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Preliminary studies of TiO2 nanopowder deposition onto metallic substrate by

low pressure cold spraying

Article  in  Surface and Coatings Technology · September 2018

DOI: 10.1016/j.surfcoat.2018.09.057

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Surface & Coatings Technology

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Preliminary studies of TiO2 nanopowder deposition onto metallic substrate

by low pressure cold spraying
⁎
M. Winnickia, , A. Baszczukb, M. Jasiorskib, B. Borakb, A. Małachowskaa
a
Department of Materials Science, Strength and Welding Technology, Wroclaw University of Science and Technology, Łukasiewicza 5 Str., Pl-50371 Wroclaw, Poland
b
Department of Mechanics, Materials Science and Engineering, Wroclaw University of Science and Technology, Smoluchowskiego 25 Str., Pl-50370 Wroclaw, Poland

A R T I C LE I N FO A B S T R A C T

Keywords: Ceramic coatings, e.g. TiO2, can be produced by various methods, such as flame spraying, plasma spraying, PVD,
Titanium dioxide CVD, etc. According to the literature, cold spraying enables deposition of plastic materials and therefore is
Phase transition dedicated to metals and polymers. Ceramics are hard and brittle due to the complex crystalline structure.
Amorphous powder However, very recently it was shown that chosen ceramics can be deposited by cold spraying. In this work,
Ceramic coatings
various polymorphs of sol-gel TiO2 powders, e.g. amorphous, anatase and rutile, were used as a feedstock for the
Cold spraying
cold spray (CS) process. The preliminary study of coating formation indicated that the key parameter for the
process seems to be temperature of working gas. However, coatings were deposited form all prepared powders.
Selected parameters enabled deposition of titania coatings with the thickness about 100 μm. What is even more
interesting, the increase in the temperature of working gas results in nanocrystallization of the amorphous
powder into anatase coating.

1. Introduction others [3,5,8–12]. Titanium dioxide as a wide gap semiconductor oxide

The ceramic coatings are applied both as functional coatings and
coating improving mechanical properties e.g. hardness, wear resistance
and corrosion [1,2]. Especially interesting ceramic material seems to be
titanium dioxide. Titanium dioxide (TiO2), also known as titania, is a
hard material with high melting point of 1870 °C. It occurs in four
polymorphous forms: anatase, rutile, brookite and amorphous, where
the former three are crystalline [3–5]. Rutile is the only stable form,
anatase and brookite are metastable [3–6]. Chemically pure anatase or
rutile can be obtained by hydrolysis reaction and starting from amor-
phous form of TiO2. In this reaction liquid solution dehydrates together
with arising temperature. Starting from 300 °C crystals nucleate and
grow up. At the temperature of about 600 °C anatase starts to transform
into rutile [7]. A discrepancy in thermal energy creates various crystal
phases. Therefore, in final product crystal structure build of mixture of
anatase and rutile is received and thus material is irregular and non-
uniform.
Rutile and anatase are most popular among titania polymorphs due
to their availability, biological and chemical inertness, chemical and
thermal stability, long term stability against chemical and photo-
chemical corrosion transparency in the range of visible light, photo-
electrochemical and photocatalytic conversion capability and many
has strong oxidizing power and superhydrophilicity and thus can be
used as antibacterial agent, self-cleaning agent, in water and air pur-
ification systems. It is worth stressing, that porous TiO2 films are used
in dye-sensitive solar systems or in bone implants and renewable en-
ergy. However, anatase phase with fine particles grain size is more
preferable for high photoactivity compared to rutile, due to larger band
gap (3.2 eV for anatase vs. 3.0 eV for rutile) [3–5,9,11].
Titanium dioxide coatings can be deposited by various method, such
as: chemical vapour deposition, electro-deposition, dip coating, mag-
netron sputtering or thermals spraying. However, chemical vapour
deposition [3–5], electrodeposition [8,9,13] dip coating [10,14,15] and
magnetron sputtering [16–18] enable deposition of very thin films with
thickness usually about 500 nm. The films thickness can be increased
with process parameters up to 3 μm [14,15,17]. The only method
providing thicker coating and high rate deposition is thermal spraying,
where ceramic coatings are deposited mostly by plasma spraying
[1,11,19] or high velocity oxygen fuel [11,20]. However, phase tran-
sition of anatase to rutile occurs in conventional thermal spray pro-
cesses. What is more, during spraying process molten particles loss the
characteristic and properties of nanostructured materials as the ag-
glomerated nanoparticles are melted and experience grain growth. It
should be noted, that anatase is more efficient as photocatalyst than

⁎
Corresponding author.
E-mail addresses: marcin.winnicki@pwr.edu.pl (M. Winnicki), agnieszka.baszczuk@pwr.edu.pl (A. Baszczuk), marek.jasiorski@pwr.edu.pl (M. Jasiorski),
beata.borak@pwr.edu.pl (B. Borak), aleksandra.malachowska@pwr.edu.pl (A. Małachowska).

https://doi.org/10.1016/j.surfcoat.2018.09.057
Received 5 July 2018; Received in revised form 31 August 2018; Accepted 24 September 2018
0257-8972/ © 2018 Elsevier B.V. All rights reserved.

Please cite this article as: Winnicki, M., Surface & Coatings Technology, https://doi.org/10.1016/j.surfcoat.2018.09.057
M. Winnicki et al.
rutile and thus is more desirable. Therefore, new processes should be
proposed that utilize kinetic energy instead of thermal energy by in-
creasing particles velocity. These processes are aerosol deposition
method and cold spraying.
Cold spray is a unique thermal spraying method that enables par-
ticles bonding is in solid state [21–24]. Powder is accelerated in stream
of heated and pressurized gas towards substrate. Upon impact particles
deform plastically and formation of the coating occurs. Such bonding
mechanism implies difficulty in obtaining ceramic coating owing to
lack of plastic deformation of ceramics [21]. The other method, e.g.
aerosol deposition (AD) process, enables to obtain ceramic coatings. In
the AD method the submicron and nanometric particles are accelerated
in stream of gas towards the substrate but the whole process takes place
in vacuum [25–27]. These notable increases cost and limit the dimen-
sions of the coated elements. When spraying individual ceramic nano-
particles in vacuum, it is commonly believed that during impact frag-
mentation and packing of the particles occurs [12]. The fractured
nanoparticles stick together with few bonding sites. Subsequent sub-
micron particles strike the accumulated nanoparticles providing shock
compaction of the nanoparticles. The nanoparticles are consolidated at
high heat energy and pressure [28,29].
The cold spray operates at atmospheric pressure, therefore it is
impossible to spray small powders of nanoparticles. Therefore, powder
agglomeration is needed. This process introduces additional variables
resulting from the internal structure of the agglomerate, its bonding
degree, as well as its aerodynamic properties. However, first attempts
proved that deposition of ceramic coatings by cold spraying is possible
through substrate deformation and mechanical interlocking of ceramic
particles with substrate material [30,31]. The subsequent layers are
deposited by metal flash, which was detached from the substrate and
was transferred to the coating. This coating mechanism implies that
thickness of the coating is limited owing to difficulties with provision of
metal flash from the substrate [32]. The impossibility of pure ceramic
coating formation in [32] was probably related to the morphology of
the powder used, which was in shape of sintered spheres. In 2011 Salim
et al. proved that the key feature in formation of ceramic coatings is
using agglomerated powder [33]. TiO2 was synthesized in a simple
hydrolysis method of titanyl sulfate (TiOSO4) in distilled water with a
small addition of inorganic salt. The powder formed agglomerates with
fine nanoparticles and was then post-treated with annealing or hydro-
thermal treatment. The post-treated powders formed more defined and
thicker coatings. When deposited using the same cold spray parameters,
the hydrothermal treated TiO2 formed a thicker coating of 150 μm than
the annealed TiO2–75 μm [33].
According to the literature, deposition of ceramic powder by cold
spraying is possible. The bonding mechanism prescribed to the slipping
or sliding of particles over other particles will occur much easier for
ceramic materials composed of nanoparticles [34,35]. Additionally, it
was concluded that tightly agglomerated particles result in lower por-
osity. The impacting single particle has low energy to penetrate the
stagnation layer on the substrate [36]. Therefore, agglomerated TiO2
particles promote better adhesion between particles and the substrate.
However, titania has various polymorphs and thus the bonding me-
chanism should be analysed further. The investigation of ceramic
coatings formation with cold spray method opens totally new manu-
facturing routes of ceramics. It allows to obtain ceramic coating with
initial properties of feedstock by low energetic method. In presented
work powders produced by sol gel methods of various polymorphic
forms of titanium dioxide, e.g. amorphous, anatase and rutile are
adopted to low pressure cold spraying process.
2. Materials and methods
2.1. Powders and substrate preparation
Powders of TiO2, e.g. amorphous, anatase and rutile, were self-
2
Surface & Coatings Technology xxx (xxxx) xxx–xxx
prepared through a sol-gel method. The synthesis details were identical
to that described in our previous work [37]. In the sol-gel synthesis
titanium isopropoxide, isopropanol, deionized water and aqueous am-
monia were used as starting materials with volume ratio 3:42:7:4, re-
spectively. The prepared solution was stirred in a plastic flask with
magnetic stirrer at room temperature and in air atmosphere for 2 h.
Titania colloids were allowed to dry at room temperature. Finally white
TiO2 amorphous powder was produced.
Substrate materials were plates of aluminium alloy AA1350 (99.5%)
with dimensions of 20 × 20 × 7 mm. The substrates surface prior to
spraying was degreased and activated by sand blasting under a pressure
of 0.6 MPa using fine alumina powder (mesh 325).
2.2. Design of spray process experiments
The coatings were sprayed using DYMET 413 (Obninsk Center for
Powder Spraying, Obninsk, Russia) with internal gas heater in spraying
gun. A circular de Laval nozzle was used with an outlet diameter of
5 mm. Powder was fed radially in the beginning of divergent part of the
nozzle. In the research air was used as a working gas with pressure of
0,5 MPa. A spraying gun was attached to manipulator (BZT
Maschinenbau GmbH, Leopoldshöhe, Germany) moving with traverse
speed of 5 mm/s. Stand-off distance was selected to 10 mm and the
distance between next spraying beads was 2 mm. Coatings were ob-
tained with two passes of the spray gun over the substrate to form
deposits of various thickness, depending on the process parameters. A
temperature of working gas was varying parameter of: (i) 200 °C, (ii)
400 °C and (iii) 600 °C. Deposition efficiency was estimated quantita-
tively comparing the powder quantity fed in versus the mass quantity
coated.
To estimate working gas temperature at the nozzle exit, temperature
measurements with the use of thermocouple were conducted. Scheme
of the spraying gun with temperature measurement points is shown in
Fig. 1. Working gas temperature at the nozzle entrance means the
temperature selected at the device.
2.3. Materials characterization
The morphology of titania powders as well as surface and micro-
structure of deposited coatings were analysed using SEM (Hitachi S-
3400 N, Tokyo, Japan) microscope equipped with SE, BSE detectors and
EDX system for elemental analysis. The metallographic specimens were
prepared by cutting the coated sample in the middle of its length.
Afterwards the cross-sections were ground and polished. Powders grain
size was measured with the use of particle sizing instrument (Malvern
Mastersizer 2000, United Kingdom).
X-ray diffraction analyses (XRD) were performed on both, the sol-
gel powders and cold spray coated specimens, to identify the phases
present on their surface. The measurements were carried out using
Rigaku Ultima IV Diffractometer (Japan) with Cu Kα irradiation
(λ = 1.5406 Å) within the range from 15° to 90° in 0.02° steps with an
exposure time of 4 s per point. Additionally, to confirm obtained results,
Raman spectra were measured with Raman system LabRAM HR800,
Horiba Jobin Yvon (Japan).
3. Results and discussion
3.1. Powders characterization
Powders produced by sol-gel synthesis were dried in various tem-
peratures. Amorphous powder dried at room temperature, while ana-
tase and rutile dried at 500 °C and 800 °C, respectively. All TiO2 pow-
ders showed agglomerated morphology with particles size of 10–70 μm
and similar shape. However, the main powder particles of spherical
shape were submicron size up to 0.5 μm. The particle size of produced
powders was in the range of 3.6–78.6 μm (D0.5 = 35.9 μm),
M. Winnicki et al.
Fig. 2. Micrographs (SEM, BSE) of sol-gel powders after synthesis.
3.4–70.4 μm (D0.5 = 19.4 μm) and 6.9–96.7 μm (D0.5 = 35.9 μm), re-
spectively. Micrographs of sol-gel powders are presented in Fig. 2. It is
visible, that amorphous powder showed tendency to joining of ag-
glomerates. Moreover, amorphous agglomerates seemed to be more
porous compared to anatase or rutile. Moreover, amorphous agglom-
erates seemed to be more porous compared to anatase or rutile.
Amorphous powder was produced from solution that dried at room
temperature. Therefore, residue of organic binder was still presented in
3
Surface & Coatings Technology xxx (xxxx) xxx–xxx
Fig. 1. Scheme of spraying gun with inner electrical
heater (a) and de Laval nozzle (b) with convergent
(c) and divergent (d) sections. 1 – working gas, 2 –
nozzle throat, 3 – working gas temperature mea-
surement with thermocouple at the nozzle exit, 4 –
powder feeding, 5 – working gas temperature at the
nozzle entrance fixed at the device.
the material when it was crushed into powder. The organic binder,
composed mostly of alcohol, disabled proper compaction of powder. As
a result agglomerates were more porous. In the case of anatase and
rutile, elevated temperature of dehydration together with crystal nu-
cleation decreased agglomerates porosity. Agglomerates compacted in
sintering process by formation of interparticle necks. On the other
hand, rutile agglomerates were bigger. It arises also from high tem-
perature of dehydration that provided grains growing. Measured bulk
M. Winnicki et al.
Fig. 3. Raman spectra of sol-gel powder dried at various temperatures.
density was 0.67 g/cm3, 1.01 g/cm3 and 1.16 g/cm3 for amorphous,
anatase and rutile powders, respectively.
The Raman spectroscopy was conducted to analyse phases con-
tained in prepared powder after drying at various temperature in 2 h.
For powders dried at room temperature and at 100 °C measurements
clearly demonstrate extremely broad peaks with low intensity in-
dicating amorphous state of the feedstock material. Increased tem-
perature began crystallisation process. As one can notice, for powders
dried at 300 °C Raman peaks are slightly sharper and their positions are
approximately similar with positions typical for anatase phase. Clearly,
further increased of temperature (500 °C) caused total transition into
anatase. Precise analysis of Fig. 3e reveals peaks at 148(Eg), 397(B1g),
521(A1g) and 641(Eg) cm−1 which can be assigned as the modes re-
ported for anatase [38]. Further analysis of Raman spectrum measured
for powder dried at 800 °C (Fig. 3f) reveals peaks at 139(Eg), 239(A1g),
450(B1g) and 617(Eg) cm−1 which are in good agreement with reported
for rutile phase [39].
3.2. Coatings characterization
Coatings surface topography, thickness and density depend strongly
on powder material phase and gas preheating temperature as well
[21,23]. Powders had various size and bulk density as a result of formed
agglomerates, what influenced spraying process significantly and de-
position efficiency as well. The highest deposition efficiency obtained
for amorphous, anatase and rutile powders using working gas heated to
600 °C was 25%, 17% and 3%, respectively. Coating deposited using
lowest gas temperature showed worst quality. Amorphous powders
resulted in satisfactory powder deposition. Coatings thickness was up to
50 μm. However, coatings were characterized by delamination, micro-
cracks and porosity (Fig. 4a,b). Anatase (Fig. 4c,d) and rutile (Fig. 4e,f)
created very thin films on the aluminium substrate. It took a form of a
submicron particles interlocked on the substrate surface irregularities.
Coating roughness results from substrate sand-blasting or local de-
position of agglomerated powder particles. Nevertheless, obtaining
thicker coating was impossible independently on number of coating
layers sprayed onto the substrate material.
Increasing process temperature to 400 °C provided interesting
changes in deposition process. Coatings deposited with amorphous
powder were continuous, free of delamination and with the thickness in
the range of 30–70 μm. However, some porosity and microcracks are
still visible in the coating structure (Fig. 5). It should be noted that
Raman spectroscopy showed beginning of phase transition from
amorphous TiO2 to anatase. On the other hand, XRD analysis did not
confirm this phenomenon. Results obtained with Raman spectroscopy
4
Surface & Coatings Technology xxx (xxxx) xxx–xxx
are more precise as it uses laser in a point measurement otherwise to
XRD, where larger area is measured and the measurement error is over
3%. Anatase powder showed additive coating formation with strong
tendency to delamination and cracking (Fig. 6). As a result, there were
numerous areas on the sample with rebounded and cracked coating.
Nevertheless, XRD analysis showed no results for aluminium substrate.
In the case of rutile powder, there was progress in powder deposition
also (Fig. 7). Submicron particles created very thin film on the alumi-
nium substrate (Fig. 7c). However, locally thicker coating was obtained,
what is clearly seen in the Fig. 7b. It can be caused by local agglom-
erated powder deposition.
Further increase of the working gas temperature up to 600 °C had
negligible effect on the anatase and rutile powders deposition.
Delamination and cracks were present in the anatase coating, while
rutile coating showed regions with thin film. Nevertheless, both powder
materials resulted in thicker coating deposition (Fig. 8). Amorphous
powder provided very thick coatings with the thickness of about
100 μm and regular surface topography (Fig. 9). What is more, phase
transition occurred in the spraying process from amorphous form to
anatase. XRD pattern of the powder and coating is visible in Fig. 10a.
The pattern obtained for the powder showed typical broad halos re-
sulting from amorphous state of material. However, the coating pattern
showed seven typical distinctive peaks corresponding to anatase at:
25.2°, (101), 36.8° (103), 37.8° (004), 38.6(112) 48° (200), 53.9° (105)
and 55° (211). Moreover, Raman spectrum (Fig. 10b) revealed that
amorphous titanium dioxide powder was transformed into crystalline
anatase form during the spraying process. All resulted Raman peaks at
Eg (145 cm−1), B1g (201 cm−1), A1g (397 cm−1), B1g (520 cm−1), and
Eg (641 cm−1) were modes reported for anatase phase.
It is well known, that powder particles gain temperature in the
nozzle from preheated gas. Therefore, prior to coatings deposition gas
temperature was measured by thermocouple at de Laval nozzle exit
(Fig. 1). The highest gas temperature at the nozzle exit was 401 °C.
4. Discussion
Cold spray can be successfully applied to deposition of ceramics.
However, some special conditions have to be fulfilled. According to the
literature, the most important parameters are: (i) pressure of the
working gas and (ii) ceramic powder preparation. Pressure of the
working gas should be above 2 MPa to enables anchoring of ceramic
particles in the substrate material [11,12,30]. However, deposition of
thicker coating requires special powder preparation. Yamada et al. [40]
applied agglomerated titanium dioxide powder with nanoscaled parti-
cles in high pressure cold spraying and obtained thick coatings. Ac-
cording to this research, deposition of ceramics is conditioned sig-
nificantly by powder material. However, pressure lower than 1 MPa can
be used. On the other hand, working gas temperature is important also.
Lowest analysed temperature of gas, e.g. 200 °C, resulted in thin coating
deposition of anatase and rutile with presence of submicron particles.
Amorphous powder enabled deposition thicker coating, however mi-
crocracks and delamination occurred. A bonding of particle seemed to
be only in a form of mechanical interlocking in both cases.
Increasing gas temperature provided higher particle velocity and
temperature and as a result higher energy in the system [21]. Anatase
and rutile powders formed some thicker coatings, basing on mechanical
interlocking. Both materials showed presence of powders agglomera-
tions in the coatings microstructure. However, the coatings continuity
and structure was not satisfactory. In the case of anatase powder the
shape of coating surface was regular and continuous at the end of
spraying process. Nevertheless, simultaneously with cooling locally
appeared peaks in the coating and delamination occurred (Fig. 5a). It is
stated, that cracks were formed in the coating while sample was
cooling, what resulted from difference in thermal expansion of ceramic
coating and metal substrate. Finally cracks connected and delamination
of the coating occurred.
M. Winnicki et al. Surface & Coatings Technology xxx (xxxx) xxx–xxx

a) b)

c) d)

e) f)

Fig. 4. Micrographs (SEM) of coatings sprayed with the use of amorphous (a,b), anatase (c,d) and rutile (e,f) powders and air preheated to 200 °C, coatings surface
(SE) (a,c,e) and cross section (BSE) (b,d,f).

Spraying process with amorphous powder was comparable to ana- consisted of regions with both amorphous submicron particles and
tase, however more stable. Powder particles obtained energy needed to growing crystals. Phase transition is usually indicated by increased
phase transition and started to change into anatase with the working temperature in thermal annealing process. The phase transition of
gas temperature of 400 °C. As a result of this transition, coating amorphous titania to anatase, what means crystal nucleation, begins

a) b)

Fig. 5. Micrographs (SEM) of coating sprayed with the use of amorphous powder and air preheated to 400 °C, coating surface (SE) (a) and cross section (BSE) (b).

5
M. Winnicki et al.
a)
Fig. 6. Micrographs (SEM) of coating sprayed with the use of anatase powder and air preheated to 400 °C, coating surface (SE) (a) and cross section (BSE) (b).
a)
c)
Fig. 7. Micrographs (SEM) of coating sprayed with the use of rutile powder and air preheated to 400 °C, coating surface (SE) (a) and cross section (BSE) (b,c).
above 300 °C [9]. In this study anatase sol-gel powder was obtain after
2 h drying at 500 °C, while the first changes started at 300 °C (Fig. 2).
Higher temperature of 500 °C enabled total phase transition of amor-
phous powder into anatase. It should be noted, that in cold spraying
temperature acts on the powder particles by heated working gas in a
very short time. According to Champagne [21], inside the nozzle par-
ticles stayed in the gas stream in a time below 1 μs. What is more,
previous work describing numerical aspects of cold spray process [41]
showed, that gas temperature significantly decreased in the divergent
part of the nozzle. At the powder feeding place gas temperature was
50% lower compared to its value at the nozzle entrance. This tem-
perature decreased additionally through the length of de Laval nozzle.
In this research, the highest measured gas temperature at the nozzle
exit was 401 °C (Fig. 1). However, the temperature of the substrate
measured by thermocouple joined on the backside of the sample was
253 °C. Thus, increased temperature of about 250 °C acting on coating
material in a time of spraying, e.g. 2 min in this process, could not be
responsible for powder material phase transition alone. Cold spraying is
a dynamic process, where enormous amount of kinetic energy occurs,
6
Surface & Coatings Technology xxx (xxxx) xxx–xxx
b)
b)
which is transformed into plastic deformation and enables phase tran-
sition. On the other hand ceramics, together with polycrystalline TiO2 is
a hard and brittle material. It results from strong ionic or covalent
bonds and complex crystalline structure that disable dislocation mo-
tions [42]. However, amorphous material, known as soft ceramics, has
totally different properties and can be plastically deformed [42–45].
Studies in this field are conducted for many years [46–49], but the
mechanism of ceramics plastic deformation is still unclear. Unusual
deformation of amorphous ceramic is partly due to porous structure and
coexistence of the amorphous phases and crystalline phases [44,45,48].
Xu et al. [48] analysed amorphous ceramic with different crystallinities
in hot pressing and found, that material plasticity resulted from free
volume theory. Authors stated that interface-introduced stress con-
centrations leaded to enlarged free volume in certain areas and de-
creased the energy for atomic migration, providing shear bands and
enhanced plasticity. Plastic deformation was also found in metastable
amorphous ceramic and resulted from easier formation and propaga-
tion of shear bands rather than further densification [49]. A coexistence
of amorphous phase and crystalline phase in compressive stress state
M. Winnicki et al.
a)
c)
Fig. 8. Micrographs (SEM) of coatings sprayed with the use of anatase (a) and rutile (b) powders and air preheated to 600 °C, coating surface (SE) (a,c) and cross
section (BSE) (b,d).
a)
Fig. 9. Micrographs (SEM, BSE) of amorphous powder sprayed with the use of air preheated to 600 °C, coating surface (a) and cross section (b).
activates formation of shear band [44,45,48,50]. According to this
theory, structural evolution of amorphous material can be controlled by
volume fraction of crystalline second phase [50]. The addition of sec-
ondary phase prevents propagation of the cracks finally resulting in
brittle fracture of the material and support the formation of multiple
shear bands [44,50]. In cold spraying of metal powders formation of
adiabatic shear bands is common [21]. Single particle impacting the
substrate is strongly deformed. Material jet is formed as a result of
materials flow. Simultaneously local shear bands are created [51,52].
The temperature increase is so high that cause dynamic recrystalliza-
tion in metals [53]. Moreover, locally temperature can be close to
material melting point [24]. Therefore, it can explain a phase transition
of amorphous titania powder to anatase coating in cold spraying.
However, this mechanism needs much more research to be confirmed.
7
Surface & Coatings Technology xxx (xxxx) xxx–xxx
b)
d)
b)
5. Conclusions
In the presented paper various polymorphs of titanium dioxide
powders were produced by sol-gel method and used in low pressure
cold spraying process. Powders of rutile, anatase and amorphous TiO2
were of submicron size with high tendency to agglomeration. Next to
the powder material, working gas temperature was a parameter influ-
encing coatings deposition. Rutile enables deposition of thin coatings,
while anatase coatings showed strong cracking and delamination. The
mechanism responsible for powder deposition was mechanical inter-
locking of submicron powders with local presence of agglomerates.
Coatings deposited with amorphous TiO2 were most satisfactory.
This material formed a coating in spraying process with working gas
preheated to 200 °C. The increase of working gas temperature caused
phase transition from amorphous to anatase, what was confirmed by
XRD and Raman analysis. Amorphous material is known as soft cera-
mics. Together with adiabatic shear instability intensive in cold
M. Winnicki et al.
a)
Fig. 10. XRD (a) and Raman (b) spectra obtained for coating deposited of amorphous powder with the use of air preheated to 600 °C.
spraying process titania powder particles gain enough energy to start
phase transition. This results opens a new applications for low pressure
cold spraying method. However, further research including bonding
mechanism and crystals formation are needed.
Acknowledgements
The research was financed by Polish National Science Centre under
contract no. 2016/23/D/ST8/00675 (Project title: The mechanism of
joining submicron ceramic particles in cold spraying process).
Additional support was provided by the Department of Mechanics,
Materials Science and Engineering, Wroclaw University of Science and
Technology under contract No. 0401/0029/17.
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