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CERAMICS
INTERNATIONAL
Ceramics International 41 (2015) 10160–10169
www.elsevier.com/locate/ceramint

Effect of zinc oxide and zirconia on structure, degradability and in vitro

bioactivity of wollastonite
H.C. Lia,b, D.G. Wanga,b,n, C.Z. Chena,b,n
a
Key Laboratory for Liquid–Solid Structural Evolution & Processing of Materials, Ministry of Education, Shandong University, Ji’nan 250061, Shandong, People’s
Republic of China
b
School of Materials Science and Engineering, Shandong University, Ji’nan 250061, Shandong, People’s Republic of China
Received 23 February 2015; received in revised form 19 April 2015; accepted 20 April 2015
Available online 27 April 2015

Abstract

The partial substitution of ZnO or ZrO2 for CaO in CaO–SiO2 system was performed by sintering sol–gel derived precursor. The effects of
ZnO and ZrO2 on structure, mechanical properties, in vitro bioactivity and degradability of the CaO–SiO2 ceramic were studied. Their pore size
distribution was analyzed by the Barrett Joyner Halenda (BJH) method using Surface Area Analyzer (SAA). The bending strength and elastic
modulus were determined by the three-point bending method. The degradability was evaluated in tris-(hydroxymethyl)-aminomethane and
hydrochloric acid (Tris–HCl) buffer solution and the bioactivity by in vitro assays in simulated body fluid (SBF). Results indicate the main crystal
phase to be wollastonite beta-CaSiO3. A new Ca2ZnSi2O7 phase appears in the sample doped with ZnO, and t-ZrO2 appears in the sample doped
with ZrO2. The addition of ZnO or ZrO2 decreases the total pore volume of wollastonite, improves the bending strength of wollastonite. The
elastic moduli of all produced ceramics match that of human body bone. After soaking in Tris–HCl solution, the samples doped with ZnO or
ZrO2 present a lower weight loss. All samples have shown the ability of apatite induction in SBF solution.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: A. Sol–gel processes; C. Mechanical properties; D. ZnO; D. ZrO2; Wollastonite

1. Introduction hard tissue regeneration [5–7]. An ideal biomaterial should have

Bioceramics have received considerable attention because of
their important role in hard tissue repair and tissue engineering.
Kokubo’s study [1] suggested the components of CaO and SiO2
are the main cause of bone-bonding with the bone tissue in the
body. In recent years, calcium silicate materials have been
proved to be bioactive and the bioactivity can enhance the in-
growth of bone tissue to achieve full integration with living
bone tissues [2,3]. Wollastonite (CaSiO3) is an important
compound in the ceramic and cement industries [4]. Moreover,
wollastonite has been investigated as a new type bioceramic for
n
Corresponding authors at: Shandong University, Jing Shi Road 17923,
Ji’nan 250061, Shandong, People’s Republic of China.
Tel./fax: þ86 531 88395991.
E-mail addresses: wangdg@sdu.edu.cn (D.G. Wang),
czchen@sdu.edu.cn (C.Z. Chen).
a proper balance between mechanical properties and degrad-
ability, and the ideal mechanical properties need to match that of
human body bone. The elastic modulus of the cancellous bone
of human body is between 0.1 and 0.5 GPa, and the compres-
sive strength is between 4 and 12 MPa [8]. The elastic modulus
of the compact bone of human body is between 12 and 18 GPa,
and the compressive strength is between 130 and 180 MPa [8].
A proper mechanical strength is necessary to maintain the shape
against the stress during the surgical procedure and recovery [9–
11]. However, the fast dissolution rate and the lower mechanical
strength of wollastonite have severely hindered its clinical
applications [12–14]. These problems can be solved by devel-
oping multiphase materials containing highly dissolvable phases
and stable phases [15–19].
In recent years, some related researches have reported the effect
of additives on the properties of biomaterial. Chang [9] fabricated
45S5 bioglass reinforced macroporous calcium silicate ceramic and

http://dx.doi.org/10.1016/j.ceramint.2015.04.117
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 H.C. Li et al. / Ceramics International 41 (2015) 10160–10169
found that 45S5 bioglass significantly improved the mechanical
strength, bioactivity and degradability of the macroporous calcium
silicate ceramic. Ning’s study [20] showed that Na2CaSiO4 could
quickly induce the bone-like apatite formation in simulated body
fluid through a silicon-rich layer. De Aza [19] investigated the
effect of magnesium on the thermal and mechanical properties of
Ca3(PO4)2–CaSiO3–CaMg(SiO3)2 glasses. Salman [21] studied the
effects of TiO2 or ZnO additives on the properties of glass–
ceramics based on diopside–wollastonite–fluoroapatite–sodium
silicate system. Vallet-Regı ́ [22] studied the influence of the
phosphorus on the crystallization and bioactivity of CaO–SiO2
ceramic, and his results showed the presence of phosphorus
decreased the flexural strength, but increased the formation rate
of the apatite layer. Zreiqat [23] incorporated titanium into CaSiO3
to produce a ceramic with improved chemical stability and
biological property. Hence, to obtain a biomaterial with excellent
properties, it is necessary to modify the bioactive wollastonite by
adding other components.
A right amount of ZnO has no toxic side effects on the
human body and can also enhance cell proliferation [24]. ZrO2
does not release harmful substances and it is often used in dental
and orthopaedic applications [25–27]. Kamitakahara [28] stu-
died the effect of ZnO content on the chemical durability and
apatite-forming ability of CaO–SiO2–P2O5–CaF2 glass–ceramic
by in vitro assays. Zreiqat [29] developed novel scaffolds
through controlled substitution and incorporation of strontium
and zinc into a calcium–silicon system. Marghussian’s study
[30] showed ZrO2 improved the chemical durability and
bending strength of CaO–TiO2–P2O5 microporous glass–cera-
mic. Hong [31] studied the effect of ZrO2 on the physical and
mechanical properties of wollastonite, and the properties of
wollastonite can be obviously improved by these additives.
Banijamali et al. [32–35] investigated the effects of ZrO2 on the
properties of the glass–ceramic. However, there are few studies
about the effects of ZnO or ZrO2 on structure, mechanical
properties, degradability and in vitro bioactivity of wollastonite.
Many techniques for preparing wollastonite have been used
in experiment research. Long [36] fabricated dense CaSiO3
ceramics through spark plasma sintering technique using
CaSiO3 powder prepared by chemical precipitation method.
Ni [37] synthesized CaSiO3 powder by a chemical precipitation
method. Siriphannon [38] fabricated CaSiO3 from coprecipitated
powder using NaOH as precipitant. The use of sol–gel
procedures for synthesising calcium–silicate has attracted
increasing attention in recent years [39,40]. Sol–gel method
provides a more maneuverable way to synthesize biomaterials,
and it has more advantages with simple equipment, process easy
to control, high product purity and uniformity [41–43]. More-
over, gel-derived calcium–bioceramics have better bioactivity
because their porous structure improves their bioactivity and
biocompatibility [39].
Therefore, in this work, ZnO or ZrO2 has been incorporated into
wollastonite using sintering sol–gel derived precursor. The objec-
tive of this study is to evaluate the influence of ZnO and ZrO2 on
structure, mechanical properties, degradability and in vitro bioac-
tivity of wollastonite to find a ceramic with improved properties for
the biomedical applications.
10161
2. Materials and methods
2.1. Ceramic preparation
Three ceramics CaO–SiO2 (CS), the substitution of 5 mol%
ZnO for CaO in CaO–SiO2 system (CS–Zn) and the substitu-
tion of 5 mol% ZrO2 for CaO in CaO–SiO2 system (CS–Zr)
were performed by sintering sol–gel derived precursor using
calcium nitrate tetrahydrate (Ca(NO3)2  4H2O, AR, Sinopharm
Chemical Reagent Co., Ltd., China), tetraethyl orthosilicate
((C2H5O)4Si, TEOS, AR, Tianjin Kemiou Chemical Reagent
Co., Ltd., China), zinc nitrate hexahydrate (Zn(NO3)2  6H2O,
AR, Sinopharm Chemical Reagent Co., Ltd., China) and
zirconium oxychloride (ZrOCl2  8H2O, AR, Sinopharm Che-
mical Reagent Co., Ltd., China) as raw materials. The
synthesis procedure was as follows: the TEOS was mixed
with water and HNO3 (mol of H2O/(mole of TEOS)¼ 4).
Nitric acid (2N) was used as catalyzer with a molar ratio of
HNO3/TEOS ¼ 0.03. After stirring 0.5 h, the saturated solution
of Ca(NO3)2  4H2O and/or Zn(NO3)2  6H2O and/or
ZrOCl2  8H2O was added and continued to stir 1 h. Then the
sol was placed at room temperature till the gel appeared. After
that, kept the gel at 60 1C for 3 days and then dried at 120 1C
for 24 h, followed by ball milling to obtain the powders with
sizes less than 74 μm. The powders were stabilized at 700 1C
for 1 h to make the residual water, ethanol and nitrates used in
the experiment evaporate and then sintered at 950 1C for 0.5 h
with a heating rate of 5 1C/min. For the preparation of the
ceramic blocks, the mixture of stabilized powders and appro-
priate amount of 7 wt% polyvinyl alcohol water solution
binders was uniaxially pressed at 200 MPa and then the
compact samples were sintered at 950 1C for 0.5 h. Two kinds
of ceramic blocks were prepared in this experiment. The first
one was cuboid of 36 mm  4 mm  3 mm used to study the
bending strength and elastic modulus. The other was disc of
10 mm diameter and 2 mm height used to study degradability
and bioactivity.
2.2. Characterization
X-ray diffraction (XRD) investigations were made by
Shimadzu XRD-6100 X-ray diffractometer using CuKα radia-
tion (λ¼ 1.5406 nm) produced at 40 kV and 40 mA in the 2θ
range from 101 to 701 at 0.02 steps with a scan rate of 41/min.
The morphology and element composition were made on
Scanning electron microscope (SEM, Hitachi S-3400N) and
energy dispersive spectrometer (EDS, Horiba EMAX x-act).
For section morphology observation, the ceramics were pre-
pared using standard polishing procedures. Fourier transform
infrared spectroscopy (FTIR) analyses were performed on a
Bruker Optics VERTEX-70 FTIR spectrometer using KBr
pellets in the range of 400–2000 cm  1 with a transmission
mode, and the resolution was 4 cm  1 and the number of scans
was 32. The pore size distribution was analyzed by the Barrett
Joyner Halenda (BJH) method using Surface Area Analyzer
(SAA, BECKMAN COULTER, SA3100). The adsorbed gas
was nitrogen, the carrier gas was helium, and the cooling bath
10162 H.C. Li et al. / Ceramics International 41 (2015) 10160–10169
was liquid nitrogen. The outgassing temperature was 120 1C
and the outgassing time was 90 min.
2.3. Mechanical properties of ceramics
The bending strength and elastic modulus of the ceramics
were determined by the three-point bending method in RGD-5
type electronic tensile machine (span was 30 mm, and the
movement speed of indenter was 0.5 mm/min). The experi-
mental results were calculated from three testing samples. The
results of the performance test were evaluated using the
following equation:
3PL
σf ¼
2bh2
L3 ðP2  P1 Þ
E¼
4bh3 ðY 2  Y 1 Þ
ðL ¼ 30 mm; b ¼ 4 mm and h ¼ 3 mmÞ
where σf is the bending strength (Mpa), E is the elastic
modulus (Gpa), P is the fracture load (N), L is the sample
span (mm), b is the sample width (mm) and h is the sample
depth (mm). P1 and P2 is the load (N) of the starting point and
end point in any straight line in plastic strain stage in the load–
deflection curve. Y1 and Y2 is the deflection (μm) of the mid-
span load corresponding to P1 and P2.
2.4. Weight loss of ceramics in tris-(hydroxymethyl)-
aminomethane and hydrochloric acid buffer solution
(Tris–HCl)
The degradability of the ceramics was evaluated in tris-
(hydroxymethyl)-aminomethane and hydrochloric acid (Tris–
HCl) buffer solution with a pH value of 7.4 at 36.5 1C, using
triplicate samples according to the ISO 10993-14 standard.
During soaking, the volume of buffer solution was 22 ml and
the solution was continuously replaced every 2 days. At
the end of each period of soaking time (1, 3 and 7 days),
Fig. 1. XRD patterns and FTIR spectra of ceramics.
the samples were collected from solution, rinsed with pure
alcohol and deionized water, and then dried to constant weight
measured on an electronic balance. Finally, the weight of each
sample was measured using a type of FA2104 electronic
balance with an accuracy of 0.1 mg and the weight loss was
expressed as the percentage of the initial weight.
2.5. Apatite-forming ability of ceramics in simulated body
fluid (SBF)
The assessment of in vitro bioactivity was evaluated by
soaking the samples in simulated body fluid (SBF), and the
preparation of SBF solution adopted the method proposed by
Kokubo et al. [44]. The SBF solution has a composition and
concentration similar to the inorganic parts of human plasma.
During soaking process, the simulated body fluid contained in
sterile polyethylene containers, and the volume of simulated
body fluid was 22 ml. These containers were sealed and placed
in a water bath with constant temperature at 36.5 1C, and the
SBF solution was continuously replaced every 2 days. The
change in pH values of SBF solution was measured by
Sartorius PB-10 pH-meter. After being soaked, the samples
were rinsed with absolute ethyl alcohol and deionized water,
and then dried in air at room temperature. The newly formed
layer on the sample surface was determined by XRD, FTIR,
SEM and EDS analysis as described above.
3. Results and discussion
3.1. Characterization of ceramics
Fig. 1 shows the XRD patterns and FTIR spectra of the
ceramics. The XRD pattern of sample CS is agreement with the
standard XRD patterns for wollastonite β-CaSiO3 (JCPDS 84-
0655). When adding 5 mol% ZnO, a new phase of Ca2ZnSi2O7
(JCPDS 72-1603) appeared, which indicates that Zn can react with
Ca, Si and O forming a new crystal phase. When 5 mol% ZrO2
 H.C. Li et al. / Ceramics International 41 (2015) 10160–10169
was added, the peak intensity of wollastonite was significantly
increased and the peaks of t-ZrO2 (JCPDS 79-1770) were
observed. From the FTIR spectra of the ceramics, the double
peaks at 1066 and 1024 cm  1 corresponding to the asymmetric
stretching mode Si–O(s, asym) and the absorption bands at 692
and 663 cm  1 assigned to the symmetric stretching vibration
Si–O–Si (s, sym) were observed. Moreover, the silicate absorption
bands at 563 and 464 cm  1 assigned to the bending vibration
Si–O were observed, in which the peak at 563 cm  1 belongs to
the silicon-non-bridging oxygen bond and the peak at 464 cm  1
belongs to the silicon–oxygen bond. The non-bridging oxygen
(NBO) bond of Si–O–NBO was found at 954 cm  1. When
adding ZnO or ZrO2, the peak at 1066 cm  1 corresponding to
Si–O(s, asym) shifted to the large wave number part slightly, and
the peaks at 692 and 663 cm  1 assigned to Si–O–Si (s, sym)
shifted to the lower wave number part. Moreover, another
Si–O–NBO at 902 cm  1 was observed. In addition, the stretching
vibration peak denoting OH  due to the deformation mode of H–
O–H was observed at 1635 cm  1. The peak at 1417 cm  1
corresponding to CO2 3 was observed, which reason may be that
the sample in powder form synthesized from the sol–gel method
has high activity and it can react with carbon dioxide under
atmospheric conditions to produce CO2 3 . Besides, the peak at
1384 cm  1 corresponding to NO3 was observed due to the
residual nitrate. OH  , CO2
3 and NO3 appeared in the FTIR
spectra, while there were no phases contained OH  , CO2 3 and
NO3 in the XRD pattern, which is caused by the fact that the
technology of FTIR probes short-range structural order, whereas
XRD pattern reveals the phase existed in the material.
Fig. 2 shows the SEM micrographs of the ceramics. The
sample surface was coarse and a lot of small granules were
compactly distributed on the surface of sample CS. When
adding ZnO or ZrO2, the surface became compact and some
pores appeared.
The pore diameter vs. pore volume of the ceramics is shown
in Fig. 3. From this figure, it can be seen the pore diameter was
very small, and for smaller pore diameter, the pore volume was
larger. The addition of ZnO or ZrO2 decreased the total pore
volume, indicating that ZnO or ZrO2 increase the density of the
ceramic. An ideal material should be biocompatible and have a
proper balance between mechanical properties, a porous archi-
tecture, and degradability [45,46]. For bone tissue engineering
scaffolds, a sufficient macroporosity is one of the most
important prerequisites to achieve successful integration into
Fig. 2. SEM micrographs of ceramics ((a) CS; (b) CS–Zn; (c) CS–Zr).
10163
the human body. It is worth noting that the macroporosity is
good for bone ingrowth, while it can reduce the strength of the
ceramics.
3.2. Mechanical properties of ceramics
The results of the bending strength and elastic modulus of
the ceramics are shown in Fig. 4 and Fig. 5 is the load–
deflection curve of the ceramics. A sudden change in deflec-
tion presented when the ceramic was close to the fracture. It is
clear to see the elastic moduli of all produced ceramics
matched that of human bone. These bioceramics may be
recommended for orthopedic applications. The addition of
ZnO or ZrO2 made the bending strength significantly increase.
The results in Fig. 3 also confirm this conclusion. ZnO or ZrO2
decreased the total pore volume of wollastonite, increased its
density, and then improved the mechanical strength. Too much
macroporosity is not good for mechanical property. When
preparing the ZnO doped precursor, ZnO acts as a network
modifier, and the modifying character of Zn2 þ is smaller than
Ca2 þ due to the larger Dietzel’s ionic field strength of Zn2 þ in
comparison to Ca2 þ . So when CaO is partly replaced by ZnO,
the network structure becomes tighter. On the other hand, the
bond energy of Zn–O is larger than Ca–O, when using Zn–O
to replace CaO, the structure is more compact, making the
density and strength increase [47,48]. The effect of ZrO2 on
the bending strength is more obvious. Some literatures
reported the transition from t-ZrO2 into m-ZrO2 can partially
or completely absorb or dissipate the energy of these cracks.
Such considerable enhancement in toughness may be owing to
its martensitic phase transformation of tetragonal to monoclinic
symmetry [49–52]. In addition, many factors, such as mor-
phology, crystalline phases, amounts of crystalline phase and
size of crystalline particles, have an effect on the mechanical
strength of the ceramics [53,54]. Moreover, the presence of
more than one crystalline phase can also result in a complex
mechanical behavior [55,56].
3.3. Degradation of ceramics in Tris–HCl
Fig. 6 shows the weight loss of the ceramics after soaking in
Tris–HCl solution. Obviously, the weight loss of each ceramic
increased with the increase of soaking time. After 7 days, the
weight loss of sample CS, CS–Zn and CS–Zr is 4.02%, 2.43%
10164 H.C. Li et al. / Ceramics International 41 (2015) 10160–10169
and 1.67%, respectively. The sample without ZnO or ZrO2
presented a higher weight loss after soaking in Tris–HCl
solution. It is indicated that the addition of ZnO or ZrO2
reduces the loss of weight and significantly improves the
degradability of wollastonite. ZnO or ZrO2 decreased the total
pore volume of wollastonite, and made the structure more
compact. Therefore, the samples doped with ZnO or ZrO2
were not easily attacked by Tris–HCl solution. The more dense
Fig. 3. Pore diameter vs. pore volume of ceramics.
Fig. 4. The results of the bending strength and elastic modulus of ceramics.
Fig. 5. The load–deflection curve of ceramics ((a) CS; (b) CS–Zn; (c) CS–Zr).
structure improves the degradable property of the ceramic. The
lower degradation rate can improve the safety coefficient of the
sample as implant.
3.4. Apatite-forming ability of ceramics in simulated body
fluid
Fig. 7 shows the XRD patterns and FTIR spectra of the
ceramics after soaking in SBF for 7 days. From the XRD
patterns, after soaking, the characteristic peaks of hydroxya-
patite (Ca10(PO4)6(OH)2) corresponding to ð1 1 1Þ, ð0 0 2Þ,
ð2 1 1Þ, ð1 1 2Þ, ð3 0 0Þ and ð2 2 2Þ reflections were obviously
found and the diffraction intensity of the original phase in the
ceramics was significantly reduced, indicating the apatite layer
induced on the surface of the ceramics. The presence of matrix
phase is caused by the fact that the new precipitate on the
ceramic surface was thin and X ray penetrated the precipitated
surface layer and detected the ceramic. From the FTIR spectra
of the ceramics after soaking in SBF for 7 days, it can be seen
that the phosphate absorption bands at 1043, 958, 601, 563,
and 468 cm  1 were observed in sample CS, in which the
double peaks at 601 and 563 cm  1 are the characteristic
feature of phosphate in crystalline phases [57]. The appearance
of phosphate proves the formation of apatite layer on the
ceramic surface. The peak intensity of carbonate adsorption
band at 1417 cm  1 was increased compared with that in
Fig. 1, and carbonate adsorption band at 871 cm  1 were
detected. The peaks corresponding to the original phase of the
ceramic disappeared, which also means that the new precipi-
tates have been generated on the ceramic surface. The
appearance of carbonate absorption bands in FTIR spectra
seems to show a contradiction with the results obtained by
XRD, which is caused by the difference of the detection
methods. The technology of FTIR probes short-range struc-
tural order, and X-ray detects the sample surface and it can
penetrate a certain depth. The amount of carbonate compounds
generated on the ceramic surface was probably few and the
diffraction peaks were likely to be hidden in the background of
the XRD patterns.
Fig. 8 is the SEM micrographs and EDS analysis of the
ceramics after soaking in SBF for 7 days. The surface of
 H.C. Li et al. / Ceramics International 41 (2015) 10160–10169
sample CS was fully covered by the newly formed layer that
closely arranged spherical particles. When ZnO was incorpo-
rated, some spherical particles can be seen in some local area.
When ZrO2 was added, some spherical particles were unevenly
distributed on CS–Zr surface and some spherical agglomerates
can be observed. C. Shuai’s research showed that the particles
of hydroxyapatite grow gradually and tend to become
spherical-like shape from the initial needle-like shape, and
the newly developed hydroxyapatite meets the requirements
for the mechanical and biological properties of bone [58,59].
In addition, some cracks appeared on the sample surface,
which may be caused by the higher local surface tension in
drying process. The results of EDS analysis of the ceramics
after immersion showed that the layer formed on the sample
surface mainly contains Ca, P and O.
The SEM micrographs and EDS analysis of the cross sections
of the ceramics after soaking in SBF for 7 days are shown in
Fig. 9. The zone 1 of the sample CS (Fig. 9a) was composed of
3.31 at% C, 80.29 at% O, 8.29 at% P and 8.11 at% Ca, which
Fig. 6. The weight loss of ceramics after soaking in Tris–HCl solution.
Fig. 7. XRD patterns and FTIR spectra of ceramics after soaking in SBF for 7 days.
10165
shows that the newly formed calcium–phosphate compound was
precipitating on the surface of the ceramic during soaking in the
SBF solution. The zone 2 of the sample CS was composed of
2.13 at% C, 82.25 at% O, 0.40 at% Si, 7.56 at% P and 7.66 at%
Ca. The zone 3 of the sample CS was composed of 75.69 at% O,
23.78 at% Si and 0.54 at% Ca, which has Ca quantities far lower
than the original specimen. Ca ions in the ceramic exchanged
with H þ or H3O þ in SBF solution when the ceramic was soaked
in SBF, and the release of Ca ions from the ceramic led to a
decrease of the Ca quantity. The P quantity decreased gradually
and the Si quantity increased gradually from top to bottom of the
ceramic. A similar trend was observed in the sample CS–Zr
(Fig. 9c). The change trend of the sample CS–Zn immersed for 7
days in SBF (Fig. 9b) was not obvious, and a small amount of Zn
was observed in the zone 3. In addition, there was no obvious
interface between the new precipitate layer and the ceramic
surface because of the short soaking time. The similar phenom-
enon was also reported in the literature [60], which suggested that
no obvious precipitate layer appeared on the ceramic surface in
the beginning of immersion time, and with the prolonging of
soaking time, a new precipitate layer can be observed.
The assessment of the bioactivity was evaluated using the
in vitro dipping tests in SBF, and the SBF solution is static.
The method has some disadvantages in ingredients, tempera-
ture, liquidity and so on [61,62]. In the process of soaking, the
distribution of ion concentration in pipe is unequality, and the
local concentration of some ions may be relatively high, which
will cause an inhomogeneous distribution of the new pre-
cipitate on the ceramic surface. In this paper, X-ray detected
the sample surface. X-ray can penetrate a certain depth, and the
penetrating depth of X-ray is related to incidence angles,
sample composition and so on. When X-ray detected the
precipitate formed on the ceramic surface, it may penetrate the
precipitated surface layer and detect the ceramic. This explains
why the matrix phase was still observed in the XRD results
after soaking the ceramics in SBF for 7 days.
10166 H.C. Li et al. / Ceramics International 41 (2015) 10160–10169

Although there are some limitations and shortcomings, the comprehensively detected by XRD, FTIR, SEM and EDS.
in vitro dipping test in SBF solution can still help us under- On the basis of these results, we conclude that the samples
stand the apatite formation [63]. The newly formed layer on possess apatite formation ability. Fig. 10 shows the change in
the surface of the ceramics in simulated body fluid was pH values of SBF solution for the ceramics with immersion

Fig. 8. SEM micrographs and EDS analysis of ceramics after soaking in SBF for 7 days ((a) CS; (b) CS–Zn; (c) CS–Zr).

Fig. 9. SEM micrographs and EDS analysis of the cross sections of ceramics after soaking in SBF for 7 days ((a) CS; (b) CS–Zn; (c) CS–Zr).
 H.C. Li et al. / Ceramics International 41 (2015) 10160–10169
Fig. 10. The change in pH values of SBF solution for ceramics with immersion time.
Fig. 11. The formation of apatite on the ceramic surface in SBF.
time. The change in pH value basically followed the same
pattern, which relates to the exchange rate of ions. The
formation of apatite on the ceramic surface in SBF is shown
in Fig. 11. Combined with the diagram of the apatite
formation, when the ceramic is soaked in SBF, alkali metal
ions in the ceramic exchange with H þ or H3O þ in SBF
solution, and the solution pH value rises rapidly. The rapid ion
exchange leads to SiO2-rich layer formation on the ceramic
surface, which can provide favorable conditions for the
nucleation of apatite. Once apatite nuclei formed on the
ceramic surface, calcium ions in SBF are first migrated onto
the SiO2-rich layer and then the ionic activity products of
apatite are migrated onto the SiO2-rich layer to grow into
apatite [2,60,64].
Therefore, the properties of wollastonite can be adjusted and
controlled by adding a right amount of doping ions. This work
can provide some reference for preparing a desired biomaterial
and many new materials with improved properties can be
designed according to requirements.
4. Conclusions
The partial substitution of ZnO or ZrO2 for CaO in CaO–SiO2
system is performed by sintering sol–gel derived precursor. The
effects of ZnO and ZrO2 on structure, mechanical properties,
degradability and in vitro bioactivity of wollastonite are reported.
The ceramics are composed of β-CaSiO3. A new phase of
10167
Ca2ZnSi2O7 appears in sample CS–Zn, and t-ZrO2 appears in
sample CS–Zr. The addition of ZnO or ZrO2 decreases the total
pore volume, indicating ZnO or ZrO2 increase the density of
wollastonite. ZnO or ZrO2 improves the bending strength of
wollastonite and the elastic moduli of the ceramics match that of
human body bone. The addition of ZnO or ZrO2 decreases the
degradation rate, and improves the degradability of wollastonite.
All samples possess the apatite formation ability in SBF.
Acknowledgments
This work was financially supported by Natural Science Foun-
dation of Shandong Province (Grant no: ZR2013EMM012) and
the Project of Independent Innovation of Shandong University
(Grant no: 2012TS029).
References
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