Ceramics International xxx (xxxx) xxx–xxx

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Development of gold-bronze metallic glazes in a clay-based system

for stoneware bodies
⁎
Keriman Pekkana, , Hasan Başkırkanb, Münevver Çakıc
a
Dumlupınar University, Faculty of Fine Arts, Department of Ceramic and Glass, Kütahya, Turkey
b
Mimar Sinan Fine Arts University, Faculty of Fine Arts, Department of Ceramic and Glass Design, İstanbul, Turkey
c
Münevver Çakı, Anadolu University, Faculty of Fine Arts, Department of Ceramic Arts, Eskişehir, Turkey

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, a triaxial glaze system consisting of red clay, kaoline, quartz, MnO, CuO and CoO is systematically
Gold-bronze developed to produce gold-bronze raw metallic glazes for stoneware bodies. At first, all of the glazed samples in
Metallic glaze the developed system were fired in an electrically-heated kiln at 1160 °C. Then, the selected successful gold-
Color bronze metallic glazes were applied onto 3-D forms of stoneware bodies and fired at the same conditions.
Stoneware
Microstructural characterizations of the glazes are done with scanning electron microscopy (SEM) and energy
dispersive x-ray analyses (EDS). This study revealed that triaxial blending of the ceramic raw materials is a
beneficial method for glaze production and gold-bronze surfaces are obtained in glazes G 9, G 26, and G 34. It is
observed that chemical composition of the glazes directly influence the color and the amount of CuO is more
significative than MnO for achieving gold-bronze effect.

1. Introduction ceramics [8,9]. Golden or bronze metallic effect is generally obtained

Oxide coatings are commonly used for ceramics with a high dec-
orative effect and metallic glazes are one of the most attractive glaze
types in ceramic industry. They enhance the surface aesthetic properties
with a brilliant metallic shine as lusters usually do [1,2]. Bronze luster on
the surface of a glaze can be achieved with chromium and lead com-
pounds in a special reduction firing. Bronze-effect glazes can be obtained
in oxidized stoneware and porcelain using the fluxing action of manga-
nese oxide with or without copper oxide, feldspar and/or clay [3].
Reduction luster is a highly decorative traditional glazing tech-
nique. However, it is necessary to control the furnace temperature,
atmosphere and time during the reduction process in order to achieve
successful results and this is quite difficult for traditional kilns [4].
Therefore, reduction technique is not appropriate for industrial pro-
duction in terms of instability surface properties and generation of
undesirable gases [5].
Nowadays, metallic glazed products exhibit many innovations for
the decoration of ceramics, compared with decorations made by adding
noble metals, reduction techniques or specific firings at lower tem-
peratures (third fire) [6]. Generally, metallic glazes are produced using
different raw materials such as clays, feldspars, Al-based phosphates,
ceria, metallic oxides and frits [1,7]. As opposed to fritted composi-
tions, raw glaze is a cost effective and time consuming alternative for
by luster technique by using noble metals or lead in glaze compositions
as well as introducing high amounts of frits in glaze batches [2,10].
Unlike luster glazes, it is necessary to use a different preparation
method for metallic glazes and that the final surfaces exhibit the
characteristics of the chemical ingredients [2]. Among all clay body
types with artistic potters, stoneware is the most important with its
fired strength and the character of the finished product. Firing atmo-
sphere, inherent metallic oxides in clay and chemical glaze composition
are the main factors that affect the colors of the fired stoneware objects
[11]. When developing a new glaze composition, it is of a great im-
portance to perform a systematic study which is most effectively en-
sured using blending systems and constructions. There are different
types of methods such as line blend, triaxial and quadraxial blends.
Triaxial blending of the ceramic raw materials is an important process,
mainly used to create a new glaze. They are very useful systems for
mixing raw materials, glazes, or colorants [12]. Generally, they give
thoroughly comprehensive scans of mixtures including two, three and
four components [13]. In the present study, the gold-bronze raw me-
tallic glazes are designed by employing a triaxial blend system in order
to explore the combinations of selected components that are suitable for
stoneware decorations. For this purpose, a glaze system consisting of
red clay, kaoline, quartz, MnO, CuO and CoO is developed and char-
acterized in terms of surface properties and microstructure.

⁎
Corresponding author.
E-mail address: keriman.pekkan@dpu.edu.tr (K. Pekkan).

https://doi.org/10.1016/j.ceramint.2017.12.064
Received 13 November 2017; Received in revised form 8 December 2017; Accepted 8 December 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Pekkan, K., Ceramics International (2017), https://doi.org/10.1016/j.ceramint.2017.12.064
K. Pekkan et al. Ceramics International xxx (xxxx) xxx–xxx

Table 2
Color (L*, a*, b*) and ΔE* values of some studied glazes.

Glazes L* a* b* ΔE*

G 26a 54.81 ± 0.25 8.96 ± 0.02 22.48 ± 0.25 –

G 9 45.28 ± 0.33 8.01 ± 0.39 16.60 ± 0.68 11.23
G 14 45.50 ± 0.72 0.25 ± 0.47 3.98 ± 0.39 22.46
G 25 53.20 ± 1.21 0.29 ± 0.05 4.36 ± 0.27 20.15
G 34 48.16 ± 1.13 8.14 ± 0.31 20.88 ± 0.86 6.88

a
G 26 is selected as the reference for ΔE* calculations.

selected and what the amounts of constituents are respectively. Com-

positional triaxial system was studied in the glaze synthesis. In this
system (CuO+ CoO+ Kaoline+ Quartz) side, the amount of each
constituent is kept equal and 36 glaze recipes are prepared (Table 1).
At first, all glazes are applied on the stoneware substrates and after
that, 9, 14, 25, 26 and 34 coded recipes are chosen for the application
of 3-D stoneware forms. Starting batches as 100 g were wet ball milled
for 15 min and liter weights of glazes were arranged as 1550 g. Glaze
application onto stoneware bodies were made by pouring method on
Fig. 1. Triaxial glaze system (Cu:CuO, Co:CoO, K:Kaolin, Q:Quartz).
plaques that are biscuit fired at 1000 °C and all of the samples were
fired in a laboratory type electrically-heated kiln (Nabertherm N100/
Table 1 14) at 1160 °C. The coloring parameters L*, a*, and b* of the samples
Raw material ratios of the glazes. were measured using a Minolta CR-300 series chromo-meter. L*, a*, b*
Recipe no Red Clay MnO Cu-Co-K-Q
analyses were made three times for every glazed bodies. Then, the
mean values and standard deviations were calculated. Color differences
CuO CoO Kaolin Quartz (ΔE*) were also calculated as ΔE = ([ΔL*]2 + [Δa*]2 + [Δb*]2) [21].
Glaze microstructures were examined by scanning electron microscopy
1 80 10 2.5 2.5 2.5 2.5
2 70 10 5 5 5 5
(FEI NANO SEM 650), fitted with an energy dispersive X-ray analyzer
3 70 20 2.5 2.5 2.5 2.5 (EDS). Coating is not applied onto the surfaces of the glaze samples
4 60 10 7.5 7.5 7.5 7.5 before SEM and EDS analyses.
5 60 20 5 5 5 5
6 60 30 2.5 2.5 2.5 2.5
3. Results and discussion
7 50 10 10 10 10 10
8 50 20 7.5 7.5 7.5 7.5
9 50 30 5 5 5 5 Color (L*, a*, b*) and ΔE* of some studied glazes are represented in
10 50 40 2.5 2.5 2.5 2.5 Table 2. According to CIELAB model L* = 0 represents black and L* =
11 40 10 12.5 12.5 12.5 12.5 100 shows white, a* is green-red at horizontal axis, and b* is yellow-
12 40 20 10 10 10 10
blue at vertical axis [22]. With respect to Table 2, L* values of the
13 40 30 7.5 7.5 7.5 7.5
14 40 40 5 5 5 5 glazes are ranged from 45.28 to 54.81. Generally G 9, G 26 and G 34
15 40 50 2.5 2.5 2.5 2.5 glazes exhibited higher a* and b* values when compared to G 14 and G
16 30 10 15 15 15 15 25. It is observed that, this significant increment caused a color trans-
17 30 20 12.5 12.5 12.5 12.5
formation in glazes and metallic black and gray surfaces turned into
18 30 30 10 10 10 10
19 30 40 7.5 7.5 7.5 7.5 gold-bronze color. L*, a*, and b* of the G 26 glaze is 54.81, 8.96, and
20 30 50 5 5 5 5 22.48, respectively. The total color difference between two objects is
21 30 60 2.5 2.5 2.5 2.5 characterized by ΔE*. This difference is a single value which considers
22 20 10 17.5 17.5 17.5 17.5 the difference between L*, a*, and b* of the sample and standard
23 20 20 15 15 15 15
[21,22]. Amongst the studied glazes, gold-bronze G 26 which has the
24 20 30 12.5 12.5 12.5 12.5
25 20 40 10 10 10 10 highest L*, a*, and b* values is selected as the reference sample of the
26 20 50 7.5 7.5 7.5 7.5 studied system and ΔE* is controlled according to this glaze. In Table 2,
27 20 60 5 5 5 5 it is seen that ΔE* of the G 14 and G 25 glazes are 22.46 and 20.15,
28 20 70 2.5 2.5 2.5 2.5
respectively. On the contrary to these metallic black and gray glazes,
29 10 10 20 20 20 20
30 10 20 17.5 17.5 17.5 17.5
the total color difference is decreased to 11.23 in G 9 and 6.88 in G 34
31 10 30 15 15 15 15 gold-bronze samples.
32 10 40 12.5 12.5 12.5 12.5 Glaze maturation is generally achieved in most of the glazes with a
33 10 50 10 10 10 10 glossy, sateen matt or matt appearance. When designing a glaze com-
34 10 60 7.5 7.5 7.5 7.5
position, clays are one of the most important raw materials as they are
35 10 70 5 5 5 5
36 10 80 2.5 2.5 2.5 2.5 not only colloidally dispersed materials but also constitute the large
amounts and activity in glaze batch [23]. It is determined that in-
creasing amounts of MnO resulted in more glossy surfaces in final
2. Experimental procedure products. Chromium, cobalt, iron, manganese, nickel, copper, vana-
dium and titanium are from transition metal group and generally used
Firstly, a literature review is done in order to prepare metallic glazes as colorants in glaze. Manganese acts as fluxes, increases the fluidity
[3,5,6,14–20] and then a new triaxial glaze system is developed for a and produces clusters of colored crystals [23]. G 14 glaze exhibited a
systematic study (Fig. 1). Table 1 indicates how compositions were silky matte metallic black color with a smooth surface texture while the

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Fig. 2. SEM micrographs of the G 9 glaze showing overall and detailed microstructures.

Fig. 3. EDS patterns of the G 9 glaze taken from the gray and dark areas.

Fig. 4. SEM micrographs of the G 14 glaze showing overall and detailed microstructures.

amounts of red clay and MnO is fixed to 40 wt%, as well as CuO and
CoO amounts are 5 wt%. G 25 glaze started to exhibit a gray matt
metallic effect besides an artistic surface texture. Introducing 7.5 wt%.
CoO and CuO with higher amounts of MnO (50 wt%) following a low
red clay content (20 wt%) in G 26 resulted in a smooth gold-bronze
surface. Similar to G 26 glaze, keeping constant the CuO and CoO to
7.5 wt% and increasing the MnO amount at 60 wt% gave rise to glossy
gold-bronze metallic appearance in G 34 sample at this system. In re-
cent years, copper containing glazes are studied for fritted compositions
and luster glazes [7]. Copper was one of the earliest colorants of glaze
in early Egyptian faience. It gives a wide range of colors from blue to
green and, in special circumstances, red, depending upon composition
and the firing atmosphere. On the other hand, copper is an active flux in
glaze and it will reduce the firing range of any composition to which it
is added [18,22–25].
The surfaces of the G 9, G 14, G 25, G 26 and G 34 glazes were
selected to characterize by using SEM and EDS. General and detailed
microstructural views of the gold-bronze G 9 glaze show a hetero-
geneous microstructure full of triangular and prismatic crystals (Fig. 2).
Light gray triangular crystals exhibit a high level of copper, whereas the
darker areas possess mostly potassium in EDS analyses (Fig. 3). As
opposed to G 9, G 14 sample exhibited a black matt metallic color with

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Fig. 5. EDS patterns of the G 14 glaze taken from the gray and dark areas.

Fig. 6. SEM micrographs of the G 25 glaze showing overall and detailed microstructures.

Fig. 7. EDS patterns of the G 25 glaze taken from the gray and dark areas.

more homogeneously distributed crystals in its microstructure (Figs. 4
and 5).
The metallic luster of glazed ceramics show a colored metallic shine
with golden-yellow, blue, green, etc. Researches on the optical prop-
erties of glazes having a metallic shine explain the metallic effect in
terms of theoretical explanations [16]. Characterization results in this
study revealed that copper and manganese are responsible for the gold
metallic effect.
The microstructural views of the gray matt metallic-effected G 25
glaze are shown in Fig. 6. Light gray crystals are elongated layer by
layer and copper concentration is quite high in the EDS analyses of
these crystals (Fig. 7). When the color is transformed into gold-bronze
in G 26 glaze, it is observed that crystals became prismatic and sharp-
sided (Fig. 8). Both copper and manganese peaks are distinctive in the
graph obtained from crystal and dark area, which attributed to glassy
phase that consists of K, Ca, Si, Al, and O predominantly (Fig. 9).
Copper is detected generally in gray matt and gold-bronze metallic
glaze surfaces, but the morphology and distribution of the crystals are
different as a result of change in glaze composition. The final surface of
the metallic shines is related to the reflection properties of the silver
and copper colloids. According to the theoretical approach of metallic
luster decoration, the refractive index of glaze and the amount of metal

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Fig. 8. SEM micrographs of the G 26 glaze showing overall and detailed microstructures.

Fig. 9. EDS patterns of the G 26 glaze taken from the gray and dark areas.

Fig. 10. SEM micrographs of the G 34 glaze showing overall and detailed microstructures.

oxides directly affect the metallic appearance. The chemical composi-
tion of the glaze batch is the key factor for production of metallic glaze
layer. Therefore, the metal oxide level can yield to various colors and
colored metallic shines [10,16]. EDS results showed that, when Cu and
Mn peaks exist together, the color of the glaze surface changes from
gray matt to gold-bronze metallic surfaces. Variations in the amount of
CuO are more predominant than MnO, although it is one of the most
important glaze constituents in this glaze system. The general and de-
tailed microstructure of the most successful gold-bronze metallic G 34
glaze is represented in Fig. 10. Similar to G 26 glaze, prismatic trian-
gular crystal in this one also exhibited Cu and Mn with a decreased
intensity compared to G 26 in EDS analyses of G 34 glaze (Fig. 11).
Small amounts of Mn and Cu is also detected in the glassy phase of G 34
as well as K, Ca, Si Al and O.
4. Conclusions
The amounts of raw materials directly influence the metallic ap-
pearance and surface texture. In the studied triaxial system, most suc-
cessful gold-bronze glazes are obtained in glazes G 9, G 26 and G 34,
respectively. It is observed that increasing amounts of MnO resulted in
more glossy metallic surfaces; however, the amount of CuO is more

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K. Pekkan et al.
Fig. 11. EDS patterns of the G 34 glaze taken from the gray and dark areas.
decisive than MnO for producing gold-bronze color. Cu and Mn are
detected generally in gold-bronze metallic glaze surfaces but the shape
of the crystals is different with regard to chemical glaze compositions.
Acknowledgments
The authors would like to thank the authorities and members of
ILTEM (Advanced Technology Center) of Dumlupınar University and
Kütahya Seramik A.S. of Turkiye for providing some of the character-
izations to be conducted. Special thanks also go to Yalçın Gün for his
collaboration and contributions relating to the study.
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