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Structure and mechanical properties of hydroxyapatite coatings produced on

titanium using plasma spraying with induction preheating

Article  in  Ceramics International · May 2017

DOI: 10.1016/j.ceramint.2017.05.168

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 Ceramics International 43 (2017) 11189–11196

Contents lists available at ScienceDirect

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

Structure and mechanical properties of hydroxyapatite coatings produced MARK

on titanium using plasma spraying with induction preheating
⁎
Aleksandr Fomina, , Marina Fominaa, Vladimir Koshuroa, Igor Rodionova, Andrey Zakharevichb,
Aleksandr Skaptsovb
a
Yuri Gagarin State Technical University of Saratov, Institute of Electronic Technology and Engineering, 77 Politechnicheskaya str., Saratov 410054, Russia
b
Saratov State University, Institute of Nanostructures and Biosystems, 83 Astrakhanskaya str., Saratov 410012, Russia

A R T I C L E I N F O A BS T RAC T

Keywords: Coatings of hydroxyapatite (HAp) were prepared by plasma spraying with induction preheating of titanium
Hydroxyapatite coatings substrate from 200 to 1000 °C. The combination of conventional plasma spraying and induction preheating
Induction preheating ensured high mechanical properties of HAp coatings. The coatings produced in the temperature range 400–
Plasma spraying 600 °C were characterized by homogeneous nanostructure of splats with an average grain size of 12–31 nm.
Titanium
According to the results of nanoindentation HAp coatings with high hardness 0.9–1.2 GPa and elastic modulus
7–16 GPa were formed on the titanium.

1. Introduction [13,16,20,31,34,35], and in some cases subsequent thermal [3,36] or

Modern intraosseous implants and endoprostheses are produced
from different metals and alloys varying in their properties [1,2]. These
devices are characterized by a biocompatible layer (a film or coating)
having the following distinctive features:
1) Necessary structural parameters, in particular porosity [3], rough-
ness [2,4], presence of micro- and nano-sized grains and their
agglomerates [5–9].
2) Biocompatible chemical and phase composition determining the
presence of bioinert [8,10] or bioactive [11–16] interaction with the
bone tissue, sufficient corrosion resistance [17], as well as bacter-
icidal [18,19] and other properties of the coating [7,9,20,21].
3) High mechanical properties, particularly adhesive strength [17,22,23],
hardness H and elastic modulus E [13,24,25], fracture toughness,
resistance to plastic deformation [26], and wear resistance [27].
This combination of properties required for the implant surface and
design in general is practically impossible to provide by a single method
of production of a biocompatible interface layer. Conventionally, to
obtain the required surface characteristics various chemical [28–31],
mechanical [3], physical [32–34], and vacuum-condensation methods
[35] are applied. For the surface treatment of intraosseous implants
complex methods are widely used. They include preparatory mechan-
ical microtexturing and/or etching [3,4], functional layer deposition
chemical treatment, particularly biomineralization with the deposition
of bioactive ceramics [8,37]. The latter treatment can also be applied as
a test method for the evaluation of the potential for osteoinduction
[15]. On the other hand, a number of methods for the production of
coatings can meet the criteria of bioactivity in terms of biochemistry,
morphological heterogeneity of micro- and nanostructures [6,38,39]
but their mechanical properties are not sufficient for the implants
exposed to extremely high loads of hard bone pieces, i.e. crystals of
hydroxyapatite (HAp), when installed into the bone bed. Under these
conditions elements of the porous coating are subjected to friction,
which leads to the inevitable wear and, in some cases, they are
completely separated from the metal substrate of the implant [1].
Some approaches enumerated below can prevent this process:
1) Lowering of the parameters of surface morphology and porosity,
which is especially well manifested when PVD and CVD methods
are used [35]. These methods are widely used in microelectronics,
however, their application is appropriate in the nanostructuring of
the surfaces combined with other methods of microtexturing;
2) Strengthening of porous materials (blocks and coatings) with
special fillers of submicron and nano-sized bioceramic powders of
various oxides (Al2O3, ZrO2, TiO2) [5,40,41], carbides [42], nitrides
(TiN) [22], multi-walled carbon nanotubes [43], and whiskers [10];
3) Sublayer deposition enhancing the adhesion of the main functional
layer [22,23,35];

⁎
Corresponding author.
E-mail address: afominalex@gmail.com (A. Fomin).

http://dx.doi.org/10.1016/j.ceramint.2017.05.168
Received 9 May 2017; Received in revised form 22 May 2017; Accepted 24 May 2017
Available online 25 May 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
A. Fomin et al. Ceramics International 43 (2017) 11189–11196

Table 1 4) Production of high strength coatings of matrix type for the

Modes of plasma spraying with induction preheating. subsequent introduction of the bioactive filler [31,44];
5) Application of subsequent heat treatment, which also enhances the
Parameter Value
crystallinity of HAp coatings [34,45];
Current frequency of inductor, kHz 90 6) Thermal activation during production of the coating, the use of
Inductor current, kA – 4,4 7,6 which is limited due to a number of technological peculiarities [46].
Preheating temperature, °C 20a 200 400
Heating time, s – 2–3 3–4 600 800 1000
Spraying distance, mm 90 7–8 14–15 12–13 In most cases, additional treatment complicates the technology of
Arc current of plasma torch, A 540 production of the coatings, increases labor costs and the overall cost of
Voltage, V 30 biomedical products. High-efficient methods of coating production are
Size of powder, μm 50 ± 20 gas-thermal methods, such as plasma spraying [47,48] and high
Plasma gas flow rate (Ar), l/min 55–60
velocity oxygen fuel (HVOF) spraying [49]. The main disadvantage of
Carrier gas flow rate (Ar), l/min 5–7
gas-thermal methods is significant change of phase composition in the
a
Conventional plasma spraying without preheating. deposited powder particles. It affects the biomechanical compatibility
of the coating and bone.

Fig. 1. Scheme of plasma spraying with induction preheating. Internal circuit: U, I – voltage and current of plasma torch 1 from the power supply (PS); MPG and MCG – flow rate of
plasma and carrier gas (argon); MP, dP, TPPP – flow rate, particle size, and thermophysical properties of the powder. Outer circuit: L – spraying distance; TS, TPPS, CS – temperature,
thermophysical properties, and structural features of substrate 5; 3 – protective screen against the plasma jet 2 of the inductor 4 supplied by voltage Ui and current Ii with frequency f of
the induction heating device comprising the main power supply and a generator unit (GU); F – function depending on the treated item geometry.

Fig. 2. Morphological analysis of the nanostructure of HAp coating: a – SEM of the coating (mark 200 nm) and binarized fragment (image obtained by processing software); b –
distribution graph in linear dimensions of nanograins (x-axis – size, nm; y-axis – percentage, %).

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Fig. 4. SEM of the HAp coating produced at 200 °C (points "1–9" show the areas of EDX
analysis).

Fig. 3. XRD of HAp powder and coating samples produced at the spraying distance of
90 mm: • – HAp; □ – TCP; ■ – CaO.

Table 2
EDX of the HAp coating (preheating temperature 200 °C) and calculated values [Ca/P]
for bioceramic materials (see Fig. 4).

Spectrum O P Ca Total [Ca/P],

[wt%/wt%]
Fig. 5. Ca/P ratio for splats of different sizes: 1 – large splats; 2 – small splats with the
1 45.65 18.73 35.62 100 1.91 size of not more than 5–10 µm.
2 37.86 21.81 40.33 100 1.85
3 48.05 18.93 33.01 100 1.74
4 54.55 14.01 31.43 100 2.24 coatings (75 µm thick) with high hardness (~300 HV) have been
5 45.98 18.80 35.23 100 1.87
6 38.32 21.29 40.38 100 1.90
described, however there is no explanation of not changing hardness in
7 32.52 17.83 49.65 100 2.78 the interface and beyond in the presented graphs of hardness-depth
8 58.84 11.31 29.86 100 2.64 dependency (where depth is within 0.7 mm). The application of preheat-
9 55.07 10.00 34.93 100 3.49 ing of the sample substrate to 200 °C has been also described in the
HAp – – – – 2.16
studies [53] but there is no sufficient data regarding the temperature
TCP – – – – 1.94
TTCP – – – – 2.59 influence on the improvement of mechanical properties, hardness in
particular. Therefore, this research describes the results of the study of
structure, phase and chemical composition, and mechanical properties of
HAp coatings produced by plasma spraying with preheating at the
During the interaction between the molten particles of bioceramics temperatures within 1000 °C. The activation of titanium samples com-
and the metal substrate the cooling rate reaches 105–107 K/s, and for prises the application of high velocity and non-contact inductive heating
some materials it is even higher [12,50]. Under these conditions, splats by generating high-frequency electromagnetic waves [54].
solidify almost immediately before their crystallisation. Numerous crystal
nuclei are formed, however their subsequent growth is limited. During 2. Materials and methods
plasma heating of HAp particles their thermal destruction occurs with the
formation of the following phases: oxyhydroxyapatite (OHAp), oxyapatite 2.1. Preparation of coatings
(OAp), tricalcium phosphate (TCP), tetracalcium phosphate (TTCP), and
amorphous calcium phosphate (ACP) [1,51]. Resorption rate of the The samples were 2 mm thick plates made of commercially pure
constituent phases of such bioceramic coating in biological fluids is (CP) titanium VT1-00 (analogue of CP Titanium Grade 2). The main
represented by the following increasing sequence: HAp ≪ β-TCP < preparatory operations comprised abrasive sandblasting with an
OHAp / OAp < α-TCP < CaO < TTCP ≪ ACP. The proportion of these average corundum particle size of 200–400 µm, which provided the
phases should not exceed a certain amount, since their presence accel- necessary parameters of the surface microrelief and further removal of
erates coating resorption and might cause the loss of the implant [1]. various impurities in detergent solutions and in ethanol when titanium
Amorphization of the HAp coating caused by ultra-high cooling rate is samples were put into an ultrasonic bath. Plasma spraying of HAp
one of the reasons for the accelerated resorption of bioceramic coatings, coatings was performed at the spraying distance of 90 mm, arc current
reduction of mechanical properties, and subsequent rejection of the whole of 540 A, and voltage of 30 V (plasma spraying equipment "VRES
implant [2,3]. In some works, e.g. [52], the results of production of HAp 744.3227.001"). The technological parameters were presented in

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A. Fomin et al. Ceramics International 43 (2017) 11189–11196

Fig. 6. Surface morphology of titanium samples after treatment: a – abrasive blasting (a) and plasma spraying (b–d) at different preheating temperatures T: b – T = 20 °C (conventional
plasma spraying); c – T = 200 °C; d – T = 400 °C.

Table 3 2.2. Coating characterization

Morphological parameters of microstructure of HAp coatings.
Phase composition of HAp coatings was determined by X-ray diffrac-
Preheating Morphological Average splat size D and
temperature, °C heterogeneity confidence interval ΔD,
tion (XRD) on "Gemini/Xcalibur" diffractometer using an X-ray tube with
MH, 1/mm2 μm a copper anode (CuKα, λ = 1,541874 Å, 2Θ = 25–90°). The crystalline
structure of the coatings was analyzed using the software processing of
20 5821 5.7 ± 3.3 XRD patterns in order to remove the amorphous phase. Test sample
200 21,826 8.8 ± 4.5
400 6447 12.4 ± 5.3
preparation for XRD comprised the obtaining of a conglomerate of
600 11,245 12.9 ± 5.1 sprayed coating fragments. Delamination from the titanium substrate
800 4210 10.2 ± 6.5 was performed by scratching, and then the microparticles were bound into
1000 18,918 6.4 ± 4.1 the globular conglomerate using epoxy resin with an amorphous structure.
Ti substrate after 99,251 4.9 ± 2.8
Attachment of the obtained sample was performed on glass fiber.
sandblasting
Morphology of the coatings was studied on micro- and nanoscale by
scanning electron microscopy (SEM) to identify structure formation
Table 1. HAp was prepared by an aqueous precipitation method from patterns. Morphological parameters of the porous crystalline structure
the addition of calcium nitrate Ca(NO3)2 and diammonium phosphate were defined, including shape and dimensions of particles, as well as
(NH4)2HPO4 in ammonia solution, which was described in detail, e.g. pore sizes. Processing of SEM images was performed using software for
in [55]. After that HAp block was crushed and sieved into powder with the analysis of geometric parameters of micro-objects "AGPM-6M" and
an average size of 50 ± 20 µm. program "Metallograph" (Fig. 2). As a result of the morphological
Induction preheating was performed immediately before plasma analysis of the coating surface images the following parameters were
spraying, according to the scheme shown in Fig. 1. The heating rate of determined: average linear dimension of microrelief elements (grains/
the samples at the maximum power of induction heating device ranged pores, protrusions/cavities), their dispersion in size, and the number of
from 30 to 70 °C/s. The deposition duration was 3–5 s per sample, microrelief elements in the view field. SEM and energy dispersive X-ray
which corresponds to the resulting coating thickness 30–40 µm. fluorescent analysis (EDX) of the deposits were performed on "MIRA II
The laboratory apparatus for induction preheating included a power LMU" with "INCA PentaFETx3" detector. SEM and EDX of the
supply unit, a generator unit, and an LC-contour unit comprising an coatings were performed at 20 kV.
inductor and a quartz chamber for a sample [56]. The heating tempera- Elastic modulus E and hardness H of HAp coatings were evaluated
ture was measured with an infrared pyrometer "DT-8828" [57]. by nanoindentation using mechanical properties tester "NANOVEA

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A. Fomin et al.
Fig. 7. Nanostructure of HAp coatings produced at different preheating temperatures: a – 20 °C (conventional plasma spraying); b – 200 °C; c – 400 °C; d – 600 °C.
Fig. 8. Dependency of the average HAp grain size D on the preheating temperature.
Ergonomic Workstation". The selected load applied to Berkovich
indenter equalled 100 mN and provided its penetration into the coating
within the thickness of 1–3 splats (about 1.5–2.5 µm).
3. Results and discussion
3.1. Phase and chemical composition
Phase composition of HAp coatings significantly depended on the
preheating temperature (Fig. 3). The initial composition of the sprayed
bioceramic powder corresponded to HAp [58]. Analysis of diffractograms
(without correction of amorphous phase) of the bioceramic coatings
showed that the amount of initial component HAp remained sufficient
at the temperatures of 400–800 °C. Its proportion ranged from 40% to
60% and the maximum of the crystalline phase equalling 70% was
observed at the preheating temperature of about 600 °C. A slightly lower
amount of the crystalline phase of calcium phosphate compounds (HAp
with 10% addition of TCP and 3–7% of CaO impurity) was produced at
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Ceramics International 43 (2017) 11189–11196
the temperature of 600–1000 °C. The samples of coatings produced at the
temperatures of 20 °C (without preheating) and 200 °C were characterized
by lower crystallinity (about 10–20%), HAp amount – 10–12% with a
slight addition of TCP and CaO, not more than 5% each. TCP, CaO, and
ACP are the phases of HAp decomposition, they also have increased
resorption rate and lower mechanical strength compared to the initial
HAp [1].
Classification of splats in size and chemical composition was
performed considering the characteristic ratio of [Ca/P], which for
the high chemical stability should be in the range of [Ca/P] = 1.94–
2.16 [wt%/wt%], corresponding to the phase composition of HAp with
a addition of TCP (Table 2, Fig. 4). Chemical composition analysis
showed that splats were characterized by almost complete retention of
the initial sprayed HAp powder.
Noticeable changes occurred with the preheating temperature of
about 800 °C, when the amount of Ca was high. XRD data also showed
an increased proportion of CaO. According to SEM results at this
preheating temperature individual small splats (less than 5–10 µm)
almost completely disappeared in the coating, as they were alloyed into
the surface layer (Fig. 5).
Analysis of the influence of induction preheating followed by
plasma spraying of HAp coatings on their phase and chemical
composition allows the development of recommendations on the
preheating temperature of titanium samples. When comparing XRD
and EDX data the following was established:
1. Much of the crystalline HAp transformed into the amorphous phase
without preheating and at low temperature of 200 °C. Preheating
temperature from 400 to 800 °C and to a minor extent at 1000 °C
A. Fomin et al.
Fig. 9. Dependency of elastic modulus (a) and hardness (b) on the preheating
temperature.
contributed to amorphization decrease and maintenance of sufficient
HAp phase.
2. When preheating temperature of titanium substrate increased to
600 °C the dust fragments of particles almost disappeared. Their
chemical composition was characterized by [Ca/P] ratio of more
than 2.00.
3.2. Surface morphology
Morphological heterogeneity MH of HAp coatings is a quantitative
characteristic of the size distribution of protrusions and pores on the
surface of splats and their structural components. The microstructure
of HAp coatings had significant differences depending on the preheat-
ing temperature (Fig. 6). Average diameter DS dependency for micro-
protrusions of the coating on the temperature of titanium substrate was
parabolic (Table 3). Without preheating size DS took a minimal value.
Maximum was observed at the preheating temperature of 400–600 °C.
With further increase of preheating temperature T to 800–1000 °C size
DS decreased. Abrasive blasting of titanium substrate ensured high MH
value (Fig. 6a).
Analysis of MH parameter was based on the density of splat
protrusions in the studied area, as MH varies according to the periodic
law. Minimal value of MH corresponded to the temperature of 400 and
800 °C. The same values were observed without preheating, which
corresponded to the conventional plasma spraying (Fig. 6b). Small
spherical particles sprayed at this spraying distance interacted weakly
with the surface of titanium substrate, thus large splats formed the
coating. MH grew from 2 to 4 times at 200, 600, and 1000 °C. At the
preheating temperature of 200 °C the cohesion of fine spherical particles
of HAp powder increased (Fig. 6c). High fluidity of splats lead to the
smoothing of the surface microrelief at the preheating temperature of
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Ceramics International 43 (2017) 11189–11196
400 °C (Fig. 6d). However, at the impact of liquid droplets the emerging
surges influenced the microgeometry of HAp coatings at the preheating
temperature of 600 °C. With further increase of the substrate temperature
to 800 °C MH was reduced due to the lengthy stay of sprayed particles of
all sizes in viscoplastic or liquid state. Splat thickness decreased from 5 to
10 µm to the minimum value of about 1–2 µm, which lead to a sharp
increase in the cooling rate up to the supercritical value, and as a result, to
the noticeable crack formation.
At the upper limit of the studied preheating temperature of 1000 °C the
formation of a TiO2 film was observed, which was characterized by high
morphological heterogeneity. The presence of intermediate oxide sublayer
reduced the cracking of bioceramic HAp layer, enhanced the attachment of
small spherical splats, and limited the spreading of large splats.
The structural condition of the coating on the nanoscale was assessed
by the parameter of grain size D. The samples of coatings with
morphology parameters close to those of the bone trabeculae with mineral
plates (crystal grains) of HAp were considered the most appropriate. The
resulting HAp coating without preheating was characterized by consider-
able heterogeneity of nanostructure and formation of numerous dust
particles and their agglomerates (Fig. 7a). This structure had low
mechanical characteristics, in particular hardness, which normally lead
to wear and coating delamination during the installation into the bone.
Similar morphology of HAp coating and bone tissue is required for
activation of the geometrical factor of bioactivity on the nanoscale.
When the substrate was preheated to 200 °C the structure of
plasma coatings varied slightly. The average grain size D increased to
26 ± 9 nm, however, numerous agglomerates of 50–300 nm were
observed on the surface (Fig. 7b). With further increase of the
preheating temperature to 400 °C the structure of coatings became
practically homogeneous (Fig. 7c). Agglomerates were sporadic and
consisted of a small amount of nanoparticles. The average diameter
reached the maximum of about 31 ± 8 nm. It should be noted that in
the area of heating from 20 to 400 °C there was a linear increase in the
size of nanograins (Fig. 8; line D1).
Viscosity decrease caused by heating to 600 °C contributed to better
spreading of splats, so the reduction of the average grain size D to the
initial value of 11 ± 5 nm was explicable and it was described by the
parabolic dependency (Fig. 8; curve D2). The structure was character-
ized by high homogeneity, the agglomerates were sporadic. Under
these conditions, the smallest nanocrystals with the size of 3–7 nm
making about 50–60% were distinguished. Nano-grains formed ag-
glomerates with the size of 14–40 nm (Fig. 7d).
When the preheating temperature was between 800 and 1000 °C
separate agglomerated nanoparticles of 30–90 nm were arranged on
the "smooth" surface of the HAp coating. There was a marked decrease
in morphological heterogeneity and the average size of nanograins
equalled D = 6–12 nm.
Analysis of the structures on the nanoscale showed that the preheating of
titanium substrate ensured quite homogeneous nanocrystalline structure of
the coatings. As a result the necessary convergence between morphology
types of HAp coatings and bone trabeculae was established.
3.3. Mechanical properties
In order to produce HAp coatings with high mechanical properties the
comprehensive studies of the elastic modulus and hardness were
performed. It should be noted that the hardness of HAp coating exceeding
that of the cortical bone provides the improved biomechanical compat-
ibility and it is expected to eliminate the danger of its destruction during
the installation of the implant into the bone bed. The suggested induction
preheating of titanium substrate before the deposition of the coating
enhanced mechanical properties, such as adhesion and cohesion.
However, when the implant is installed its local area of the surface is
exposed to the concentrated force. Thus, high hardness and elastic
modulus of porous HAp coatings are necessary for their further reliable
performance in the tissues of the human body (Fig. 9).
A. Fomin et al.
Low preheating temperature of titanium substrate did not signifi-
cantly increase the hardness. Elastic modulus of the coatings at the
temperature about 200 °C increased 2–2.5 times. The highest values of
the elastic modulus for cortical bone reached 25–30 GPa with the
hardness of about 0.5–0.8 GPa. If this preheating temperature is used
low performance of intraosseous implants may occur.
In the middle range of preheating temperature (400–600 °C) the
hardness of HAp coatings reached the values typical for the solid fragments
of cortical bone. The elastic modulus remained around 8–12 GPa.
Preheating to 800–1000 °C ensured a 2–3-fold margin of hardness at the
maximum value of the elastic modulus of the HAp coating.
4. Conclusions
The surface of titanium VT1-00 after plasma spraying with induction
preheating of substrate was characterized by the formation of bioceramic
coatings with the phase and chemical composition close to HAp (which
was confirmed by XRD and EDX), high morphological heterogeneity of
microstructure, homogeneous nanostructure (confirmed by SEM), and
high mechanical properties, hardness in particular. HAp coatings with the
required qualities were formed of micro-sized splats, the surface of which
had nanograins (D = 12–31 nm). The best morphological parameters of
HAp coatings combined with high hardness of about H = 0.9–1.2 GPa and
elastic modulus of at least E = 7–16 GPa were determined. These samples
of coatings corresponded to the preheating temperature T = 400–600 °C.
Acknowledgments
The research was supported by the Ministry of Education and
Science of the Russian Federation in the framework of the Program of
Scientific Research in Universities (project No. 11.1943.2017/PP).
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