materials

Article
Fabrication and Microstructure of ZnO/HA Composite
with In Situ Formation of Second-Phase ZnO
Shidan Yuan 1 , Ye Ma 1 , Xingyi Li 1, * , Zhen Ma 1 , Hui Yang 1 and Liting Mu 1,2
1 School of Materials Science and Engineering, Jiamusi University, Jiamusi 154007, China;
jmsdxysd@163.com (S.Y.); 15046492438@163.com (Y.M.); mz252930179@163.com (Z.M.);
freedomyahu@163.com (H.Y.); muliting@163.com (L.M.)
2 School of Pharmacy, Jiamusi University, Jiamusi 154007, China
* Correspondence: hljjmslxyysd@163.com




Received: 20 August 2020; Accepted: 3 September 2020; Published: 7 September 2020


Abstract: Nanometer hydroxyapatite (n-HA) powders were synthesized by the chemical precipitation
method, and a novel ZnO/HA composite, which consisted of second-phase particles with different sizes
and distributions, was successfully fabricated. ZnO/HA composites were prepared by using powder
sintering with different Zn contents and a prefabrication pressure of 150 MPa. Microstructure and local
chemical composition were analyzed by a scanning electron microscope (SEM) and energy-dispersive
spectrometer (EDS), respectively. The phase composition and distribution of the composite were
determined with electron back-scattered diffraction (EBSD) and an X-ray diffractometer (XRD),
respectively. The experimental results of the XRD showed that the chemical precipitation method was
a simple and efficient method to obtain high-purity n-HA powders. When the sintering temperature
was lower than 1250 ◦ C, the thermal stability of HA was not affected by the Zn in the sintering process.
Due to sintering in an air atmosphere, the oxidation reaction of Zn took place in three stages, and ZnO
as the second phase had two different sizes and distributions in the composites. The compressive
strength of ZnO/HA composites, of which the highest was up to 332 MPa when the Zn content was
20%, was significantly improved compared with pure HA. The improvement in mechanical properties
was mainly due to the distribution of fine ZnO particles among HA grains, which hindered the HA
grain boundary migration and refinement of HA grains. As grain refinement increased the area of
the grain boundary inside the material, both the grain boundary and second phase hindered crack
development in different ways.

Keywords: powder sintering; grain growth; compression strength; ZnO/HA composite

1. Introduction
Hydroxyapatite (HA, Ca10 (PO4 )6 (OH)2 ) has been widely considered to have good biocompatibility.
There are many methods to synthesize HA, such as dry methods [1,2], the chemical precipitation
method [3], and hydrothermal method [4]. The HA powder materials prepared by the above methods
have been widely applied in many fields, such as bone filling repair [5], the tissue engineering stent [6],
the implant surface coating [7], drug delivery [8], and environmental pollution treatment (such as
wastewater treatment) [9]. The theoretical density of HA is 3.16 g/cm2 , and a simple and effective
method to prepare HA block materials is by pressing HA powder and sintering it at high temperature.
The mechanical strength and elastic modulus of dense HA are higher than those of human bone
except for the fracture toughness, which cannot meet the needs of bone tissue repair and replacement
of human load-bearing parts; and HA with a larger grain size and higher densification degree has
good biocompatibility but lower bioactivity. In order to solve such problems, many scholars have
carried out a lot of research works. The preparation of porous hydroxyapatite materials is a hot spot.

Materials 2020, 13, 3948; doi:10.3390/ma13183948 www.mdpi.com/journal/materials

Materials 2020, 13, 3948 2 of 10

The porous structure with a different morphology, size, and distribution in porous HA could provide
the necessary space to ensure the transmission of blood and other substances, thereby ensuring the
metabolism of bone tissue. At the same time, the high specific surface area would be more conducive
to the interchange of materials between the implant and human tissues, which could accelerate the
formation and reconstruction of new bone tissues [10]. However, the porous structure has a great
influence on the mechanical properties of materials (such as strength reduction). HA composites are
also another research hotspot. Combining two or more materials (including HA) would give full
play to their respective advantages and produce a synergistic effect to meet the needs of different
applications. The composite with HA now mainly includes inorganic and polymer materials [11,12],
which must meet the requirements of good biocompatibility and excellent metabolic ability of the
human body. Zn is an important trace element in the human body involved in the process of nucleic acid
protein metabolism, and can also promote the normal development of skin, bone, and sexual organs,
and maintain digestion and metabolic activities [13,14]. ZnO can be used as a source of Zn elements for
the human body. Studies have shown that ZnO with small size is an ideal non-polar antibacterial agent
with broad-spectrum antibacterial effects [15,16]. Based on several reports, the ZnO/HA composites,
prepared by using ZnO as a second phase or HA being modified with ZnO, still had broad-spectrum
antibacterial properties [17]. However, a series of problems have been found during the preparation
and clinical application of HA composites, such as the uncontrollable grain growth for HA and ZnO
during sintering, low or no antimicrobial properties, and unsuitable mechanical properties for human
bone tissue, which limit the application of HA composites. Few reports have focused on the grain
growth for porous HA ceramics prepared with Zn powder as the pore-forming agent. Therefore,
the biomedical hydroxyapatite ceramic materials with a specific shape and used as load-bearing parts
for the human body should be developed in the porous and multi-functional direction.
In this study, spherical Zn particles were used as a pore-forming agent. The oxidation reaction of
Zn powder and oxygen was used to obtain the second phase of composites. The gaps between HA
nanocrystals were used to control the size of the second-phase particles. The ZnO/HA composites with
porous structure were prepared by conventional pressing and pressureless sintering, aiming to reduce
the compactness of the material and ensuring the mechanical strength of the material simultaneously.
The densities of the material, as well as the size and distribution of ZnO particles, were controlled by
adjusting the addition amount of the Zn powders and the sintering process. The relationship between
the phase composition, microstructure evolution, and mechanical properties of the composites was
analyzed and discussed.

2. Materials and Methods

Calcium hydroxide powder (purity 95.0 wt.%, Tianjin Guangfu Fine Chemical Research Institute,
Tianjin, China), calcium dihydrogen phosphate monohydrate (purity 98.0 wt.%, Tianjin Guangfu Fine
Chemical Research Institute), and zinc powder (purity 99.5 wt.%, −400 mesh, Tianjin Ruijin Chemical
Co. LTD, Tianjin, China) were used in this study as raw materials. The experimental equipment for the
preparation of pure HA and ZnO/HA composites are listed in Table 1.

2.1. Preparation of Nano-HA Powders, Pure HA, and ZnO/HA Composites

The nanometer hydroxyapatite (n-HA) powders were prepared by the chemical precipitation
method. The technological processes are shown in Figure 1a. Pure Zn was used as the pore-forming
agent. According to the mass ratios of 10:0, 9:1, 8:2, and 7:3, the n-HA powder and Zn powders were
mixed in the mixer. Pure HA and novel in-situ ZnO/HA composites were prepared by sintering at
different temperatures after pressing at 150 MPa (Figure 1b). The composition and sintering process
parameters for the preparation are shown in Table 2.
 101A-2
drying oven General Factory, Shanghai, China
Constant temperature Tianjin Tester Instrument Co. LTD,
DK-98-ⅡA
water bath Tianjin, China
Mixer 4 Tank Mixer MTI corporation
Materials 2020, 13, 3948 Beijing Zhonghe Venture 3 of 10
Powder compressing
ZHY-601B Technology Development Co. LTD,
machine
Beijing,
Table 1. Information of experimental equipment for the China
preparation.
Beijing Medical centrifuge Plant,
Hydroextractor LD5-A
Equipment Product Model Beijing, China
Manufacturer

Jinan Precision
Shanghai Tianping Science instrument
instrument Factory, Shanghai,
Resistance furnace
Analytical balance
SX2-5-12G
FA2004
China
Co. LTD, Jinan, China
Jiangsu Jintan Jincheng Guosheng Experimental
Electric mixer JJ-1
Instrument Factory, Changzhou, China
2.1.Constant
Preparation of Nano-HA
temperature Powders, Pure 101A-2
drying oven HA, and ZnO/HA Shanghai
Composites
Experimental Instrument General
Factory, Shanghai, China
The nanometer
Constant temperaturehydroxyapatite
water bath (n-HA) powders were
DK-98-IIA prepared
Tianjin by the Co.
Tester Instrument chemical precipitation
LTD, Tianjin, China
Mixer 4 Tank Mixer
method. The technological processes are shown in Figure 1a. Pure Zn MTI wascorporation
used as the pore-forming
Beijing Zhonghe Venture Technology
agent. According
Powder to the
compressing mass ratios ofZHY-601B
machine 10:0, 9:1, 8:2, and 7:3, the n-HACo.
Development powder and China
LTD, Beijing, Zn powders
were mixed in the mixer. Pure HA and
Hydroextractor novel in-situBeijing
LD5-A ZnO/HA Medicalcomposites were
centrifuge Plant, prepared
Beijing, China by
sintering Resistance
at different temperatures
furnace after pressing
SX2-5-12G at 150 MPa (Figure 1b). The composition
Jinan Precision Science instrument Co. LTD,
and
Jinan, China
sintering process parameters for the preparation are shown in Table 2.

Figure 1.1.Preparation
Figure Preparation process
process ofnanometer
of (a) (a) nanometer hydroxyapatite
hydroxyapatite (n-HA) powders
(n-HA) powders and (b)
and (b) ZnO/HA ZnO/HA
composites.
composites.
Table 2. Composition and sintering process parameters (Bal., the mass fraction except for the other
ingredient) of pure HA and ZnO/HA composites.
Table 2. Composition and sintering process parameters (Bal., the mass fraction except for the other
ingredient) of pure
MassHA and ZnO/HA composites.
Fraction/wt.%
Experimental Prefabricated Sintering
Sintering Time (h)
Group HA Zn Pressure (MPa) Temperature (◦ C)

1 Bal. 0 150 850 2

2 Bal. 0 150 950 2
3 Bal. 0, 10, 20, 30 150 1050 2
4 Bal. 0, 10, 20, 30 150 1100 2
5 Bal. 0, 10, 20, 30 150 1150 2
6 Bal. 0, 10, 20, 30 150 1200 2
7 Bal. 0, 10, 20, 30 150 1250 2
 2 Bal. 0 150 950 2
3 Bal. 0, 10, 20, 30 150 1050 2
4 Bal. 0, 10, 20, 30 150 1100 2
5 Bal. 0, 10, 20, 30 150 1150 2
6 3948
Materials 2020, 13, Bal. 0, 10, 20, 30 150 1200 2 4 of 10
7 Bal. 0, 10, 20, 30 150 1250 2

2.2.2.2.
Compression
CompressionStrength
StrengthTest
Test
Compressivestrength
Compressive strengthwas was evaluated
evaluated using
using aa mechanical
mechanical property
propertytesting
testingsystem
systemat at
room
room
temperature and with the loading speed of 0.5 mm/min. The composite samples with a diameter of of
temperature and with the loading speed of 0.5 mm/min. The composite samples with a diameter
10 10
mm mm and
and thicknessofof6 6mm
thickness mmwere
wereprepared
preparedininthe
the same
same manner.

2.3.2.3. Characterization
Characterization

Microstructure
Microstructure andand
locallocal chemical
chemical composition
composition were analyzed
were analyzed by a scanning
by a scanning electron
electron microscope,
microscope,
SEM (JSM-7800F,SEM (JSM-7800F,
JEOL LTD, Tokyo,JEOL LTD, and
Japan), Tokyo, Japan), and energy-dispersive
energy-dispersive spectrometer, EDSspectrometer, EDS
(Oxford X-maxn,
(Oxford
Oxford X-maxn, Oxford
Instructments, Instructments,
London, London, UK),
UK), respectively. respectively.
The phase The phase
composition and composition
distribution and
of the
distribution
composite wereofdetermined
the compositewithwere determined
electron with electron
back-scattered back-scattered
diffraction, diffraction,
EBSD (Oxford Nordlys EBSD
Max3,
(Oxford
Oxford Nordlys Max3,
Instructments, Oxford
UK), and Instructments, UK), and anXRD
an X-ray diffractometer, X-ray(Bruker
diffractometer, XRD (Bruker
D8, Karlsruhe, D8,
Germany),
byKarlsruhe,
using CuKα Germany),
radiationby(λusing CuKα
= 0.1542 radiation
nm), (λ = a0.1542
and using nm),
vertical and usingin
goniometer a vertical goniometer
the 2θ range in ◦ ,
of 10–100
thea2θ
with range
step of 10–100°,
of 0.02 ◦ and atwith
a scana step
speedof 0.02°
of 5◦ and
minat
−1 .a scan speed of 5° min .−1

3. Results
3. Results andDiscussion
and Discussion

3.1.3.1. CharacteristicsofofSynthesized
Characteristics SynthesizedNano-HA
Nano-HA Powder
Powder
Themorphology,
The morphology,chemicalchemical composition,
composition, andand phase
phase analysis
analysis ofofthethen-HA
n-HApowder
powdersample
sample
synthesized
synthesized by by the chemical
the chemical precipitation
precipitation method method are shown
are shown in Figurein 2.Figure 2. A homogeneous
A homogeneous distribution
distribution
of particles wasofobtained
particlesafter
was obtained after crystallization
crystallization treatment at 750treatment
◦ C, andatthere
750 °C,
wasand thereagglomeration
a slight was a slight
phenomenon after drying (shown in Figure 2a). Figure 2b shows an enlarged SEM image ofSEM
agglomeration phenomenon after drying (shown in Figure 2a). Figure 2b shows an enlarged a part
image of a part of the area in Figure 2a, and it can be seen that the grain size is between 40 and 100
of the area in Figure 2a, and it can be seen that the grain size is between 40 and 100 nm. The EDS
nm. The EDS analysis results of region C in Figure 2b is shown in Figure 2c. It has been shown that
analysis results of region C in Figure 2b is shown in Figure 2c. It has been shown that the chemical
the chemical components are Ca, P, and O (H element cannot be detected) and the molar ratio of Ca
components are Ca, P, and O (H element cannot be detected) and the molar ratio of Ca to P is about
to P is about 10:6. The results of XRD indicate that n-HA powders have a high degree of
10:6. The results of XRD indicate that n-HA powders have a high degree of crystallization, as shown
crystallization, as shown in Figure 2d. The diffraction peaks have a certain width, which
in Figure 2d. The diffraction peaks have a certain width, which corresponds to the nanocrystalline
corresponds to the nanocrystalline morphology of the powders. The phase analysis has shown that it
morphology
is HA (Caof the powders. The phase analysis has shown that it is HA (Ca (PO4 )3 (OH),
5 (PO 4 ) 3 (OH), JCPDS #84-1998), and no other calcium phosphate 5 phases exist. JCPDS
The
#84-1998), and no
experimental otherhave
results calcium
shownphosphate
that n-HAphases exist. The
particles, whichexperimental results
are synthesized byhave
the shown
chemicalthat
n-HA particles, which are synthesized
precipitation method, have high purity. by the chemical precipitation method, have high purity.

Figure
Figure 2. 2.(a,b)
(a,b)SEM
SEMmorphology;
morphology; (c)
(c) EDX
EDX spectrum,
spectrum, and
and(d)
(d)XRD
XRDpattern
patternofofn-HA
n-HApowders.
powders.

3.2.3.2. CharacteristicsofofPure
Characteristics PureHA
HAand
andZnO/HA
ZnO/HAComposite
Composite Samples
The phase compositions were characterized by XRD. The results have been shown in Figure 3,
which indicate the results of the composites with different contents of Zn at the sintering temperature
of 1250 ◦ C.
HA and ZnO correspond well to their respective standard cards, and the positions of the diffraction
peaks are not shifted either. These results show that HA did not decompose with the presence of
zinc in the sintering condition of 1250 °C [18–20]. They also show that the thermal stability of HA
was not affected by the presence of elemental zinc and zinc oxide when the composite was sintered
below 1250
Materials 2020,°C.
13, 3948 5 of 10

Figure
Figure3.3.XRD
XRDpatterns
patternsofofthe
theZnO/HA
ZnO/HAcomposites.
composites.

The
TheEBSD techniqueresults
experimental combined
havewithshownSEM hasthe
that been used tocomposites
ZnO/HA analyze theconsist
crystal of
structure and
two phases,
morphology
(HA (Ca 10 (POof4 pure
)6 (OH) HA
2 , and ZnO/HA composites. The SEM morphology of pure HA samplesis
JCPDS #74-0565) and ZnO (JCPDS #80-0075)). As the sintering atmosphere
sintered
air, Zn inatthe1250 °C is shown
sintering processinoxidized
Figure with
4a. The
the experimental
oxygen in the results show
air to form thatThe
ZnO. there were intensity
relative a small
number
of the ZnO of cavities
diffraction with
peak different
increased shapes andZnsizes
with the ranging
content. It hasfrom
been0.3 to several
shown μm,strong
that three which were
peaks of
distributed
HA and ZnO in the polishedwell
correspond samples.
to their HA grain growth
respective was cards,
standard causedand by the
grain boundary
positions migration
of the in
diffraction
the
peakssintering
are notprocess, and theThese
shifted either. grainresults
growth represents
show that HAthe didreduction in internal
not decompose with voidage of the
the presence of
material at the same time, which increased the densities of the material [21]. The cavity size
zinc in the sintering condition of 1250 ◦ C [18–20]. They also show that the thermal stability of HA

gradually decreased
was not affected with
by the grain boundary
presence of elemental migration.
zinc andWhen the HA
zinc oxide when grain
the orientation
composite was around the
sintered
cavity
belowhad 1250a ◦large
C. angle grain boundary and the boundary could not move toward the interior of the
other Thegrains,
EBSD thetechnique
HA grain growth with
combined aroundSEMthe hascavity ended.
been used In orderthe
to analyze to crystal
confirm the phase
structure and
distribution,
morphologyEBSD of pure analysis
HA andwas performed
ZnO/HA for region
composites. ThebSEMin Figure 4a. As shown
morphology of purein HAFigure 4b-1,
samples it is a
sintered
phase
at 1250 (PH) distribution superposed with band contrast (BC), in which red represents the HA phase,
◦ C is shown in Figure 4a. The experimental results show that there were a small number of

gray represents
cavities a smallshapes
with different amountand of sizes
zero-resolution
ranging from phase, and
0.3 to black µm,
several corresponds
which were to the cavities in
distributed in
Figure 4a. Thesamples.
the polished inverse pole HA figures (IPF) of
grain growth wasregion b inby
caused Figure
grain4a is shownmigration
boundary as Figurein 4b-2,
the which
sintering is
superimposed
process, and the with grain
grain boundaries
growth represents(GB)theand BC graphs,
reduction where different
in internal voidage ofcolors represent
the material atdifferent
the same
crystal orientations.
time, which increased According to IPF,ofthe
the densities theHA grain orientation
material distribution
[21]. The cavity should be
size gradually random with
decreased and
have
grainno special direction.
boundary migration. When the HA grain orientation around the cavity had a large angle grain
boundary and the boundary could not move toward the interior of the other grains, the HA grain
growth around the cavity ended. In order to confirm the phase distribution, EBSD analysis was
performed for region b in Figure 4a. As shown in Figure 4b-1, it is a phase (PH) distribution superposed
with band contrast (BC), in which red represents the HA phase, gray represents a small amount of
zero-resolution phase, and black corresponds to the cavities in Figure 4a. The inverse pole figures (IPF)
of region b in Figure 4a is shown as Figure 4b-2, which is superimposed with grain boundaries (GB)
and BC graphs, where different colors represent different crystal orientations. According to IPF, the HA
grain orientation distribution should be random and have no special direction.
Materials 2020, 13, 3948 6 of 10
Materials 2020, 13, x FOR PEER REVIEW 6 of 10

Figure 4. (a)
Figure 4. (a) SEM
SEM morphology;
morphology; (b-1)
(b-1) phase
phase distribution;
distribution; and
and (b-2)
(b-2) inverse
inverse pole
pole figures
figures of
of pure
pure HA
HA
sintered at 1250
sintered at 1250 ◦°C.
C.

The
The SEM morphology of
SEM morphology of the
the ZnO/HA
ZnO/HAcomposite
compositewith with10% 10%Zn Znaddition
additionsintered
sinteredatat1250
1250 °C for 2
◦ C for 2 h

h is shown in Figure 5a. It can be seen from the figure that a certain number of cavities with different
is shown in Figure 5a. It can be seen from the figure that a certain number of cavities with different
shapes
shapes andandsizes
sizeswere
weredistributed
distributed inside
inside thethe materials.
materials. There There
waswas a certain
a certain number number of cavities
of cavities of
of nearly
nearly
sphericalspherical
shape alsoshape also distributed,
distributed, except forexcept for thedescribed
the cavities cavities described
in Figure 4a inabove.
FigureEBSD4a above. EBSD
analysis on
analysis
region b inonFigure
region5ab has
in Figure
been shown 5a hasasbeenFigure shown
5b-1, as
andFigure 5b-1,distributions
the phase and the phase are distributions
superposed with are
superposed
BC, in whichwith BC,area
the red in which the red
represents thearea
HA represents
phase, the blue the HA areaphase, the blue
represents area phase,
the ZnO representsand the
the
ZnO
blackphase, and the black
area corresponds area
to the corresponds
cavities to theshapes
of different cavities and ofsizes
different shapes
in Figure 5a.and
Thesizes
IPF ofinregion
Figureb5a.in
The
FigureIPF5aofisregion
shownbas inFigure
Figure5b-2,5a iswhich
shownisas Figure 5b-2, which
superimposed with GB is superimposed
and BC graphs,with where GBdifferent
and BC
graphs, where different
colors represent colors orientations.
different crystal represent different
From thecrystal orientations.
IPF, it can From determined
be preliminarily the IPF, it that can the
be
preliminarily determined that the HA and ZnO grain orientation distribution was random and had
HA and ZnO grain orientation distribution was random and had no special direction. The density of
no
thespecial
material direction.
changedThe density
slightly during of the
thematerial changed
heating period, andslightly duringofthe
the density theheating
composite period, and at
was still thea
density
low level.of With
the composite
the increase wasinstill at a low level.
temperature, With therate
the reaction increase
between in temperature, the reaction
Zn and O2 accelerated asrate
the
between
interior ofZntheand O 2 accelerated
material remained connectedas the interior
with the of air
theatmosphere,
material remained connected
which promoted the with the air
formation of
atmosphere, whichofpromoted
a certain thickness ZnO on the thesurface
formation of a certain
of spherical Zn thickness
particles. Theof ZnO
layer onofthe
ZnOsurface
actedof asspherical
a coat to
Zn particles.
isolate The layer
the internal of ZnO
Zn from theacted
externalas aoxygen
coat to and
isolate the internal
prevented Zn oxidation
further from the external
of the Zn. oxygen
Whenand the
prevented
temperature further oxidation
rose further of the
beyond Zn. C
419.5 ◦
When the temperature
(the melting point of Zn),rose the
further beyondpart
unoxidized 419.5 °C (the
inside the
melting
sphericalpoint of Zn),changed
Zn particle the unoxidized
from solid parttoinside
liquid.thePartspherical Zn particle
of the liquid Zn flowed changed
out offrom
the solid
gaps to
in
liquid. Part of the liquid Zn flowed out of the gaps in the zinc oxide protective layer and dispersed
the zinc oxide protective layer and dispersed into HA intergranular gaps around the Zn particles.
into HAfine-sized
Several intergranular gaps around
ZnO particles (suchthe as Zn
Pointparticles.
c) formed Several
by thefine-sized
continuous ZnO particles
oxidation (such between
reaction as Point
c) formed
liquid Zn andby the
O2 . continuous oxidation reaction
When the temperature exceededbetween
907 ◦ C (theliquid Zn and
boiling pointO 2of
. When
Zn), thetheresidual
temperature
liquid
exceeded
Zn in the Zn907particle
°C (the boiling
boiled andpoint of Zn),
spilled thefrom
out residual liquidof
the inside Znthe
in sample,
the Zn particle
and part boiled
of theandZnspilled
atoms
out from and
oxidized the inside
remained of the sample,
in the sample. andThepart of the
other Znflew
part atoms oxidized
off the surface and
andremained
oxidized.in the sample.
The other part flew
The relevant off the
grain sizesurface and oxidized.
and orientation distribution information were obtained by processing with
Aztec Crystal software, according to the original EBSD data of ZnO/HA composites. Distribution of
the grain size and orientation, which describes the equivalent circle diameter, is shown in Figure 6.
The experimental results show that the HA grain orientation was randomly distributed in the material,
shown in Figure 6d–f. The average equivalent circle diameter of HA grains in pure HA and ZnO/HA
composites, which have been prepared with 10%, 20%, and 30% amounts of Zn, were 2.4, 2.2, 1.9,
and 1.5 µm, respectively, shown as Figure 6a–d, and they were normally distributed.
As shown in Figure 7, it is found that the compressive strength of the composites is higher than
that of pure HA sintered with the same temperature. Experimental results have shown that the
compressive strength of the composites increased first and then decreased with the increase in Zn
addition, and the compressive strength reached the maximum value when the addition of Zn reached
20% as well. Compared to the composite samples with the same Zn content but different sintering
temperature, it is found that the trend of compressive strength changed. It has also been found that
preliminarily determined that the HA and ZnO grain orientation distribution was random and had
no special direction. The density of the material changed slightly during the heating period, and the
density of the composite was still at a low level. With the increase in temperature, the reaction rate
between Zn and O 2 accelerated as the interior of the material remained connected with the air
atmosphere, which
Materials 2020, 13, 3948 promoted the formation of a certain thickness of ZnO on the surface of spherical 7 of 10
Zn particles. The layer of ZnO acted as a coat to isolate the internal Zn from the external oxygen and
prevented further oxidation of the Zn. When the temperature rose further beyond 419.5 °C (the
with the point
melting increase of in sintering
Zn), temperature,
the unoxidized partthe compressive
inside strength
the spherical Zn of the composites
particle changed increased
from solidfirstto
and then decreased, and the maximum compressive strength appeared at 1150 ◦ C when the contents of
liquid. Part of the liquid Zn flowed out of the gaps in the zinc oxide protective layer and dispersed
Zn were
into HA low. With the further
intergranular increase
gaps around theinZn
Znparticles.
contents (20% Zn,fine-sized
Several 30% Zn), the
ZnOmaximum
particles of compressive
(such as Point
strength was offset in the low-temperature zone (20% Zn corresponds to 1100 ◦ C, 30% Zn corresponds
c) formed by the continuous oxidation reaction between liquid Zn and O 2 . When the temperature
to 1050 ◦ C).
exceeded 907The°C results showed
(the boiling that
point ofan
Zn),oxidation reaction
the residual occurred
liquid between
Zn in the Zn and
Zn particle oxygen
boiled andinspilled
air to
formfrom
out ZnOtheduring
insidesintering under the
of the sample, andcondition of air
part of the Znatmosphere, and and
atoms oxidized ZnOremained
existed in in
thethe
composite
sample.
as a second phase, which affected the compressive
The other part flew off the surface and oxidized. strength [22,23].

Materials 2020, 13, x FOR PEER REVIEW 7 of 10

Figure 5. (a) SEM morphology; (b-1) phase distribution; and (b-2) inverse pole figures of ZnO/HA
composite sample with 10% Zn addition sintered at 1250 °C.

The relevant grain size and orientation distribution information were obtained by processing
with Aztec Crystal software, according to the original EBSD data of ZnO/HA composites.
Distribution of the grain size and orientation, which describes the equivalent circle diameter, is
shown in Figure 6. The experimental results show that the HA grain orientation was randomly
distributed in the material, shown in Figure 6d–f. The average equivalent circle diameter of HA
grains in pure HA and ZnO/HA composites, which have been prepared with 10%, 20%, and 30%
amounts
Figureof5.Zn, weremorphology;
(a) SEM 2.4, 2.2, 1.9,(b-1)
and phase
1.5 μm, respectively,
distribution; and shown as Figure
(b-2) inverse 6a–d, and
pole figures they were
of ZnO/HA
normally distributed. ◦
composite sample with 10% Zn addition sintered at 1250 C.

Figure6.6.Grain
Figure Grainsize
sizeofofHA
HA and
and orientation
orientation distribution
distribution ofpure
ofpure HAHA
andand ZnO/HA
ZnO/HA composites:
composites: (a,e)(a,e)
Pure
Pure(b,f)
HA; HA;Zn (b,f)
10 Zn 10 wt.%;
wt.%; (c,g)
(c,g) Zn 20Zn 20 wt.%;
wt.%; (d,h) (d,h)
Zn 30Zn 30 wt.%.
wt.%.

Asterms
In shown of in Figure
pure HA 7, and it is
thefound
ZnO/HA that the compressive
composite in thestrength of the composites
study, experimental is higher
results than
have shown
thatthere
that of pure HA sintered
are mainly with the
three factors thatsame temperature.
contribute Experimental
to compression results
strength: have shown
I densities; that
II grain theof
size
compressive
HA; strength
III morphology, of the
size, andcomposites
distributionincreased first and then
of the second-phase decreased
particles. with the
As shown in increase
Figure 8,in it Zn
was
addition,
the grain sizeandvariation
the compressive
of pure HAstrength reached
at different the temperatures
sintering maximum value for 2 when
h. Thethe addition of
experimental Zn
results
reached that
showed 20%theas well.
grainCompared
size of HAtobecame the composite samples
big gradually with
with thethe same Zn
increase in content but different
temperature, and the
sinteringrule
variation temperature,
after fittingit can
is found that theby
be described trend of compressive
Equation strength
(1). It has been found changed.
that theItfracture
has also beenof
mode
found
HA that with
is mainly the increasefracture.
transgranular in sintering temperature,results
The experiment the compressive
also indicate strength
that theofdensity
the composites
increased
increased
with first and
the growth then
of the decreased,
grains. and the
In addition, the grain
maximumgrowth compressive
reduced thestrength
area of theappeared
fractureat 1150 face,
crystal °C
when the contents of Zn were low. With the further increase in Zn contents
which was contrary to the contribution of increasing density to the compressive strength of materials. (20% Zn, 30% Zn), the
maximum
That is why ofthecompressive
maximum value strength was offset in
of compressive the low-temperature
strength appeared at 1150 zone
◦ C.(20% Zn corresponds
For ZnO/HA composites,to
1100 °C, 30% Zn corresponds to 1050 °C). The results showed that an
the number of internal pores increased with the addition of Zn, and there was a smaller contributionoxidation reaction occurred
between
on Zn and oxygen
the improvement in theindensity
air to form
with ZnO during sintering
the increase in sinteringunder the condition
temperature of air atmosphere,
and extension of holding
and ZnO existed in the composite as a second phase, which affected the compressive strength
[22,23].
In terms of pure HA and the ZnO/HA composite in the study, experimental results have shown
that there are mainly three factors that contribute to compression strength: I densities; II grain size of
HA; III morphology, size, and distribution of the second-phase particles. As shown in Figure 8, it
was the grain size variation of pure HA at different sintering temperatures for 2 h. The experimental
three constants.
ZnO, as
ZnO, as the
the second
second phase,
phase, existed
existed mainly
mainly inin two
two size
size distributions
distributions inin the
the materials:
materials: II formed
formed byby
oxidation based on Zn elemental particles, was large in number and concentrated,
oxidation based on Zn elemental particles, was large in number and concentrated, and the grain and the grain
size of
size of ZnO
ZnO was was also
also greatly
greatly affected
affected byby temperature;
temperature; II II fine
fine grain
grain size
size ZnO
ZnO has
has been
been described
described in in
point cc in
point in Figure
Figure 5a.
5a. These
These fine
fine ZnO
ZnO particles
particles hinder
hinder the
the movement
movement of of HA
HA grain
grain boundaries
boundaries around
around
them (such
Materials 2020, as the
13, 3948 area of Figure 9b). The fracture mode of HA was transgranular
them (such as the area of Figure 9b). The fracture mode of HA was transgranular fracture mainly fracture mainly
8 of 10

(cleavage fracture),
(cleavage fracture), which
which indicates
indicates that
that the
the cohesive
cohesive energy
energy of of the
the HA
HA grain
grain boundary
boundary waswas greater
greater
than
than that
time.that
It canof the
of theinferred
be cleavagethat
cleavage fracture
fracture surface.factors
surface.
the positive Therefore,
Therefore,
on thegrain
grain refinementinincreased
refinement
improvement increased the grain
the
the compressivegrain boundary
boundary
strength are
area
area
mainlyand hindered
andII and
hindered the propagation of cracks. At the same time, the orientation
III. the propagation of cracks. At the same time, the orientation of adjacent HA of adjacent HA
grains was
grains was randomly
randomly distributed,
distributed, leading
leading to to the need
needx−bto change thethe direction
direction ofof cracks
cracks when
when they
they
y = y0 the
+ a × e( cto) change
−1 (1)
propagated from the interior of adjacent grains of one grain phase (ZnO
propagated from the interior of adjacent grains of one grain phase (ZnO second phase played this second phase played this
role
role
where as ywell).
as well). Therefore,
is theTherefore, the
grain size;the increases
y0 increases in this
in
is the original this effect
effect
grain (asxshown
(as
size; shown in the
in the region
is the sinteringregion of Figure
of Figurea,
temperature; 9c)
9c) increased
b,increased
and c are
the area of the fracture surface and the compressive
the area of the fracture surface and the compressive strength.
three constants. strength.

Figure
Figure 7.
Figure7. The
7.The compression
Thecompression strength
compressionstrength of
strengthof pure
ofpure HA
pure HA and
HA and ZnO/HA
and ZnO/HA composites.
ZnO/HA composites.
composites.

Figure 8. Grain size variation curve of pure HA prepared with different sintering temperatures for 2 h.
Figure 8.
Figure 8. Grain
Grain size
size variation
variation curve
curve of
of pure
pure HA
HA prepared
prepared with
with different
different sintering
sintering temperatures
temperatures for
for 22 h.
h.

ZnO, as the second phase, existed mainly in two size distributions in the materials: I formed
by oxidation based on Zn elemental particles, was large in number and concentrated, and the grain
size of ZnO was also greatly affected by temperature; II fine grain size ZnO has been described in
point c in Figure 5a. These fine ZnO particles hinder the movement of HA grain boundaries around
them (such as the area of Figure 9b). The fracture mode of HA was transgranular fracture mainly
(cleavage fracture), which indicates that the cohesive energy of the HA grain boundary was greater
than that of the cleavage fracture surface. Therefore, grain refinement increased the grain boundary
area and hindered the propagation of cracks. At the same time, the orientation of adjacent HA grains
was randomly distributed, leading to the need to change the direction of cracks when they propagated
from the interior of adjacent grains of one grain phase (ZnO second phase played this role as well).
Therefore, the increases in this effect (as shown in the region of Figure 9c) increased the area of the
fracture surface and the compressive strength.
Materials 2020, 13, 3948 9 of 10
Materials 2020, 13, x FOR PEER REVIEW 9 of 10

Figure 9. (a)
Figure 9. (a)SEM
SEMmorphology
morphologyandand
(b) (b)
EDSEDS elemental
elemental map ofmap Zn of Zn element
element distribution
distribution map of
map of ZnO/HA
ZnO/HA
compositecomposite sample
sample with 20% with 20% Znsintered
Zn addition additionatsintered
1250 ◦ Catfor
1250
2 h.°C for 2 h.

4. Conclusions
4. Conclusions
The n-HA
The n-HA powders
powders were were successfully
successfully prepared
prepared byby the
the chemical
chemical precipitation method, and
precipitation method, and ZnZn
particles could
particles could bebe used
used as as a
a pore
pore forming
forming agent
agent material
material to
to prepare
prepare porous
porous HAHA composites with
composites with
controllable shape, size, and distribution. HA grain orientation was randomly
controllable shape, size, and distribution. HA grain orientation was randomly distributed in distributed in ZnO/HA
composites.
ZnO/HA OxidationOxidation
composites. of Zn tookof place during
Zn took the during
place sintering process,
the which
sintering was inwhich
process, three was
stages: Solid
in three
phase, liquid phase, and gas phase. Fine ZnO particles were formed and distributed
stages: Solid phase, liquid phase, and gas phase. Fine ZnO particles were formed and distributed between the
HA grains during the stages of liquid and gas, which hindered HA grain
between the HA grains during the stages of liquid and gas, which hindered HA grain boundaryboundary movement and
led to the refinement
movement and led toofthe HA. The HA grains
refinement of HA. were
Therandomly
HA grains distributed,
were randomlyand the crack propagation
distributed, and the
was hindered by the grain boundary and the second-phase particles
crack propagation was hindered by the grain boundary and the second-phase particles (ZnO). The direction of crack
(ZnO). The
propagation,
direction when propagation,
of crack it expands to other
whengrains, needed
it expands to to be changed,
other which increased
grains, needed the areawhich
to be changed, of the
cleavage fracture
increased the areasurface
of theand improved
cleavage the mechanical
fracture surface andproperties
improvedofthe the mechanical
composites. properties
The sampleofwith
the
the amount of 20% zinc had the best mechanical properties. The compression
composites. The sample with the amount of 20% zinc had the best mechanical properties. strength of ZnO/HAThe
composites was
compression 187% higher
strength than that
of ZnO/HA of pure HA,
composites was and
187% thehigher
mechanical properties
than that of purewere
HA,theand
bestthe
of
the sample containing 20% zinc. Controlling the size and distribution of the second-phase
mechanical properties were the best of the sample containing 20% zinc. Controlling the size and particles is
effective to control the mechanical properties of ZnO/HA composites.
distribution of the second-phase particles is effective to control the mechanical properties of
ZnO/HA composites.
Author Contributions: Conceptualization, X.L.; data curation, Y.M. and L.M.; formal analysis, Y.M. and H.Y.;
funding acquisition, S.Y.; investigation, S.Y.; methodology, X.L.; project administration, X.L.; resources, Z.M. and
Author Contributions:
L.M.; software, Conceptualization,
Z.M.; validation, X.L.; writing—original
Z.M. and H.Y.; data curation, Y.M. and S.Y.;
draft, L.M.;writing—review
formal analysis,and
Y.M. and H.Y.;
editing, S.Y.
funding
and X.L. acquisition, S.Y.; read
All authors have investigation,
and agreedS.Y.; methodology,
to the X.L.; project
published version administration, X.L.; resources, Z.M.
of the manuscript.
and L.M.; This
Funding: software,
workZ.M.; validation, by
was supported Z.M. and from
grants H.Y.; the
writing—original draft,Projects
Scientific Research S.Y.; writing—review andResearch
of Basic Scientific editing,
S.Y. and X.L.
Expenses All authors of
of Universities have read and agreed
Heilongjiang to the
Province published version of the manuscript.
(2018-KYYWF-0923).
Funding: This
Conflicts of work was
Interest: The supported by grants
authors declare from the
no conflict Scientific Research Projects of Basic Scientific Research
of interest.
Expenses of Universities of Heilongjiang Province (2018-KYYWF-0923).
References
Conflicts of Interest: The authors declare no conflict of interest.
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