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Effect of Nano-NiO Additive on Adhesion Strength and Bubble Structure of

Vitreous Enamels

Article  in  Journal- Korean Physical Society · April 2018

DOI: 10.3938/jkps.72.770

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Journal of the Korean Physical Society, Vol. 72, No. 7, April 2018, pp. 770∼774

Effect of Nano-NiO Additive on Adhesion Strength and Bubble Structure of

Vitreous Enamels

Jaemin Cha
The Institute of Materials Technology, Pusan National University, Busan 46241, Korea

Juhyeong Kim, Jaeyoung Shin and Bongki Ryu∗

Division of Materials Science and Engineering, Pusan National University, Busan 46241, Korea

(Received 8 February 2018, in final form 12 March 2018)

The effect of NiO nanopowder on the adhesion strength and formation of fish-scales in vitreous
enamels has been investigated. The results of a ball drop test indicated that the adhesion strength
was greatly increased by a mill addition of NiO nanopowder. The adhesion strength and bubbling
microstructure of the enamel were studied using optical and scanning electron microscopy (SEM)
in conjunction with energy dispersive spectroscopy (EDS) analysis. The results showed that, as a
mill additive, NiO nanopowder changes the composition and structure at the enamel-steel interface
and enables interdiffusion. In addition, as the amount of mill addition was increased, the size of
the gas bubbles increased and the cracks of the enamel layer, generally referred to as fish-scaling,
were reduced.

PACS numbers: 61.82.Bg, 64.70.kd, 81.05.Pj

Keywords: Enamel, Mill addition, Adhesion Strength, Bubble Structure
DOI: 10.3938/jkps.72.770

I. INTRODUCTION

Enamel refers to a thin layer of glass on a metal sub-

strate. Historically, enamel was primarily used to coat
metals such as gold, silver and copper [1]. Under opti-
mal baking conditions, the enamel produces a composite,
combining with and adhering to the base metal insepa-
rably to prevent corrosion under all environmental con-
ditions [2].
An enamel coating is commonly made of a bilayer.
The ground layer (or first layer) adheres to the metal
body. The cover layer (or surface layer) not only en-
hances the appearance of the piece, but also has protec-
tive properties [2,3]. Recently, single-layer enameling has
become more popular in the production of kitchen appli- Fig. 1. SEM image of nano-NiO powder.
ances, architectural parts, and chemical reactors, gradu-
ally displacing two-layer enameling due to the decreased
number of applications and firings required during fab- ical anchoring. A rough surface is obtained by chemical
rication [4, 5]. Therefore, single-layer enamels must be corrosion and dendrite growth upon firing [6–8]. In the
defect-free in order to provide chemical durability and chemical model, a direct atomic bond must be achieved
adhesion strength at the same time. in an intermediate oxide layer between the metallic bonds
Many of the previous publications on this topic de- of the substrate metal and the ionic bonds of the enamel
scribe theoretical models of adhesion between enamel [9,10].
and steel. In a mechanical model, a rough interface is Fish-scale is a defect due to the hydrogen created dur-
required for strong adherence because it enables mechan- ing the chemical reaction between enamel and steel. The
hydrogen is dissolved in the austenite matrix upon firing,
∗ E-mail: bkryu@pusan.ac.kr; Fax: +82-51-510-2384 especially at temperatures of 800 - 850 ◦ C, and diffuses to

pISSN:0374-4884/eISSN:1976-8524 -770- 2018

c The Korean Physical Society
Effect of Nano-NiO Additive on Adhesion Strength and Bubble Structure· · · – Jaemin Cha et al.
Table 1. Nominal composition of enamel (wt.%).
SiO2 B 2 O3 Al2 O3 Na2 O
Composition
38.6 15.5 10 15
the enamel-steel interface when cooled [11,12]. Accord-
ingly, hydrogen gas accumulates near the enamel-steel
interface, which causes the characteristic cracking of the
glass in fish-scale defects [13,14].
There have been several reports of the use of superfine
Al, Li2 Ni8 O10 powders and nanomaterials as additives to
enhance the strength of the adhesion between enamel and
steel [15–17]. However, there is not interested in either
property. The aim of the present study is to investigate
the effect of the addition of nano-NiO on the adherence
strength and fish-scaling of one-fold enamel layers using
scanning electron microscopy (SEM) and energy disper-
sive spectroscopy (EDS).
II. MATERIALS AND METHODS
1. Preparation of enamel coatings
Sheets of steel (C = 0.08%, Si = 0.03%, Mn = 1.0%)
were treated to remove all surface oil and rust and used
as the enamel substrate. The chemical compositions
of the enamel frit are listed in Table 1. The SEM
image of applied NiO nano particles (D50 = 20 nm,
Purity ≥ 99.99%, Cnvision Co., Ltd.) was shown in
Fig. 1. The enamel frit was manufactured using a typical
procedure, milled down to 200 mesh, and mixed with a
suspension agent, electrolytes, water, and the nano-NiO
powder. The enamel slip was then applied to the pre-
pared steel sheets by a hand-spraying method and dried
at 110 ◦ C for 10 min. After drying, the samples were
fired in a box furnace at 870 ◦ C with soaking time of
5 min.
2. Adherence strength test
The enameling sample was tested by the ball drop
method in accordance with the ASTM B916-01 stan-
dard of enamel adherence strength. After the impact,
the adherence strength was evaluated according to the
remaining area of enamel on the destroyed surface. The
enamel adherence strength was rated as 1st to 5th grade,
in which 1st grade samples were the best. If the majority
of the enamel layer was removed from the steel sheet and
the enamel appeared silver and bright after the impact,
the adherence strength was poor, and the sample was
deemed 5th grade. If the majority of the enamel layer
remained on the steel sheet and the enamel appeared
black in color, the adherence strength was excellent.
-771-
K2 O Li2 O CaF2 P2 O5 TiO2 CoO NiO
8 3 5 2.5 2.1 0.8 0.6
3. Microstructure and element distribution
along the enamel interface
The enameled specimens were cut along the enamel
interface of the cross-section and mounted. The surface
of each cross-section was ground and polished and then
coated with gold film. The microstructure of the enamel
interface of the cross-section was studied by (SEM, Jeol
JSM-5400) and EDS.
III. RESULTS
1. Relationship between enamel adherence and
mill addition of nano-NiO
The photographs of the destroyed surface after the ad-
hesion strength test for samples with varying nano-NiO
additions are shown in Fig. 2, which demonstrates the
relationship between the mill addition and the adhesion
strength of the enamel. In a destroyed surface, the peeled
surface appears white while an unpeeled surface appears
black. When the sample showed larger unpeeled surface,
it means the adhesion strength is high. In the figures,
the white area corresponds to a peeled surface without
enamel, while the black area represents an unpeeled sur-
face with an adhesive enamel layer. The samples treated
with nano-NiO exhibited better adhesion strength than
those without the treatment, and the enamel adhesion
strength increased gradually with the amount of nano-
NiO added (Fig. 2).
2. Microstructures of the enamel interface
A typical SEM micrograph of the enamel-steel inter-
face with/without addition of nano-NiO under identical
conditions is shown in Fig. 3. The interface often be-
comes rough due to chemical reactions, however, the ex-
tent of the dendrite structure within the boundary areas
vary. With increasing additions of nano-NiO, the den-
drite size and surface contact areas increase greatly.
This morphological change reflects the change in the
adhesion strength of the enamel. It is well-known that
dendrites are formed in nucleation and growth stages
from molten enamel during the cooling process. Accord-
ing to thermodynamic principles, the solidification of the
dendrite is a heterogeneous nucleation process, and these
nuclei typically occur on the interface [18,19]. The free
-772- Journal of the Korean Physical Society, Vol. 72, No. 7, April 2018

Fig. 2. (Color online) Photographs of the destroyed enamel surface after the impact test (a) without nano-NiO, (b) 0.5%
nano-NiO added and (c) 1% nano-NiO added.

Fig. 3. Interface morphology of enamel with various contents of the nano-NiO additive (a) without nano-NiO, (b) 0.5%
nano-NiO added and (c) 1% nano-NiO added.

energy of nucleation is divided into a bulk term and a
surface term expressed as follows [20].
4π 3
∆G = R ρn ∆µ + 4πR2 γ, (1)
3 Therefore, it is postulated that the nano-NiO powder
where, ∆µ is the difference in chemical potential between
the nuclear formation and nucleating phases and γ is the
surface tension. The number density of the nucleating
phase is ρn , and R is the radius of nucleus.
According to Lacy [21], the viscosity of silicate glasses
is primarily determined by the non-bridging oxygen
in the tetrahedrally coordinated cation (NBO/T). The
NBO/T value increases with the Fe2+ /Fe3+ ratio; a
larger Fe2+ /Fe3+ ratio enhances depolymerization and
lowers the viscosity. The viscosity of the glass-forming
liquid was reduced because NiO promotes the diffusion
of FeO into the enamel (see Fig. 4 and Eq. (4)) and
therefore increases the Fe2+ /Fe3+ ratio, because Fe3+ is
not stable at 870 ◦ C in the presence of iron [13]. Con-
comitantly, the surface tension decreased, and nucleation
occurred easily. To form enamel, the temperature should
be held above 1300 ◦ C in order to melt NiO, which has
a melting point as high as −1950 ◦ C. Nano-NiO pow-
ders were added to the enamel frit and fired at −870 ◦ C,
which is much lower than the melting point of enamel.
may serve as the nucleation centers necessary for the
growth of the dendrite.
Figure 4 compares the distribution of Fe compositions
over the enamel-steel interface different content of nano-
NiO additions using an EDS line scan analysis. Despite
a rapid decrease in the concentration of Fe as distance
from the glass-to-steel interface increases, in both cases,
the concentration of Fe in the enamel treated with nano-
NiO is much higher than in the enamel without the nano-
NiO. The SEM image suggests that, at the macro scale,
the dendrite structure and related mechanical anchor-
ing process play an important role in determining the
adhesion strength. On a smaller scale, chemical bond-
ing contributes to the adhesion strength at the interface.
As explained by Dietzel’s field strength, Fe2+ is classi-
fied as a network-modifying ion while Fe3+ is intermedi-
Effect of Nano-NiO Additive on Adhesion Strength and Bubble Structure· · · – Jaemin Cha et al. -773-

Fig. 4. The diffusion profiles for the enamel-steel interface: (a)

traces for Fe in samples with various additions of nano-NiO.

ate between a network-forming and a network-modifying

ion [10, 22]. Therefore, these cations can attach to the
enamel using ionic bonding and to the metal using metal-
lic bonding. Because of the dendritic structure of inter-
face and the local change in composition, a transition
zone containing the chemical bonding may exist at the
interface. Also, thermodynamic analysis suggests that
NiO and CoO can be reduced by Fe at high tempera-
tures, forming an alloy with Fe which results in deforma-
tion of the crystal lattice of iron and promotes interdif-
fusion [16]. For adherence agents of glass composition,
the following reaction will enhance during firing.
(b)
Co2+ − Glass (melting) + Fe (solid)
2+
→ Co + Fe − Glass (melting), (2)

Ni2+ − Glass (melting) + Fe (solid)

→ Ni + Fe2+ − Glass (melting). (3)

After the reaction, the Co2+ and Ni2+ are reduced and
deposited on the Fe substrate, forming the alloy. FeO (a
source of Fe ions) was dissolved into the glass-forming
liquid, developing the transition layer, which leads to
high adhesion strength.
During the mill addition of the NiO adherence agents,
the following reaction occurs during the firing [13,16] : (c)

NiO (Solid) + Fe (solid) + Glass (melting) Fig. 5. Typical tapered cross-section SEM images with
varying contents of the nano-NiO additive (a) without nano-
→ Ni + Fe2+ − Glass (melting). (4) NiO, (b) 0.5% nano-NiO added and (C) 1% nano-NiO added.

The equation for the change in Gibbs free energy dur-

ing the reaction is
the formation of excess FeO at the interface. Further-
◦ more, according to X. Yang, due to the absence of nickel
∆G (J/mole · Fe) = −28137 + 21.8T. (5)
oxide on the surface, oxide scales formed at high temper-
The negative values of ∆G◦ indicate that the metal- atures do not dissolve completely in the glass, leading to
lic Ni and FeO can form during firing. It can therefore a relatively low iron concentration within the glass [13].
be concluded that the reaction in Eq. (4) contributes to Thus, the enamel in the interface is saturated with FeO,
-774-
achieving strong chemical bonding to the substrate.
3. Bubble structure of an enamel cross-section
The bubble images are shown in Fig. 5, which shows
the difference between the bubble structures in the sam-
ples with and without the addition of nano-NiO. There
are a smaller number of larger bubbles in the sample with
the addition of nano-NiO than in the sample without the
addition.
Hydrogen, the major component of the gas evolved at
elevated temperatures, dissolves in the austenite matrix.
It is then expelled from the steel upon cooling due to
its reduced solubility in the ferrite matrix. Hydrogen
evolution reactions in the enamel can be described by
Eq. (6) at high temperatures
Fe + H2 O = H2 + FeO (6)
and by Eqs. (7) and (8) at low temperatures
2Fe + 3H2 O = Fe2 O3 + 3H2 , (7)
3Fe + 4H2 O = Fe3 O4 + 4H2 . (8)
As mentioned above, NiO promotes the diffusion of
FeO into the enamel and the reduction of viscosity. In a
low viscosity enamel, the nucleation of bubbles is much
easier due to the concomitant reduction in surface ten-
sion [13]. The images in Fig. 5 of the microstructures
of the bubbles show that the sample with added nano-
NiO contains a high proportion of large bubbles and area
fraction but has a low bubble density.
Fish-scale was not observed in any the enameled sam-
ples with a low magnification optical microscope. How-
ever, after 24 h, traces of fish-scale were visible in the
samples without the addition of nano-NiO, as shown in
Fig. 5. The major cause of fish-scale is the compressive
stress on the enamel resulting from the difference be-
tween the thermal expansion coefficients of the enamel
and the steel [9]. The connectivity of larger bubbles gen-
erally provides an escape route from the steel for gases
and also serves as a reservoir for the gas by reducing the
gas pressure in the steel/enamel interface [13,14]. As a
result, large bubbles have a positive effect on the reduc-
tion of fish-scaling.
IV. CONCLUSION
We investigated the effect of nano-NiO additive on ad-
hesion strength and bubble structure of vitreous enam-
els to further the development of enamel. The effects
of nano-NiO additive on adhesion strength were studied
by ball drop test, SEM and EDS. The addition of NiO
powder increases the number and size of dendrites at the
interface and promotes the diffusion of Fe-ions from the
View publication stats
Journal of the Korean Physical Society, Vol. 72, No. 7, April 2018
steel substrate into the enamel. The strength of adhe-
sion between enamel and steel has been greatly enhanced
by the addition of nano-NiO powder. Bubble structures
were studied by SEM. The structure of the bubble affects
the tendency off enamels to form fish-scale defects.
ACKNOWLEDGMENTS
This research was supported by the Ministry of Trade,
Industry & Energy (MOTIE), Korea Institute for Ad-
vancement of Technology (KIAT) and Ulsan Institute
For Regional Program Evaluation (IRPE) through the
Encouragement Program for The Industries of Economic
Cooperation Region.
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