Residues as hazardous; Characterizations; Heavy Metals.

Abstract: In this study, galvanic sludge waste (GSW) was characterized in order to identify its
chemical and structural properties, allowing indicate reuse, treatment and final disposal methods,
and evaluate the environmental hazards. The characterization of the galvanic sludge sample
originating from a surface treatment plant from galvanic industries of semi-jewels in the Cariri
region, NE of Brazil was performed. The chemical characterization of the samples by flame atomic
absorption spectroscopy (FAAS) and X-Ray Fluorescence (XRF) showed that Zn and Cu are the
predominant elements. However, elements like Ni, Cd, Mn, Fe, Cr and Co are present as a minority
or as trace constituents. The concentrations of residues were higher, except Ni, in the LM industry
(27 g Zn.kg -1, 194 g Cu.kg -1, 8 g Fe.kg-1, 538 mg Cd.kg -1, 227 mg Ni.kg -1, 73.5 mg Cr.kg1, 14 mg
Co.kg-1) in relation to LJ (11 g Zn.kg-1, 3 g Fe.kg-1, 102 g Cu.kg-1, 2 g Cd.kg-1, 141 mg Ni.kg-1,
11 mg Co.kg-1), denoting that there is no uniform standard in the treatment process of the effluent
from baths for Metal deposition. According to the standard procedure (Brazilian norm
NBR10004/04) the elements Cd and Cr are the main constituents responsible for the classification
of the residues as hazardous. The X-ray diffractogram of the dried galvanic sludge only revealed the
presence of BaSO4 and CuO as crystalline phases, a result which agrees with the results from
FT-IR. The results point to an attractive way of valorizing GSW avoiding the negative impact
associated with its disposal in landfills.

Introduction
Water is used to rinse the jewels between the various steps involved in their casting, stripping,
cleaning, and plating operations. The waste generated is corrosive, or contains cyanide or dissolved
metals, being generally harmful to human health and the environment, and therefore, considered
hazardous. Galvanic processes generate a large volume of effluents by the use of degreasers, paint
strippers, chromatizers, and the various concentrated electrodeposition baths that have been
depleted, making proper wastewater treatment process crucial. In general, regarding effluent
treatment systems, the dissolved heavy metals are precipitated and subsequently removed by
settling, sedimentation or sometimes by filtration. According to estimates, the galvanic sector
computes waste management expenses as equivalent to 6% of its total cost of production [1].
Current laws and regulations establish how to manage hazardous waste in order to protect public
health and safety, and the environment. The sludge produced by the physical-chemical treatment of
effluents is potentially ecotoxic because it presents high levels of heavy metals, characterizing a
hazardous environmental liability (class I), according to Brazilian Standard NBR10004/2004. Also,
the European Union regulates this hazardous waste according to Council Decision 2000/532/CE.
Jewelry manufacturers can protect public health and safety, and avoid costly fines and penalties, by
managing their hazardous wastes in compliance with these laws regulations.
Disposal and treatment of waste are the major concerns of the product sector and environmental
agencies. Proper disposal of industrialized solid waste is a problem in Brazil as well as in
developing countries. Therefore, because it represents a risk to the environment and human health,

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542 22nd Brazilian Conference on Materials Science and Engineering

the waste must receive special attention regarding its study and characterization, which can make
possible an efficient treatment process and a possible application or recycling, so that its
constituents are immobilized, thus reducing the environmental risks. This work aims at
characterizing the physics and chemistry of galvanic wastes from Semi-Jewelry Industries in the
Cariri region, in the northeastern of Brazil. Morphological characterization, phases, composition
and chemical concentration are intended to infer possible forms of reuse, treatment and final
disposal, as well as provide subsidies to companies in the region to potentiate changes in their
production processes in order to reduce the presence of dangerous elements or try to recover, in an
economically viable way, contaminating metals.

Experimental Procedure
We selected surface treatment plant from galvanic industries of semi-jewels in the Cariri region,
NE of Brazil, that presented similar production processes (LJ and LM). The galvanic sludge (GSW)
is formed as a result of the waste water reactants purification from the galvanic production
processes conducted in the enterprises and comprises a gray-green paste-like product having a
moisture content ranging from 60 to 70%. After drying at 105 °C, the samples were crushed and
then sieved (180 μm mesh). The opening of the sample, in order to characterize it, was carried out
using 1.0 g of the residue sample with the addition of 25.0 mL of aqua regia 50%, in water bath at
80ºC with recirculation for 2 hours [3]. The chemical analysis of the galvanic sludges was
performed by flame atomic absorption spectroscopy (FAAS) and X-Ray Fluorescence (XRF) using
a Varian SpectraA 50B and Panalytical Epsilon1 spectrometer, respectively. The structural
characterization was done by X-ray diffraction technique using a Bruker D-8 Advance XRD
diffractometer with the CuKα radiation (λ = 1.5418 Å) in the 2θ range of 5°- 60°, with a step size of
0.02° and a counting time of 2 s/step. Fourier Transform Infrared (FT-IR) spectra were taken in the
range from 450 to 4000 cm-1 using KBr pellets as a reference using a Perkin Elmer Spectrum Two
spectrophotometer in transmittance mode. Morphological aspects of the samples were observed
using scanning electron microscopy (SEM). The SEM images were obtained using a Tescan Vega 3
scanning electron microscope, operated at 20kV.

Results and Discussion

The results presented in Fig. 1 show the graphics related to concentrations of heavy metals in
residues. The experimental errors, determined by different experiments were ± 3.5%. We can
observe that the magnitude order of the analyzed elements’ concentration in the residues shows no
significant variation. The chemical characterization showed sludges with high copper
concentration, with more than 10% (wt%), followed by Zn with values ranging from 1.1% to 3.0%
dry base. Fe, Mn, Ni and Cd elements appear in micro concentrations in the samples. The trace
constituents in the galvanic residues were found to be chromium and cobalt, with concentrations
between 65 – 73 ppm for Cr and 11 – 14 ppm for Co. Chromium is one of the most toxic
contaminants in effluents and electroplating waste, being considered a dangerous constituent along
with cadmium, nickel and cyanide complexes (NBR 10004/2004).

Fig. 1: Concentration of heavy metals in samples of galvanic sludge wastes (GSW) from metal plating
industry from Cariri region, northeastern of Brazil.
 Materials Science Forum Vol. 930 543

The Table 1 shows the percentage of chemical elements found in the LJ and LM galvanic
sludges, duly measured by the XRF. These data confirm the results obtained through the FAAS, in
addition to presenting another diversity of elements, such as Pb and Nb. The presence of rare earth
elements (Yb) in the waste composition is noteworthy. In general terms, the elementary constitution
of galvanic sludges is similar, nevertheless the quantity of the chemical elements, as we note from
Table 1, are slightly different. Therefore, from this stated table, we can observe that the
predominant elements in the LJ sample are copper and barium. The LM galvanic sludge sample has
only copper as the predominant element, as shown in table 1, i.e., with the other components
appearing in low elemental percentage.
Table 1: Elemental percentage in the LJ and LM galvanic sludge derived
of the metal plating industry obtained by XRF.
Chemical
Zn Cu Fe Mn Ni Cd Pb Nb Ba S Si P Ca Sn K Cl Yb
Elements
LJ 2.49 26.75 0.32 0.81 0.76 0.11 n.d. n.d. 24.6 4.00 1.50 1.19 0.92 0.17 0.15 0.14 0.10
LM 5.52 43.07 0.97 0.27 4.37 n.d. 0.92 0.22 0.27 1.07 3.16 0.40 0.21 n.d. n.d. 0.88 n.d.

Fig. 2 presents the X-ray diffractogram and FT-IR spectra of both the galvanic sludges derived
of the metal plating industry (LJ and LM companies) from the Cariri region, northeastern of Brazil.
According to the X-ray diffraction pattern (See Fig. 2(a)), the LJ galvanic sludge is constituted
basically of two compounds: (1) Barium Sulfate, BaSO4 (ICSD nº 068308) and (2) Cooper Oxide,
CuO (ICSD nº 087124). Barium Sulfate exhibits an orthorhombic structure with space group Pbnm
[4] and the copper oxide belongs to the monoclinic structure with space group C12/c1 [5]. The X-
ray diffractogram of the LM company galvanic sludge shows a deformed background, indicating a
high fraction of amorphous material in the sample. Few diffraction planes with low intensity are
observed in the diffraction pattern of MS galvanic sludge corresponding to copper oxide, CuO.

Fig. 2: (a) X-ray diffraction pattern

and (b) FT-IR spectra of the Galvanic Sludges derived of the metal plating industry.
The FT-IR spectra of galvanic sludges derived of the metal plating industry over the 450-
4000 cm-1 range are shown in Fig.2 (b). The galvanic sludge spectrum shows two modes with peaks
close to 1630 and 3428 cm−1, which we associate with the O–H vibrations of adsorbed water in the
sample or with the small quantity of water present in the KBr. In the LJ galvanic sludge spectrum
(Black spectrum) the bands at 983 cm-1 (ν1), 1073 cm-1 (ν3), 1112 cm-1 (ν3), and 1202 cm-1 (ν3) are
related to the vibrations of the sulfate ion (SO4) of the barite phase (BaSO4), confirming the XRD
results [6]. In both spectra (Black and red spectra) the vibration modes at approximately 610 cm-1
correspond to the Cu-O vibration mode of copper oxide (CuO) [7], a result which is in accordance
with the results from XRD. In the LM galvanic sludge spectrum, we can observe a mode at
2181 cm-1, that corresponds to the presence of organic matter in the material, which justifies the
presence of amorphous fraction previously shown with the distortion in the background of the
diffractogram.
544 22nd Brazilian Conference on Materials Science and Engineering

According to the data presented in FAAS, XRF and DRX analysis, the GSW has a complex
phase composition with a high content of heavy-metal compounds, first and foremost, Zn and Cu,
as well as barium compounds. The presence of heavy metals in substantial amounts on the one hand
makes this GSW a valuable secondary raw material however, on the other hand it presents a danger.
An alternative to this problem is the conversion of hazardous waste (class I) to hazardous waste
(class II - not inert). However, this requires changes to be made in the production process of the
electroplating companies and in the treatment of effluents. This could allow a change in the
classification of waste. In that case, when a waste is characterized as non-hazardous, a range of
options for its reuse is opened, such as in the ceramic, glass and fertilizer industry, adding value to
the waste and providing other possibilities of more noble uses for this type of waste.
The SEM images of galvanic sludges are shown in the Fig.3, where we can observe separate
particles with different sizes and shapes, which confirm the samples’ multiphase characteristic.

Fig. 3: Low- and high-magnification SEM images of (a-b) LJ

and (c-d) LM galvanic sludge derived of the metal plating industry.
One of the potential uses of this hazardous waste is a raw material to produce environmentally
sensitive and useful materials [8, 9]. There are important research works on the extraction and reuse
of heavy metals (Zn, Cu and others) extracted from the dry residue and effluents [8, 9, 10, 11]. The
ceramic industry in the Cariri region may be a viable alternative in the utilization of large quantities
of industrial galvanic waste. The incorporation of waste GSW containing heavy metal ions in a
ceramic matrix may be a promising solution to reduce environmental risks [8, 9, 12, 13].

Conclusions
In summary, this study reports the chemical, structural and vibrational characterization of the
galvanic sludges from industries of semi-jewels in the Cariri region. The characterizations of
galvanic wastes are very important, especially in environmentally sensitive areas such as the semi-
arid region of northeastern Brazil, so that it is possible to identify the elements that characterize the
waste as hazardous. At the same time, this study provides subsidies for attempting to recover toxic
elements, however valuable elements or replacing them in the process with less toxic elements to
decrease the amount of hazardous waste (class I) generated. In addition, the qualitative and
quantitative evaluation of the galvanic sludge carried out in this research is fundamental for the
identification of adequate technologies for the recovery and / or treatment of this industrial waste.
Finally, this work provides knowledge that contributes to reduce the scarcity of information from
direct research in the region.

Acknowledgment
The authors would like to acknowledge the financial support for this work of Cearense Foundation
for Scientific and Technological Development Support – FUNCAP, through the Program of
Research Productivity Grants, Incentives to Interiorization and Technological Innovation – BPI
(process nº BP2-0107-00009.01.00/15).
 Materials Science Forum Vol. 930 545

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