Materials and Design 59 (2014) 461–465

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Materials and Design

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Short Communication

Antibacterial and mechanical properties of honeycomb

ceramic materials incorporated with silver and zinc
Shaoxin Yang a, Yihe Zhang a,b,c,⇑, Jiemei Yu a, Zhichao Zhen b, Taizhong Huang a,⇑, Qi Tang a, Paul K. Chu c,
Lei Qi a, Hongbo Lv a
a
Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, University of Jinan, Jinan 250022, China
b
National Laboratory of Mineral Materials, School of Material Science and Technology, China University of Geosciences, Beijing 100083, China
c
Department of Physics & Materials Science, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, China

a r t i c l e i n f o a b s t r a c t

Article history: The antibacterial and mechanical properties of heat-resistant honeycomb ceramic materials produced
Received 28 January 2014 from red mud industrial waste and doped with Zn and Ag are determined. Excellent antibacterial effects
Accepted 11 March 2014 against Escherichia coli are obtained by the plate counting and vibration methods. When 5% and 6% Zn are
Available online 21 March 2014
added to the honeycombs doped with 0.3% Ag, the antibacterial rates reach 98.9% and 99.5%, respectively.
The mechanical properties are evaluated by monitoring the bending strength, open porosity, water
absorption capability, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The Zn and Ag
particles are distributed uniformly in the honeycomb ceramics and the crystalline structure of the cera-
mic materials is not altered after Zn and Ag incorporation consequently enabling good dispersion of the
antibacterial metals.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction the effects of water disinfection between Escherichia coli (ATCC

Much attention is paid to problems associated with environ-
mental pollution and health nowadays and antibacterial materials
are needed in many fields such as sewage disposal, biomedical
engineering, environmental protection and buildings [1–11]. Hea-
vy metals such as silver, zinc, copper, mercury, tin, lead, bismuth,
cadmium, chromium, and thallium are known to possess antibac-
terial properties and incorporation of these metals into zeolites
produces antibacterial activity [12]. The in vitro antibacterial activ-
ity against multi-resistant bacteria and in vitro cytotoxicity of
polymethylmethacrylate bone cement loaded with metallic silver
particles with a size of 5–50 nm called NanoSilver were investi-
gated [13], and Balamurugan and Balossier [14] evaluated the
in vitro antibacterial and biological activity of silver-incorporated
bioactive glass SiO2–CaO–P2O5–Ag2O (AgBG). Silver (Ag) was intro-
duced into polyethylene terephthalate (PET) by the filtered catho-
dic vacuum arc (FCVA) technique [15] and Shi et al. [16]
investigated the use of chitosan nanoparticles (CS NP) and quater-
nary ammonium chitosan nanoparticles (QCS NP) as bactericidal
agents in poly(methyl methacrylate) (PMMA) bone cement with
and without gentamicin. De la Rosa-Gómez et al. [17] compared
⇑ Corresponding authors.
E-mail addresses: zyh@cugb.edu.cn (Y. Zhang), chm_huangtz@ujn.edu.cn
(T. Huang).
8739) and total coliform micro-organisms from synthetic waste-
water or municipal wastewater and the anti-bacterial activity of
silver-modified clinoptilolite–heulandite rich tuff (ZS Ag) was
studied. Hernández-Sierra [18] compared the bactericidal and bac-
teriostatic effects of silver, zinc oxide, and gold nanoparticles on S.
Mutans by employing the liquid dilution method and determined
the minimum inhibitory concentrations (MICs) using subcultures
to obtain the minimum bactericidal concentrations (MBCs). The
influence of particle size on the antibacterial activity of ZnO pow-
ders was investigated using different particle size ranging from 0.1
to 0.8 mm [19]. By measuring the change in the electrical conduc-
tivity with bacterial growth, it was found that the antibacterial
activity of ZnO increased with smaller particles and larger powder
concentrations. Li and Hong [20] found significant improvement in
the Young’s modulus and tensile strength of PU films by incorpo-
rating ZnO nanoparticles to up to 2.0 wt% and that the abrasion
resistance of the PU coats was greatly enhanced after addition of
ZnO nanoparticles. Osinaga and Grande [21] evaluated the effects
of ZnSO4 addition to a conventional glass ionomer and resin-mod-
ified glass ionomer on the solubility, flexural strength, zinc and
fluoride release, as well as Streptococcus mutans growth inhibition.
The objective of this study is to determine the effects of inor-
ganic antibacterial agents on honeycomb ceramic materials as
shown in Fig. 1. The antibacterial properties and mechanical
behavior are evaluated systematically.

http://dx.doi.org/10.1016/j.matdes.2014.03.025
0261-3069/Ó 2014 Elsevier Ltd. All rights reserved.
462 S. Yang et al. / Materials and Design 59 (2014) 461–465

2. Experimental procedures

Red mud (RM) was chosen as the raw materials to produce

heat-resistant honeycomb ceramics containing two inorganic anti-
bacterial agents, Ag+ and Zn2+. Based on previous results, the opti-
mal honeycomb ceramic samples were produced. The mixtures
containing the perform body and custom-made inorganic antibac-
terial agents in different proportions were used and an economical
and efficient technique, wet ceramic powder process in combina-
tion with co-firing, was employed to fabricate the antibacterial
ceramic materials.
The antibacterial performance was assessed on samples with
dimensions of 2 mm3 and weighing 1–2 g. The experiments involv-
ing the nutrient broth culture medium (NB), nutrient agar culture
medium (NA), eluent and bacteria suspension, culture preserva-
tion, and activation of culture were performed according to GB/T
21551.2-2010 [22]. Fig. 2 illustrates the antibacterial tests. The
antibacterial efficacy against E. coli was measured by the vibration
and plate counting methods. Initially, the samples, including the
reference, were soaked in 70% ethanol for 1 min, washed with ster-
ile water, and dried naturally. After high-temperature humid or dry
sterilization, the samples were transferred to sterilized petri dishes
to which 0.2 ml of the bacteria suspension was introduced. Three
samples from each group were tested to improve the statistics.
The samples were transferred to sterilized conical flasks and sealed
while making good contact with the bacteria suspension in a con-
stant-temperature 80 rpm bath oscillator for (24 ± 1) h at
(37 ± 1) °C and RH (relative humidity) of over 90%. Afterwards,
20 ml of the eluent were taken to a conical flask and the samples
were washed repeatedly. The eluent after gradient dilution was
inoculated in the agar culture medium (NA) and cultured at
(37 ± 1) °C for 24–48 h. The bacteria counting method according
to GB/T 21551.2-2010 [22] was utilized to determine the number
of living bacteria in the eluent. The antibacterial rate was calcu-
lated according to the following formula:
R ¼ ðB  AÞ=B  100 %;
where R is the antibacterial rate, A is the average recovery bacterial
count of the sample (CFU), and B is the average recovery bacterial
count of the blank control (CFU).
The compressive strength of the sintered ceramic samples was
evaluated based on Chinese National Standard GB/T 4740-1999
[23], whereas the water absorption, bulk density, and apparent
porosity were determined in accordance with Chinese National
Standard GB/T 3810.3-2006 [24]. The structure was determined
by X-ray diffraction (XRD) at 40 kV and 40 mA by measuring 2h
from 5° to 80° with a step size of 0.02° and time of 5 s per step.
The powder diffraction patterns were analyzed using a software
package program and microstructure of the thermally treated
specimens was determined by scanning electron microscopy
(SEM).
Fig. 2. Antibacterial test flow.
3. Results and discussion
Introduction of a larger amount of an antibacterial agent trans-
lates into a wider distribution in the honeycomb ceramic materials
and stronger inhibition of bacteria. The antibacterial effects evalu-
ated by the plate counting method against E. coli are shown in
Figs. 3–6 and Tables 1 and 2. Fig. 3 shows that the antibacterial rate
is 98.9% when the Zn concentration is 5%. This is due to leaching of
zinc ions with the opposite charge of the bacteria from the honey-
comb structure and killing them. It is known that silver has more
potent antibacterial effects than zinc [25] and Fig. 4 shows that
1% Ag in the honeycomb structure can kill about 98.7% of the E. coli
in the solution. However, sliver is more expensive and so it is
worthwhile to study the combined effects of Zn and Ag to achieve
ð1Þ the optimal performance and cost. The Ag and Zn incorporated
materials possess excellent antibacterial properties and as shown
in Fig. 5, the honeycomb with 0.5% Ag shows an antibacterial effi-
cacy of more than 97.6% which is slightly better than that obtained
with 0.3% Ag. When the 0.3% Ag materials are further doped with
5% and 6% Zn, the antibacterial rates reach 98.9% and 99.5%, respec-
tively. It is thus obvious that the antibacterial performance can be
improved by co-doping with Ag and Zn and from commercial con-
siderations, 0.3% Ag is better than 0.5% Ag because the former is
cheaper.
According to Fig. 7, the bending strength, open porosity, and
water absorption properties of the antibacterial honeycomb cera-
mic materials are similar to those of the control. It is believed that
the incorporated antibacterial agents do not affect the structure of
the bulk materials thus preserving the good mechanical properties.
The effects of addition of silver and zinc are investigated with XRD

Fig. 1. Schematic illustration of the cross section of the honeycomb ceramic carrier.
 S. Yang et al. / Materials and Design 59 (2014) 461–465 463

Fig. 3. Antibacterial ratios against E. coli (Zn2+-loaded). Fig. 5. Antibacterial ratios against E. coli (Ag+ and Zn2+-loaded).

Table 1
Description of tested formulations in terms of the raw materials and corresponding
antibacterial rates [Red mud (RM) and Antibacterial agent (AA)].

RM:AA (Zn) Antibacterial ratio (%) RM:AA (Ag) Antibacterial ratio (%)
99:1 16.8 99.7:0.3 92.3
98:2 47.7 99.5:0.5 95.7
97:3 69.5 99.0:1.0 98.7
95:5 98.9 98.5:1.5 99.9
93:7 99.1 98.0:2.0 99.9
90:10 99.7 97.5:2.5 99.9
87:13 99.9 97.0:3.0 99.9
85:15 99.9

and Fig. 8 shows the broad-angle XRD patterns of the three types of
antibacterial honeycomb ceramics. The typical narrow silver dif-
fraction peaks at 2h of 38.1°, 44.3°, 64.5°, and 77.5° correspond to
the (1 1 1), (2 0 0), (2 2 0), and (3 1 1) Bragg’s reflections of face-cen-
tered cubic crystalline silver. The typical zinc diffraction peaks at
2h of 31.77°, 34.42°, 36.25°, 56.60°, and 66.38° represent the
(1 0 0), (0 0 2), (1 0 1), (1 1 0), and (2 0 0) Bragg’s reflections of face-
Fig. 4. Antibacterial ratios against E. coli (Ag+-loaded).
centered cubic crystalline zinc. Furthermore, the characteristic

Fig. 6. Photographs of honeycomb ceramic materials (Ag+-loaded) cultured with E. coli.

464 S. Yang et al. / Materials and Design 59 (2014) 461–465

Table 2
Description of tested formulations in terms of the raw materials and the correspond-
ing antibacterial rate. Red mud (RM) and Antibacterial agent (AA).

RM AA AA Antibacterial RM AA AA Antibacterial
(Ag) (Zn) ratio (%) (Ag) (Zn) ratio
98 0.3 1.7 92.7 96.5 0.5 3.0 97.6
97 0.3 2.7 93.3 95.8 0.5 3.7 98.6
96.7 0.3 3 94.9 95.5 0.5 4.0 99.3
96 0.3 3.7 96.9 94.8 0.5 4.7 99.7
95.7 0.3 4 97.5 94.5 0.5 5 99.9
95 0.3 4.7 98.4 93.5 0.5 6 99.9
94.7 0.3 5 98.9 92.5 0.5 7 99.9
93.7 0.3 6 99.5
92.7 0.3 7 99.9

Fig. 9. SEM image and X-ray analysis of Zn2+-loaded antibacterial honeycomb

ceramic materials.

Fig. 7. Bending strength, open porosity and water adsorption of the antibacterial
honeycomb ceramic materials and blank sample.

Fig. 8. X-ray diffraction patterns of honeycomb ceramic materials (A, Zn2+-loaded), Fig. 10. SEM image and X-ray analysis of Ag+-loaded antibacterial honeycomb
(B, Ag+-loaded), and (C, Ag+ + Zn2+-loaded). ceramic materials.
 S. Yang et al. / Materials and Design 59 (2014) 461–465
Fig. 11. SEM image and X-ray analysis of Ag+ + Zn2+-loaded antibacterial honey-
comb ceramic materials.
peaks of silver and zinc imply the existence of large and crystalline
silver and zinc particles in the matrix. As a result, the crystal struc-
ture of the carrier is not altered enabling good dispersion of the
antibacterial metals throughout the materials.
SEM is conducted to examine the surface morphology and size
distribution of the antibacterial honeycomb ceramic materials.
Figs. 9–11 depict the SEM images of the Zn-doped, Ag-doped,
and Ag and Zn co-doped materials, respectively. The figures reveal
heterogeneity and EDS confirms the existence of Zn and Ag in the
honeycomb structure with a porous surface.
4. Conclusions
Using red mud industrial waste as the raw materials, honey-
comb ceramic materials are produced and subsequently endowed
with antibacterial properties by doping with silver and zinc. When
5% and 6% Zn are further added to the honeycombs doped with
0.3% Ag, the antibacterial rates reach 98.9% and 99.5%, respectively.
From the commercial standpoint, the use of 0.3% Ag is better than
0.5% Ag because the former is cheaper. The bending strength, open
porosity, and water absorption capability of the materials are not
compromised by the addition of the two antibacterial agents. Scan-
ning electron microscopy and X-ray diffraction reveal the existence
of large and crystalline silver and zinc particles in the matrix. As a
result, the crystal structure of the carrier is not altered enabling
good dispersion of the antibacterial metals throughout the
materials.
465
Acknowledgements
The authors acknowledge the financial support provided by Na-
tional High-Tech Research and Development Program of China
(863 Program, 2012AA06A109) and Guangdong – Hong Kong Tech-
nology Cooperation Funding Scheme (TCFS) GHP/015/12SZ.
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