Article

pubs.acs.org/IECR

Experimental Study of the Effects of Using Different Precursor

Concentrations, Solvent Types, and Injection Types on Solution
Precursor High-Velocity Oxygen Fuel (HVOF) Nanostructured
Coating Formation
Mahrukh Mahrukh,†,‡ Arvind Kumar,§ and Sai Gu*,⊥
†
School of Energy, Environment & Agrifood, Cranfield University, Cranfield, Bedford MK43 0AL, United Kingdom
‡
Department of Mechanical Engineering, NED University of Engineering & Technology, University Road, 75270 Karachi, Pakistan
§
Department of Mechanical Engineering, Indian Institute of Technology, Kanpur 208016, India
⊥
Department of Chemical and Process Engineering, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford
GU2 7XH, United Kingdom

ABSTRACT: Nanometer and sub-micrometer particle coat-

ings are generated via a solution-precursor high-velocity
oxygen fuel spray (SP-HVOFS) process. The zirconium
nitrate (Zr-N) pentahydrate [Zr(NO3)4·5H2O] precursor
was used with varied precursor concentrations, solvent types,
and injection nozzles for analyzing the effects over the
nanomemter and sub-micrometer particle coating formations.
The solvent types are pure water, water−ethanol mixture, and
pure ethanol, whereas injection types are plain-orifice, angular,
and effervescent injections. Various nanometer and sub-
micrometer particle size distributions and morphologies are analyzed for varied precursor concentrations, solvent types, and
injection nozzles by using scanning electron microscopy (SEM) of sprayed substrates. The particle at low precursor
concentration showed spherical morphology with narrow size distribution, whereas at higher concentrations irregularly shaped
agglomerated and large particle are observed. Moreover, the mixtures of aqueous−organic and pure organic-based solvents are
preferred to improve the SP-HVOFS process efficiency to generate small size and homogeneous nanometer and sub-micrometer
particles. Toward the variation in injection nozzles, when different types of injection nozzles were tested, the effervescent-type
atomization nozzle produced the best-quality nanometer and sub-micrometer particles.

1. INTRODUCTION and formation of the required compound. This is known as the

In the high-velocity oxygen fuel (HVOF) spray process, fuel
and oxygen are fed into the HVOF gun for the generation of an
energetic combustion gas flame. The coating material is
injected in the form of powders. The interaction of the hot
gas with powder particle starts immediately after injection of
the material. The dynamic interaction of the gas with solid
particle involves acceleration, heating, melting, oxidation, or
modification of surface chemistry of the particle. Finally, the
coating formation depends on particle impact, flattening, splat
formation, cooling, and splat layering first on the prepared
substrate and then on already deposited layers.1 Recently, liquid
feedstock injection techniques have been developed for
generating improved nanostructured coatings.1
Deposition of coatings with nanometric size structure can
also be performed by injecting homogeneous solution into the
hot gases of the SP-HVOFS process.2,3 During the interactions
of the droplets with the gas, droplets break up due to the high
relative velocities and drag forces between the drops and the
gases. The continuous heating of solution precursor in the
HVOF flame leads to evaporation, precursor decomposition,
in situ formation of coating particle. Throughout this process,
the hot gases are cooled by evaporation of the solution and
heating of vapors. Hence, the gases must have sufficient
enthalpy for successful coatings, such as in HVOF and plasma
spraying. The solution can be injected either by atomization
with a gas or by mechanical injection.
To understand the behavior of the solution precursor
breakup, evaporation, decomposition, precipitation, and depo-
sition, it is required to understand the solution precursor
plasma spraying (SPPS) processes, as the literature available
related to SP-HVOFS spraying is scarce. Researchers performed
experiments and numerical studies related to the SPPS process,
as presented in the literature.1,4−10 The solution precursors are
stabilized homogeneous solutions, and their viscosities depend
on the concentration of the solution. It may be noted that no
Received: December 15, 2016
Revised: April 6, 2017
Accepted: April 12, 2017
Published: April 12, 2017

© 2017 American Chemical Society 4957 DOI: 10.1021/acs.iecr.6b04857

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extra addition of dispersion material or constant stirring is
required to stabilize the precursor solution. Solution precursor
thermal spraying allows an excellent chemical homogeneity of
coatings.10 Moreover, SPPS is a single-step process as precursor
droplet evaporation, decomposition, crystallization, and coating
formation occur in one step.11
Bertolissi et al.5 examined the droplet breakup and the
solvent evaporation processes using water and ethanol solvents
and reported that these processes are more efficient when the
ethanol-based solution is injected into the plasma gas mixtures,
whereas, with water-based solutions, residual liquid droplets
were detected over the substrate.5 It is highlighted that the
amount of non-decomposed or partially pyrolyzed precursor
droplets can be controlled primarily by droplet injection
density, droplet fragmentation, and precursor concentra-
tion.4,7,8 Chen et al.12 experimentally found that solvent having
low surface tension and low boiling and evaporation points
generates dense coating as compared to other solvents. The
coating from the two different precursors was deposited using a
spray distance (SD) of 50 mm and a liquid flow rate of 15 mL/
min. The higher concentrated precursor forms solid particles
that are melted and, thus, generate a dense coating. On the
contrary, the lower concentration precursor leads to shell
formation, which results in a soft porous coating. The SPPS
process involved on-site generation of fine particles (50−500
nm) and splat formation of sizes from 200 to 2000 nm and
showed nanoporosity and homogeneous microstructure.13
Basu et al.14 modeled the droplet disintegration phenomenon
and divided it into three steps: (i) aerodynamic breakup; (ii)
heating of droplet to vaporization; and then (iii) precipitation
and internal droplet pressurization. They suggest that droplet
disintegration has an enormous effect on the quality of the
coating. The small droplets are disintegrated and melted
properly and led to a denser coating, whereas large droplets
damage the coating features. Therefore, it is important to break
the large droplets into smaller ones by reducing the surface
tension and preferring axial injection. Furthermore, they
concluded that small droplets (<5 μm) show less unpyrolyzed
material over the substrate.14 The model predicts the surface
precipitation of larger droplets (>5 μm) leading to internal
pressurization and in situ droplet atomization. Hence, they
arrive at the substrate as the unpyrolyzed precursor and in the
form of broken shells.8,14,15
The use of atomization for solution precursor injection can
further improve the morphologies of the solid particle helping
to form dense coatings.16 It is further analyzed that the
disintegration of droplets can be achieved by using an atomizer
or a mechanical injector.16 Depending on the availability and
application requirements, different atomization gases and
processes can be used for atomizing the liquid streams. The
average splat size obtained in these experiments is about 30−35
μm, which was generated from droplet sizes of 1−20 μm upon
impact (collected at SD = 20 and 40 mm).16
The benefits of low HVOF flame temperature and negligible
flame fluctuations compared to plasma result in the uniform
precursor concentration within the droplets that promotes solid
particle and thick shell morphologies.17 Moreover, the particle
velocities are much higher in the HVOF process; consequently,
higher coating densities can be achieved compared to arc spray,
flame spray, air plasma, and vacuum plasma spray processes.18
Some researchers also studied the SP-HVOFS method. Chen
et al. studied the deposition of alumina-zirconia (Al2O3−ZrO2)
ceramic coatings by the SP-HVOFS process.3 Both nano-
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crystalline ZrO2 and amorphous γ-Al2O3 are observed by as-
sprayed coating characterization using X-ray diffraction and
transmission electron microscopy. The coating consists of
ultrafine splats (2−5 μm) and spherical particle and hollow
shell structures, and the coating has a high density with a
thickness of about 40 μm.3
Until today, very few researchers have modeled the SP-
HVOFS process. Modeling of the SP-HVOFS process has
proved that droplets injected into the HVOF jet undergo
strong shear breakup due to high relative velocities, hence
producing smaller secondary droplets.3,17,19 Basu and Cete-
gen17 modeled the injection of solution precursor droplet into
the HVOF flame jet and determined that the smaller droplets
evaporate rapidly and give out solid particles on rapid heating,
whereas larger droplets form precipitate shells with the liquid
core inside. It was summarized that the coating generated by
this approach is denser than that obtained with the conven-
tional process.17
Toward the usage of different solution precursors for
nanometer and sub-micrometer particles coating formation,
the use of metal nitrate as a precursor has some advantages over
others. First, it is not expensive and easily available in the
market. Second, metal nitrate salts dissolve easily in water and
alcohol; hence, the homogeneous precursor solution can be
formed by continuous stirring. Moreover, the nitrates act as an
oxidizer for fuel during the combustion reaction, which will
increase the HVOF flame enthalpy.20 The disadvantage of using
metal nitrates, as reported by Marchal et al.,20 is that larger
(200−2000 nm) hollow particles are obtained by the liquid
feed flame spray pyrolysis process, whereas a significant portion
of particles have a size below 100 nm. For a nitrate-based
precursor, two mechanisms of synthesis are explained in the
literature. In the first mechanism, the nitrates partially melt and
then decompose (rather than combust) upon heating up just
after exiting the spray nozzle. This produces large, sometimes
hollow, particles (typically of flame spray pyrolysis). In the
second mechanism, direct combustion of the spray droplets
occurs without melting, which forms fine particles.20−25 It may
be assumed that the second process is more dominant in
HVOF flame spray pyrolysis because the fast-moving HVOF
flame would hinder the melting of nitrates before decom-
position due to the short residence time available for precursor
droplets inside the combustion chamber (CC).20,26 Hence, it
can generate fine, solid nanometer and sub-micrometer
particles before deposition.
As pointed out, studies related to the SP-HVOFS process are
scarce, and more research is required in this area. To date, no
work has been reported to study the effects of different
injection parameters on the formation and growth of
nanometer and sub-micrometer particle coatings by the SP-
HVOFS process. The size of nanometer and sub-micrometer
particles needs to be controlled for the specific coating
requirement, and it can be regulated by using proper
atomization of the precursor before injection into the thermal
spraying gun.10,19,27 The SP-HVOFS process includes complex
stages of precursor injection, droplet fragmentation, precursor/
solvent evaporation, chemical reactions, decomposition, particle
formation, heating and melting of nanometer and sub-
micrometer particles while transferring heat, mass, and
momentum with the surrounding hot gas.17,19 This paper
contributes to obtaining more insights to understand the effects
of solution precursor fragmentation, advanced evaporation, and
its consequence on the nanometer and sub-micrometer particle
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formation in the SP-HVOFS process. These results will also
provide potential implications on the type of nanometer and
sub-micrometer particles formed during coating formation
(cracked, hollow, solid, agglomerated, semimelted, nanometer
or sub-micrometer size).
In the present work, experiments are performed to analyze
the nanometer and sub-micrometer particle growth and size
distribution by using varied concentrations of solutions,
different solvent types, and injection nozzles. Zirconium nitrate
(Zr-N) pentahydrate [Zr(NO3)4·5H2O] precursor is used,
which is injected into the HVOF gun for the formation of
zirconia (ZrO2) nanometer and sub-micrometer particles. The
homogeneous solution of Zr-N with solvents of pure water (P-
W), pure ethanol (P-E), and water−ethanol (W−E) mixtures
are made for analyzing the formation of ZrO2 nanometer and
sub-micrometer particles in the HVOF flame. Different
precursor concentrations are employed to determine the
difference in the particle’s size and morphology. Moreover,
for the first time, various injection nozzles with plain-orifice
injection, angular injection, and effervescent atomization are
used to examine the effects on nanometer and sub-micrometer
particle formation by the SP-HVOFS process.
The spray distance (SD) is the distance maintained between
the spray gun nozzle tip and the work-piece surface. For HVOF
thermal spraying processes, the SD is typically 50−380 mm. An
appropriate SD will ensure that the powder particles are fully
melted or semimelted before deposition and that the substrate
does not overheat during spraying. The SD used in the present
work is 100 mm (normally it is in the range of 20−50 mm for a
solution-fed HVOF process12,16), and thus it can be assumed
that due to this larger value, no splat formation takes place
during the experiments. It has been observed that for a short
SD the melted or semimelted nanometer/sub-micrometer
particle can form splats upon impact with the substrate,
whereas a large SD will cause coating formation with solid
particles.4,28−30
2. EXPERIMENTAL SETUP
2.1. Gun Geometry and Operating Conditions. The
HVOF gun used for the experiments is a CH-2000, designed
and made at Xi’an Jiaotong University, China (as shown in
Figure 1).31−33 The total inlet radius of the CC is RCC = 15.5
mm, with length LCC = 19 mm. The radius at the gun throat is
RT = 4.0 mm, with the extended gun barrel having a constant
radius of RB = 4.0 mm and length LB = 168 mm. Oxygen and
fuel gases flowed into the CC through several holes distributed
evenly around the precursor injection port at the center of the
gun (the solid blue circle in Figure 1a is the precursor injection
port). Propane gas is used as fuel.34 First, the operating
conditions for the CH-2000 HVOF gun are set as displayed in
Table 1. The flame at these conditions reached a supersonic
state, and visible shock diamonds are observed in the flame jet.
Then, precursor gas (nitrogen) is replaced by solution
precursor injection using nozzle N1 with a feed rate of 50
mL/min. After solution injection, the flame brightness is
increased, and the shock diamonds disappeared. This is due to
in situ formation of the ZrO2 particle; moreover, it is the result
of the liquid feedstock evaporation/combustion that the flame
brightness is enhanced. Also, a green color is clearly present in
the flame jet ejecting from the gun due to the formation of
ZrO2.
2.2. Design and Manufacture of Liquid Feedstock
Injection Nozzles. The experiments are performed using
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Figure 1. (a) Schematic diagram of CH-2000 HVOF gun; (b)
assembled view of the original CH-2000 HVOF gun with gas supply
head and injection nozzle N1 (not to scale and without legends as per
the manufacturer’s instructions).
three different injection nozzles, namely, the plain-orifice nozzle
N1, the angular injection nozzle N2, and the effervescent
atomization nozzle N3 (Figure 2).35 Three kinds of liquid
feedstock injection nozzles are designed according to CH-2000
HVOF gun requirements, and the effects of varied nozzle types
on the nanometer and sub-micrometer particle morphology
and size distribution are studied. The old injection nozzle N1
head (having an exit diameter of dinj = 0.5 mm, Figure 2a) is
modified to angular injection nozzle N2 to improve the droplet
fragmentation by injecting the droplets into the core of the
combustion zone (Figure 2a,b). Nozzle N2 is designed to inject
the precursor into the CC of the CH-2000 gun with α = 60°
angle of injection; it has six holes with a diameter of dinj = 0.3
mm (Figure 2b).
Furthermore, a new effervescent atomization nozzle N3 has
been designed for solution precursor atomization on the basis
of outside-in design (Figure 2c,d).35−43 The effervescent
atomization technique is used to create a bubbly flow inside
the nozzle section (Figure 2d) and then spray into the CC to
get finer disintegration of the precursor droplets. In this
technique, the liquid ejects out of the orifice with the internal
cavity of gas. Due to the pressure difference, gases expand and
shatter the liquid into ligaments and fine droplets.35,37,44 For
the effervescent atomization, the spray half-angle is calculated as
θ = 6° with dinj = 1.2 mm (Figure 2c). Some of the preliminary
atomization in the CC is shown schematically in Figure 2a−c to
compare the old single-fluid (without atomization) and the new
twin-fluid (with atomization) precursor spraying phenomenon;
detailed results will be analyzed and discussed in subsequent
sections.
2.3. Precursor Formation and Deposition. In the
present experiments, zirconium nitrate (Zr-N) pentahydrate
[Zr(NO3)4·5H2O] salt procured from Sinopharm Chemical
Reagent Co., Ltd., China, is used. The Zr-N precursor solutions
with varied molar concentrations of 0.05, 0.075, and 0.1 M are
formed by mixing the Zr-N salt into various solvents. The salt is
dissolved in three different solvents, namely, P-W, W−E (a
mixture carrying 50% water and 50% ethanol by volume), and
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Table 1. Operating Conditions of the CH-2000 HVOF Gun, Precursor Concentrations (M), and Solvent Types Used in
Solution Precursor Formation
gas flow rate kg/s
oxygen flow rate 0.007368 case 1: without droplet injection (for analyzing flame temperature)
propane flow rate 0.001581
nitrogen flow rate 0.001349
solution precursor flow rate 50 mL/min case 2: without atomization (nozzles N1 and N2)
solution precursor flow rate 50 mL/min case 3: with atomization (nozzle N3)
nitrogen flow rate 6 L/min
sample name: solvent type
precursor
concn (M) nozzle N1 nozzle N2 nozzle N3
0.05 A: P-W D: W-E G: P-E J: P-E M: P-W nozzle N2 damaged after running P-E cases; W-E P: P-E S: P-W V: W-E
0.075 B: P-W E: W-E H: P-E K: P-E N: P-W mixture cases are not sprayed Q: P-E T: P-W W: W-E
0.1 C: P-W F: W-E I: P-E L: P-E O: P-W R: P-E U: P-W X: W-E

Figure 2. Schematic representation of precursor injection into the CH-2000 HVOF gun: (a) plain-orifice nozzle N1; (b) angular injection nozzle
N2; (c) effervescent atomization nozzle N3; and (d) cross-section view of effervescent-type nozzle N3.

P-E. Nine sets of precursor solutions are prepared by using the
above solvent types and precursor concentration, as shown in
Table 1. These precursor solutions are injected sequentially
into the HVOF gun, and the generated particles are sprayed
over finished yttria-stabilized zirconia (YSZ) substrates (25 mm
diameter disks, with 2 mm thickness) using 10 pass cycles (the
spray gun repeated its motion 10 times, which deposited the
nanometer and sub-micrometer particles over the substrate).
The spray distance, SD, was 100 mm (from the gun exit to the
substrate), and due to this larger value only solid nanometer
and sub-micrometer particles are observed over the substrate,
whereas no splats are perceived.12
The experiments are organized to analyze the effect of varied
solvent types and different precursor concentrations on the size
and morphology of particles formed during the SP-HVOFS
process. The HVOF flame is set up according to the flow
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parameters described in Table 1. Moreover, with these gas flow
rates (GFRs) set up, different cases are experimentally
performed. Here, Zr-N dissolved in P-W is named cases A, B,
and C with precursor concentrations of 0.05 , 0.075, and 0.1 M,
respectively (see Table 1). Similarly, Zr-N solutions with varied
precursor concentration made in the W−E mixture are
designated cases D−F, and those made in P-E are designated
cases G−I (Table 1). The Zr-N precursor is injected into the
center of the CH-2000 HVOF gun at a feed rate of 50 mL/min
using nozzle N1 (Figure 2a). No atomization technique is
applied at this stage. The formed nanometer and sub-
micrometer particles are deposited on the finished surface of
YSZ, and SEM micrographs are analyzed for various precursor
concentrations and solvent mixtures. Similar steps are repeated
for nozzle N2 (cases J−O), as shown in Figure 2b and Table 1.
Nozzle N2 was installed, and a number of different samples
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were sprayed with P-E as a solvent; however, nozzle N2 was
damaged while repeating the same experiments later.
After these experiments, another set of experiments were
performed by using the new effervescent atomizing nozzle N3.
For nozzle N3, precursor and atomizing gas are injected into
the effervescent nozzle from separate inlets (see Figure 2d).
This mixture of two fluids is then fed into the CC of the CH-
2000 HVOF gun, as shown schematically in Figure 2c. In these
experiments also the formed nanometer and sub-micrometer
particles deposited and SEM micrographs are analyzed for
various precursor solution concentrations and varied solvent
mixtures for the precursor injection by nozzle N3 (cases P− X,
see Table 1).
2.4. Scanning Electron Microscopy and Particle Size
Measurement. SEM is performed on a TESCON MIRA3
(FEG-SEM) with an operating voltage of 15 kV. Before SEM,
sample substrates are sputter-coated with platinum (Pt with
coating rate = 8 nm/min for 2 min) to reduce the charging
effects. Different morphologies and nanometer and sub-
micrometer particle size distribution are analyzed for different
precursor concentrations and solvent types. Four samples for
each case have been observed under the SEM. The software
toolkit “Nano-Measure” has been used to measure the size of
the individual particles from different SEM images. Approx-
imately 1000 nanometer and sub-micrometer particles sizes
were measured from four different samples, and the nano-
particle size distribution histograms have been developed (see
Results and Discussion).
3. RESULTS AND DISCUSSION
3.1. Thermal Behavior of Zirconium Nitrate Salt. The
conversion of the Zr-N salt crystals to ZrO2 ceramic powder is
analyzed using a thermogravimetric (TG) or differential
thermal analysis (DTA) system (NETZSCH model STA
409PC/PG). The powder is heated from room temperature
to 1000 °C at a heating rate of 10 °C min−1. It is examined that
decomposition of zirconium nitrate is a slow process, with NO3
or NO2 molecules being lost in stages.45 The differential
scanning calorimetry (DSC) and TG curves for the Zzirconium
nitrate pentahydrate salt are shown in Figure 3. The DSC curve
shows an endothermic peak at 81.28 °C, which can be
attributed to the evaporation of free water in the salt, leading to
a mass loss of 15.11% between 50 and 100 °C.13,46
The next endothermic peak is observed at 135.55 °C, which
confirms the evaporation of crystal water present in the
Figure 3. TGA and DSC curves: zirconium nitrate pentahydrate salts.
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zirconium nitrate salt with a mass loss of 11.48%. Between 165
and 400 °C, the TG curve showed a mass loss of 75% − 50% =
25.0% approximately, which can be attributed to the
decomposition of zirconium nitrates. On further heating from
400 to 500 °C, mass loss becomes constant (25.42%). Gradual
increment in mass is observed after 600 °C, confirming the
reaction of zirconium (Zr) with oxygen (O2) to form zirconia
particles (ZrO2). The exothermic peak observed at 828.03 °C
elaborates the crystallization of amorphous zirconia (Figure
3).13,45−47 Thus, it is clear from these curves that ZrO2 particle
formation can efficiently complete within a temperature range
of 600−850 °C, and it can be easily achieved inside the HVOF
gun (details of flame temperature are in section 3.2). The
precursor decomposition equations are shown below:
zirconium nitrate pentahydrate:
heat
Zr(NO3)4 ·5H 2O ⎯⎯⎯→ Zr(NO3)4 + 5H 2O
zirconium nitrate:
heat
Zr(NO3)4 ⎯⎯⎯→ ZrO2 + 3NO2 + O2
3.2. Experimental and Numerical Measurement of
HVOF Flame Dynamics. High flame temperatures are
required for the evaporation of the precursor solution and
nanometer and sub-micrometer particle formation in the
HVOF gun.31−33 The GFR are selected according to the
previous work to obtain high-temperature flames with super-
sonic jet outlet velocities. For case 1, the oxygen-fuel (O/F)
gases are injected into the CH-2000 gun’s CC, and shock
diamonds are observed at the gun exit (Table 1). Temperature
sensing is performed by using thermocouples. In case 2, the O/
F flow rates remain the same, whereas the nitrogen gas
injection is replaced by the liquid injection (Table 1). For case
2, temperature measurements are repeated by thermocouples.
Moreover, three different liquid solvents are fed into the CH-
2000 gun successively. P-W injection is named case 2a, P-E
injection case 2b, and W−E mixture injection case 2c in Figure
4. For all of the cases the data are gathered and plotted here for
analyzing temperature variation during the HVOF process with
and without injection of different solvents (Figure 4a shows
data at the centerline axis of the HVOF gun). The temperature
sensing performed by the thermocouple has significant errors
involved due to radiation, convection, and conduction heat
losses.48 Therefore, it is assumed that the actual flame
temperature could be 200 °C higher than the temperature
measured by these thermocouples.
Similarly, for numerical validations of the gas flow dynamics,
two cases are simulated, case 1 and case 2, with and without
droplet injection. Temperature profiles from numerical
simulations of case 1 and case 2 compare with the experimental
measurements (Figure 4a). The temperature profiles measured
by CFD in the far field are in good agreement with the
experimental results in case 1 and case 2b. For case 2a and case
2c, when P-W and the W−E mixture droplets are fed into the
CH-2000 gun, the CFD temperature is higher than that
measured by the thermocouple, whereas it has already been
discussed that the thermocouple could not measure the gas
temperature accurately.48 Hence, it is presumed that the flame
temperature predicted by CFD is in the correct range as the
measurements overlap completely with the high-temperature
flame experimental detections. On the other hand, for lower
flame temperatures the readings are a little higher when
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Figure 4. (a) Thermocouple and CFD temperature measurement of
the CH-2000 flame and (b) CFD measurement of the CH-2000 flame
velocity (all cases with nozzle N1).
compared with the thermocouples. Thus, it can be said that
case 2a and case 2c CFD measurements are more accurate,
compared to the experimental tests.
It is observed from Figure 4a that by adding the liquid
droplets in case 2, the flame temperature is significantly reduced
inside the CC, because the liquid solvent extracted heat from
combustion gases for evaporation. The highest peak flame
temperature of 2784 K is detected for P-E case 2b in the barrel
section (at an axial distance of 0.178 m from the point of
injection). Also, one more peak with a temperature of 2828.38
Figure 5. Schematic representation of the SP-HVOFS process for nanometer and sub-micrometer particle formation.
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K is observed in the free jet section (at x = 0.223 m), whereas
low flame temperatures are observed for the P-W case 2a: it is
1757.12 K (at an axial distance of 0.178 m) and 1690.09 K in
the jet section (at x = 0.223 m). The maximum temperature
observed for case 1 (without drops) is 2639.58 K and for case
2c (with W−E), 2616.73 K. Therefore, for all prescribed cases
the flame temperature is high enough to accomplish the in situ
nanometer and sub-micrometer particle formation in the SP-
HVOFS CH-2000 gun. Finally, it will be observed in later
(section 3.5) that the higher flame temperature in P-E and W−
E injection cases would generate large size particles as the
sintering rate is increased in the hot flame regions.
From Figure 4b the variation in gas velocity is analyzed by
the addition of solvent droplets. It is observed that on the
addition of P-W content inside the CH-2000 gun, the gas
velocity is reduced, and this loss of kinetic energy was
significantly higher for the P-W injection case, whereas on
the addition of P-E and W−E mixture droplets, the flame
velocities were significantly increased. The augmentation in the
flame kinetic energy is due to the increment in the combustion
gas energy. This energy is added from the combustion of the
ethanol vapors. Furthermore, increments in the flame velocity
are also observed after the hot gas ejection from the thermal
spray torch. An overall analysis suggests that the use of organic
solvents will improve the torch gas dynamics in the free jet
regions and help to improve the heating and melting of the
solid nanoparticles. Also, the increment in flame kinetic energy
would decrease the residence time of droplets and form
particles inside and outside the CH-2000 flame.
3.3. SP-HVOFS Process Physics. The process physics for
the nanometer and sub-micrometer particle nucleation is
explained schematically in Figure 5. In the SP-HVOFS process,
the solution precursor is fed into the HVOF gun through a
central opening. The O/F mixture combusts inside the CC and
provides the heat required for precursor droplet evaporation
and in situ particle formation. The chemical reaction starts
immediately as the precursor droplets absorb heat from the
surrounding hot gas and are converted into vapors (section
CC). The evaporation of the precursor liquid is dependent on
the combustion temperature, and under high GFR, the liquid
boils rapidly and the evaporation rate increases. It is mentioned
that a high evaporation rate will eventually increase the average
particle growth rate.49
Particle formation starts where the O/F combustion streams
and precursor vapor streams become mixed inside the CC,
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whereas turbulence mixing occurs near the centerline axis of the without atomizing nozzle N1 in Table 1. Figure 6 shows the
gun as the precursor droplets are injected axially into the CC morphology and size variation of the as-sprayed particles at
(from a central hole/opening, Figure 5). It is stated that particle
formation, occurring directly from the vapors, takes place via
homogeneous nucleation.49 The physical and chemical proper-
ties of nanometer and sub-micrometer particles are dependent
on a large number of parameters, such as combustion gas
temperature, pressure, velocity, C−D nozzle design, O/F
injection flow rates and feeding ratio, fuel and precursor
properties, and their concentration.3,17,19 Furthermore, the local
cooling rate, residence time distribution, and number density in
the nucleation and growth zones are the primary factors that
affect the nucleation and growth of nanometer and sub-
micrometer particles in the SP-HVOFS process (Figure 5).
First, the droplets of the solution precursor, after being
injected into the HVOF flame jet, undergo several physical
processes taking place sequentially. The first stage is the
aerodynamic breakup, as the slow-moving droplets are
entrained into the high-velocity jet and accelerated in the
high-velocity gas stream (Figure 5). Depending on the droplet’s
initial size, the thermophysical properties of the solution
precursor, and surrounding gas conditions, the droplets can
undergo severe deformation and eventually break up into
smaller droplets.35,50
The second stage is the evaporation of micrometer-sized
precursor droplets, after which the formation of particles begins
when the precursor gas is going through a chemical reaction
(Figure 5). A high temperature is required to evaporate the
precursor and to provide the conditions for the chemical
decomposition. The temperature of the high-velocity flames
varies from 3000 to 4000 K depending on the type of fuel and
the operating conditions.51−54 At the early stage, the particle is Figure 6. SEM images and nanoparticle size distribution of ZrO2
formed by gas-phase nucleation and grows by coagulation particles produced from Zr-N dissolved in P-W solvent with varied
(particles collide with each other and stick together to form precursor concentrations of (a) A-0.05M (b) B-0.075M, and (c) C-
agglomerates); later, they coalesce into the larger particle. The 0.1M.
shape of the final product is determined by the rates of
coalescence and coagulation. If the rate of sintering is faster various precursor concentrations made up of the Zr-N
than that of coagulation, the particles formed are spherical. dissolved in P-W. The solution samples are named A-0.05M,
Otherwise, irregularly shaped agglomerates are developed.55 B-0.075M, and C-0.1M, respectively (Table 1). These varied
The growth of nanometer and sub-micrometer particles precursor concentrations are used to ascertain the effects of
continues through nucleation by acquiring more atoms through concentration variation on the nanometer and sub-micrometer
coalescence, coagulation, and sintering. In coalescence the particle size and morphology. Different arrows in the SEM
particles collide with each other and lose their kinetic energy, images represent the particle morphology as hollow (H),
also referred to as sintering and diffusion of the compound cracked (C), agglomerated (A), aggregated (Ag), semimelted
within particles where contact is made.49 Coalescence takes (SM), spherical (Sp), and solid (S). For a low concentration of
place in high-temperature zones (section CC and section barrel 0.05 M, fewer numbers of particles are observed as compared to
of the SP-HVOFS gun, Figure 5).50 Coagulation is a stepwise high concentration (Figure 6). In case A-0.05M, a greater
process wherein two nuclei meet and join, causing sintering due number of the particles are spherical, and few of them are fused
to processes such as Brownian motion, and this decreases the together (agglomerated and aggregated) with the mean
number of particles in the flow.49 Brownian motion is the diameter of dp)mean = 104 nm. The range of particle size
random motion of the particles suspended in a fluid resulting distribution observed for case A is 20−340 nm.
from their collision with the quick atoms or molecules in the The solution precursor density is increased from 1007 to
gas or liquid.49 Sintering is the process of compacting and 1018 kg/m3, and ZrO2 production rate are augmented from
forming a solid mass of material by heat and pressure without 5.134 × 10−6 to 10.2683 × 10−6 kg/s (18.483−36.966 g/h)
melting it to the point of liquefaction. At sufficiently high with the increment in the solution concentration from 0.05 to
temperatures, particles coalesce (sinter) more quickly than they 0.1 M. The increase in the production rate is evidence of the
coagulate, and spherical particles are produced. If the density of increment in the number of particles formed, and hence the
the particle is relatively small and the collection time is short, particle number density is also increased (particle number
then the particle agglomerates are smaller in size and vice count or an average number of particles in unit volume/or unit
versa.49 area). Thus, this increment in the number density will increase
3.4. Effect of Increasing Precursor Concentration on the particle-to-particle collision and larger size nanometer and
Particle Size and Morphology. The first set of experiments sub-micrometer particles with aggregated or agglomerated
is performed with operating conditions prescribed as case 2, manner will form. Hence, in case B-0.075M and case C-0.1M
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Industrial & Engineering Chemistry Research
precursor concentrations, the SEM micrographs showed the
presence of numerous agglomerated and aggregated nanometer
and sub-micrometer particles with mean diameters of 119 and
143 nm, respectively (Figure 6b,c).
It was observed that in comparison to case B-0.075M, the
range of particle distribution (20−340 nm) is also extended in
case C-0.1M solution (20−440 nm). This increase in the
diameter of nanometer and sub-micrometer particles was
expected as the higher precursor concentration will result in a
higher particle number density. It enhanced the frequency of
particle collision and, hence, augmented the coalescence and
sintering processes that enhance the growth rate of nanometer
and sub-micrometer particles. Also, this increase in the
concentration showed the bulk agglomerated zirconia particle
with semimelted and aggregated large size particles (as shown
by arrows in Figure 6b). Therefore, it can be understood that
the increment in the solution concentration will reduce the
process efficiency of forming greater numbers of solid, spherical
particles; nonhomogeneous particles will be deposited due to
the formation of more agglomerated, nonspherical, and bigger
size particles. The effectiveness of this process can be increased
by using droplet atomization techniques. Section 3.6 sub-
sequently analyzes the techniques to disintegrate precursor
droplets into a fine mist to get the desired nanosized spherical
particle having a homogeneous morphology.
Figure 7 shows the average diameter of nanometer and sub-
micrometer particles as a function of increasing precursor
Figure 7. Nanometer and sub-micrometer particle mean diameters for
varied precursor concentrations in P-W solvent. Standard deviation for
sample A-0.05M = 19.14, sample B-0.075M = 14.45, and sample C-
0.1M = 9.19.
concentration at constant O/F gas flow rates of 0.008949 kg/s,
constant solution feed rates of 50 mL/min, and constant
injection pressure of 0.7 MPa for samples A, B, and C (nozzle
N1 cases). It is observed that keeping all parameters constant
and increasing the precursor concentration from 0.05 to 0.1 M
led to a rise in the mean diameter of nanometer and sub-
micrometer particles from 104 to 143 nm (Figure 7). The
reason for increasing particle size is the increment in the
density of Zr-N precursor in the HVOF gun; thus, it can also be
said that growth in particle size is due to the variations in the
solution precursor transport properties. Increasing the
precursor concentration from 0.05 to 0.1 M would increase
the density, surface tension, and viscosity of the solution
droplets. It may decrease the droplet disintegration process in
the HVOF gun, and bigger droplets lead to the formation of
larger nanometer and sub-micrometer particles. It is reported
that an increment in droplet size delays the droplet evaporation
rate and precursor decomposition,56 whereas augmentation in
the droplet residence time in the HVOF gun will lead to an
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increase in the sintering rate of nucleated seed particle, and the
particle grows bigger and bigger.14,49 In many applications high
precursor concentration is required as Chen et al.57 found that
low concentration precursors generally experience surface
precipitation and lead to shell formation. The deposits consist
of semipyrolyzed material and resulted in a soft, porous coating;
whereas the high-concentration precursors resulted in ultrafine
splats and dense, hard coatings. In the present work, the use of
long SD = 100 mm has reduced this type of coating formation
(dense, pore-free coatings) as the formed particles have
traveled a long distance and become solid before reaching the
substrate, whereas it is presumed that the use of high precursor
concentrations with short SD ≤ 50 mm can help to generate
dense coatings.57
3.5. Effect of Different Solvent Types on Particle Size
and Morphology. This section examines the impact of
various solvent types on the nano-meter and sub-micrometer
particle size and morphology. As stated earlier, three types of
solvents are used, including P-W, W−E mixture, and P-E. It is
observed that the nanometer and sub-micrometer particle size
distribution is changed with varied solvent types. In Figures 8
Figure 8. SEM images and nanometer and sub-micrometer particle
size distribution of ZrO2 particles produced from Zr-N dissolved in
W−E mixture solvent with varied precursor concentrations of (a) D-
0.05M, (b) E-0.075M, and (c) F-0.1M.
and 9 the SEM micrographs and nanometer and sub-
micrometer particle size distributions for the W−E mixture
(D-0.05M, E-0.075M, and F-0.1M) and P-E (G-0.05M, H-
0.075M, and I-0.1M) cases are presented. When P-W case A-
0.05M is compared to W−E mixture case D-0.05M and P-E
case G-0.05M, the average diameters of nanometer and sub-
micrometer particles observed are 104, 89, and 111 nm,
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Figure 9. SEM images and nanometer and sub-micrometer particle
size distribution of ZrO2 particles produced from Zr-N dissolved in P-
E solvent with varied precursor concentrations of (a) G-0.05M (b) H-
0.075M, and (c) I-0.1M.
respectively (Figures 6a, 8a, and 9a). It can be said that during
flame synthesis of nanometer and sub-micrometer particles, the
water cools the flame, and due to its quenching effect, the
particle size is reduced (Figure 6a).
The best results are obtained for the W−E mixture case, and
smallest nanometer and sub-micrometer particle sizes are
observed with a weak solution concentration of 0.05 M (Figure
8a). However, the addition of P-E increases the flame
temperature, increment in the gas temperature augmented
the sintering rate, and large size particles were obtained (Figure
9a). Panels b and c of Figure 8 show the SEM images with
particle distribution curves for the W−E mixture carrying
precursor concentrations E-0.075M and F-0.1M. It is detected
that for the solution of 50 wt % added ethanol, the particle size
and distribution do not vary much with the increase in
concentrations. However, the particle size and distribution both
changed when compared to P-W cases (Figure 6). In W−E
mixture cases, the particle size distribution range is also
narrowed as seen in Figure 8, and the biggest particle is 360 nm
(case F-0.1M).
On the other hand, in P-W case C-0.1M, the largest diameter
is observed as 420 nm. The reason is that P-W droplets had
high surface tension and required a high heat of vaporization.
Also, an increase in solution concentration further augments
these properties. Therefore, it delays the droplet evaporation
process and decomposition of the Zr-N salt and led to the
formation of large nanometer and sub-micrometer particles in
comparison to that in W−E solvent mixture cases.
Furthermore, it is known that the value of the surface tension
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of water (σW = 72 × 10−3 N/m) is 3 times that of ethanol (σE =
22 × 10−3 N/m). A small increase in the precursor
concentration can cause an increment in water surface tension.
Hence, at high concentrations of 0.1 M, P-W shows a large
average particle size of 143 nm (case C-0.1M, Figure 6c),
whereas the W−E mixture shows a mean diameter of 111 nm
(case F-0.1M, Figure 8c) and P-E solvent gives particles with an
average diameter of 101 nm (case I-0.1M, Figure 9c). It can be
said that increasing the precursor concentrations has less effect
on the organic solvents as compared to water and its mixture
cases. Thus, organic solvents are more resistant to showing a
change in surface tension by an increment in precursor
concentration.
Moreover, when P-E is used as solvent, few particles have a
spherical shape, and an increase in agglomeration is also
detected (as shown in Figure 9). The organic solvents and their
mixtures have fast evaporation and subsequent early salt
decomposition as mentioned in ref 58. Thus, these early
evaporations allow the ZrO2 seed particle to remain in the
higher flame temperature regions for a longer time as compared
to the P-W-based solvent cases. Hence, particle sintering and
growth rates are increased.49 The particle size distribution is
widened for the P-E case, and the largest particle size of dp =
496 nm is observed for case H-0.075M concentration (Figure
9b). Besides, the particle temperature may also increase during
the flight, which is suitable for making a strong bond between
the coating and substrate. For all P-E cases, the particles reside
in the higher temperature regions that cause higher sintering
rates and particles grow bigger, whereas it also helps to form
more spherically shaped particles.14,49 Thus, P-E can be used to
obtain more spherical particulate matter, and it helps to control
the particle size variation and distribution range.
The plot in Figure 10 shows the variation in the particle
mean diameter by using different solvent types. As mentioned
Figure 10. Nanometer and sub-micrometer particle mean diameters
for varied Zr-N precursor concentrations dissolved in different solvent
types (using nozzle N1).
in the above discussion, P-W solvents are highly sensitive to
changes in the concentration of the solution. Thus, their
thermophysical properties, such as surface tension, viscosity,
specific heat capacity, and heat of vaporization, significantly
varied by the increment in the solution concentrations. On the
other hand, the organic solvents and their mixture show no
significant change in their properties.12,57 Chen et al.12 found
that solvent droplets with a high surface tension and high
boiling point experience incomplete evaporation in the jet,
leading to a porous coating. Droplets created from a low surface
tension and low boiling point solvent undergo rapid solvent
evaporation, precursor precipitation, pyrolysis, and melting
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process during the flight and form splats upon impacting the gas-to-formed particles is reduced.35 The SEM micrograph in
substrate; the buildup of splats results in a dense coating. Thus, Figure 11a shows the nanometer and sub-micrometer particles
it can be said that organic solvents can be beneficially used for
the generation of a dense pore-free coating.12
In the present study, the absence of the splats and coating
layers is obviously due to the large distance between the spray
gun and substrate that allows the ZrO2-formed particles to fully
solidify during the flight in the HVOF flame, and thus no
melted splats are observed over the substrate. Thus, it is
perceived that a reduction in the SD can constructively create
dense coating layers. A very few numbers of melted particles are
observed during P-E injection cases (Figure 9) due to the
increment in the flame temperature (Figure 4a) throughout
particle flight regions. Similar observations were made during
the present experimental work. The particle size is increased for
P-W solvents with a rise in the solution concentrations, whereas
the particle size shows fewer variations for the W−E mixture.
Moreover, for P-E the particle size is decreased with increase in
the precursor concentration (Figure 10). Thus, it is proved that
the nanometer and sub-micrometer particle size distribution
and morphology are mainly dependent on (i) solution
concentrations and (ii) type of solvent, because the increment
in the precursor surface tension and heat of vaporization are
also dependent on the kind of solvent and precursor
concentrations. Solution precursor with higher surface tension
required higher energy for droplet breakup and also needs high
heat for vaporization; thus, it delays the overall process of
nanometer and sub-micrometer particle synthesis inside the SP-
HVOFS gun.
3.6. Effect of Different Injection Nozzle Types on the
Particle Size and Morphology. For P-W-based precursor
solution carrying high precursor concentrations, atomization Figure 11. SEM images and nanometer and sub-micrometer particle
becomes compulsory to improve the overall process efficiency size distribution of ZrO2 particles produced from Zr-N dissolved in P-
E solvent with 0.1 M precursor concentration: (a) I-nozzle N1; (b) L-
of generating small size spherical nanometer and sub-micro- nozzle N2; (c) R-nozzle N3.
meter particles. A new atomization technique is applied to
obtain small nanosize particles with improved morphology
(improved morphology is the generation of solid, spherical
particles with fewer agglomerated particles). The effervescent generated by using the nozzle N1 injection scheme. The
atomization used the twin-fluid flow through a nozzle, and at micrograph shows a few solid spherical nanometer and sub-
the point of ejection the gas core is confined to a liquid layer; micrometer particles and more nonuniform agglomerates of
hence, due to the pressure difference between the two fluids, ZrO2. This demonstrates that due to less sintering time the
the liquid sheet is shattered by the high-pressure gases. This particle remains in the form of agglomerates (A), and small
causes the disintegration of the liquid feedstock.37,44 The numbers of spherical (Sp) particle are observed (Figure 11a).49
angular injection and plain-orifice nozzles use only one fluid The mean diameter calculations for this type of nozzle shows
that is the solution precursor without any atomizing gas. Nozzle that dp)mean ≥ 100 nm (approximately). In angular injection
N1 injected the liquid feedstock into the CC of the HVOF gun nozzle N2, the liquid feedstock is fed into the CC of the HVOF
at a 0° angle of injection (Figure 2a). All of the droplets travel gun at a 60° angle of injection. It is assumed that the maximum
along the gun’s central axis. It is assumed that from N1 amount of the solution droplet is evaporated inside the gun CC
injections, the initial droplet size is equal to the nozzle exit (as it is in direct contact with the combustion flame), and the
diameter (i.e., 0.5 mm). The droplet breakup starts inside the vapors start converting into the ZrO2 particles by chemical
HVOF gun due to the velocity differences between the injected reaction. Thus, these particles remain in the hot flame for a
droplets and the combustion gas. These high relative velocities longer time as compared to the other injection cases of nozzles
exert an aerodynamic force onto the injected droplets; thus, the N1 and N3. Thus, the ZrO2 particles are melted and generate
droplet breakup started and continued.35 larger agglomerated clusters of nonhomogeneous morphology,
The droplets start heating once they are fed into the CC. By as shown in the SEM micrograph in Figure 11b.
gradual heating inside the gun, they are evaporated and then The mean diameter detected for the particles formed by
decomposed to form the ZrO2 particles. It is further assumed using nozzle N2 is dp)mean > 100 nm. In the case of effervescent
that the residence time of the droplets or the formed ZrO2 nozzle N3, all of the nanometer and sub-micrometer particles
particles in hot flame regions is very small in the case of nozzle are solid (not hollow or cracked), whereas some of them are
N1. As for the nozzle N1 centerline injection (Figure 2a), the spherical and some are nonspherical, and the size distribution is
droplets are not in direct contact with the combustion flame varied throughout the sample (Figure 11c). A very few
inside the CC. Due to the lower residence time, the heat agglomerated particle are observed (Figure 11c). This is due
transfer between the hot gas-to-droplets or between the hot to the improved atomization of the precursor droplets and,
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thus, the smaller droplets generate small nanometer and sub-
micrometer particles.17
For nozzle N1 the highest nanometer and sub-micrometer
particle size observed with 0.1 M concentrations in a P-E
solvent is dp = 457 nm (Table 2). The range of particle size is
Table 2. Nanometer and Sub-micrometer Particle Ranges
and Mean Diameters for Different Injection Nozzles at 0.1
M Precursor Concentration with P-E Solvent
nozzle nanometer and sub-micrometer particle mean diameter
type diameter range (nm) (nm)
N1 11−457 101
N2 30−549 139
N3 26−400 96
found to be 11−457 nm, whereas the mean diameter of
nanometer and sub-micrometer particles generated by N1 is
dp)mean = 101 nm (Figure 11a). The average diameter of
particles produced by using nozzle N2 is dp)mean = 139 nm,
whereas the range of nanometer and sub-micrometer particle
size distribution has widened to 549 nm (Table 2; Figure 11b).
It can be said that in nozzle N2 the size of nanometer and sub-
micrometer particles is increased due to the increment in the
nanometer and sub-micrometer particles residence time inside
the gun. The 60° angle of injection can be reduced to decrease
the particle residence time in the gun. For nozzle N3, the mean
diameter is observed as 96 nm, and the lowest range observed
for this kind of nozzle is 26−400 nm (see Table 2). Hence, it
can be said that the best results are achieved by the effervescent
atomization nozzle N3, and the worst results are obtained by
the angular injection type nozzle N2. The nanometer and sub-
micrometer particles generated by nozzle N3 are smaller in size,
having spherical shape compared to the particles formed by
nozzle N2. Therefore, the atomizing nozzle N3 works
efficiently and increases the effectiveness of the SP-HVOFS
spraying process.
In all cases, the mean diameter of all nanometer and sub-
micrometer particles remains below dp)mean < 150 nm, whereas
the diameter distribution varied significantly (Figure 12; Table
2). In nozzle N1 with P-E solvent, there is a very different kind
of effect, and with increasing precursor concentration the
average diameter of nanometer and sub-micrometer particles
reduces (Figures 9 and 12). The consequence of this decrement
in particle size is unclear. For nozzle N1 (with solvent P-E),
Figure 12. Nanometer and sub-micrometer particle mean diameters
for varied Zr-N precursor concentrations using nozzles N1, N2, and
N3 (solvent type P-E). The standard deviations for different samples
sprayed with different precursor concentrations using varied nozzles
are 0.05 M = 25.275, 0.075 M = 13.162, and 0.1 M = 24.33.
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more experiments are required to clarify the effect of increasing
precursor concentration on the as-sprayed particle size and
morphology. The effect of increasing concentrations on
nanometer and sub-micrometer particle size is significant for
nozzle N2 in comparison to other cases, and with increasing
concentration, the particle size is increased.
The performance of nozzle N3 is better than that of all other
injection types, where for a higher concentrated solution the
mean particle size remains constant (Figure 12). Thus, the
injection nozzle N3 (effervescent atomising nozzle) is proved
to be the best type of nozzle for injecting precursor into the CC
of the HVOF gun, as it finally generates smaller size nanometer
and sub-micrometer particles after the spraying process.
Furthermore, in the future, a numerical study can add to the
knowledge of improving the solution precursor breakup,
evaporation, and nanoparticle formation in the SP-HVOFS
gun by controlling the angle of injection, precursor
concentration, and use of appropriate mixture ratios for
water−ethanol solvents.
4. CONCLUSION
The SP-HVOFS process efficiency to generate small size,
homogeneously shaped (spherical), nanometer and sub-micro-
meter particles has been analyzed by varying precursor
concentration, using different solvents and changing injection
nozzles (with and without atomization). The SP-HVOFS
process is utilized for the deposition of the ZrO2 particles on
YSZ substrate. The zirconium nitrate pentahydrate precursor is
prepared using P-W, P-E, and W−E mixture solvents with
varied precursor concentrations. Different precursor concen-
trations, solvent types, and nozzle designs are utilized to analyze
the variation in nanometer and sub-micrometer particle
deposition. It is determined in this study that the size of
nanometer and sub-micrometer particles and morphology are
dependent on the precursor solution concentration and
solvents types; thus, using pure organic solvents or its mixtures
with low precursor concentrations can generate smaller size
particles with homogeneous morphology. The only reason for
no splat formation is the large spray distance of 100 mm. From
this study the following conclusions are made:
• The higher precursor concentration results in a higher
particle density, which increases the frequency of particle
collision. Therefore, the growth of nanometer and sub-
micrometer particles is enhanced, which widened
nanometer and sub-micrometer particle diameters and
size distribution ranges.
• Higher heat of vaporization and high surface tension
values for P-W limit its use as a solvent. The overall
process efficiency decreases with increment in the
precursor concentration in the P-W-based precursor.
The addition of ethanol reduces this deficiency to some
extent, and it is proved that the use of P-E improves the
nanometer and sub-micrometer particle morphology and
size distribution.
• All cases performed using nozzle N1 generate larger size
ZrO2 particles due to the injection of the single liquid
stream without atomization. This technique creates
bigger precursor droplets that delay droplet evaporation
and increase the residence time for the particles in
HVOF gun, which intensify the particle growth rate and,
thus, particles grow bigger.
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• The efficiency of the SP-HVOFS process is also
increased by using precursor droplet atomization
techniques. The atomization of the solution precursor
decreased the droplet size for both organic and inorganic
solvents and improved the overall results.
• From the present study, it is analyzed that the best type
of injection is the effervescent-type nozzle N3. This
injection type reduces the average diameter of nanometer
and sub-micrometer particles, decreases the overall size
distribution, and improves particle morphology.
• The present angular injection nozzle design has an
opposite effect on the nanometer and sub-micrometer
particle size and morphology. It generates larger size
particles with irregular shape, and the overall size
distribution is widened. It can be modified further, and
a new design with the optimal angle of injection can
increase its efficiency of nanometer and sub-micrometer
particle depositions.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: sai.gu@surrey.ac.uk. Tel: +44 01483 682676.
ORCID
Sai Gu: 0000-0002-5675-9118
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We acknowledge financial support from the NED University of
Engineering & Technology, Pakistan, and U.K. Engineering and
Physical Sciences Research Council (EPSRC) Project Grant
EP/K027530/1. Experimental work performed at Xian Jiaotong
University, China, was guided by Prof. Chang-Jiu Li and Dr.
Shan-Lin Zhang. This work is funded by European Seventh
Framework programme−Marie Curie Actions−People Interna-
tional Research Staff Exchange Scheme under Project Grant
268696.
■
ABBREVIATIONS
CC = combustion chamber
CFD = computational fluid dynamics
GFR = gas flow rates
HVOF = high-velocity oxygen fuel
O/F = oxygen-fuel
P-E = pure ethanol
P-W = pure water
SEM = scanning electron microscopy
SPPS = solution precursor plasma spraying
SP-HVOFS = solution precursor high-velocity oxygen fuel
spray
W-E = water−ethanol mixture
YSZ = yttria-stabilized zirconia
Zr-N = zirconium nitrate
ZrO2 = zirconia
■
REFERENCES
(1) Fauchais, P. L.; Heberlein, J. V. R.; Boulos, M. I. Thermal Spray
Fundamentals: From Powder to Part; Springer: London, 2014.
(2) Pawlowski, L. Suspension and Solution Thermal Spray Coatings.
Surf. Coat. Technol. 2009, 203, 2807.
4968
Article
(3) Chen, D.; Jordan, E. H.; Gell, M. Solution Precursor High-
Velocity Oxy-Fuel Spray Ceramic Coatings. J. Eur. Ceram. Soc. 2009,
29, 3349.
(4) Fauchais, P.; Montavon, G. Latest Developments in Suspension
and Liquid Precursor Thermal Spraying. J. Therm. Spray Technol. 2010,
19 (1−2), 226.
(5) Bertolissi, G.; Chazelas, C.; Bolelli, G.; Lusvarghi, L.; Vardelle,
M.; Vardelle, A. Engineering the Microstructure of Solution Precursor
Plasma-Sprayed Coatings. J. Therm. Spray Technol. 2012, 21, 1148.
(6) Jordan, E. H.; Xie, L.; Gell, M.; Padture, N. P.; Cetegen, B.;
Ozturk, A.; Roth, J.; Xiao, T. D.; Bryant, P. E. C. Superior Thermal
Barrier Coatings Using Solution Precursor Plasma Spray. J. Therm.
Spray Technol. 2004, 13, 57.
(7) Gell, M.; Jordan, E. H.; Teicholz, M.; Cetegen, B. M.; Padture, N.
P.; Xie, L.; Chen, D.; Ma, X.; Roth, J. Thermal Barrier Coatings Made
by the Solution Precursor Plasma Spray Process. J. Therm. Spray
Technol. 2008, 17, 124.
(8) Saha, A.; Seal, S.; Cetegen, B.; Jordan, E.; Ozturk, A.; Basu, S.
Thermo-Physical Processes in Cerium Nitrate Precursor Droplets
Injected into High-Temperature Plasma. Surf. Coat. Technol. 2009,
203, 2081.
(9) Vassen, R.; Stuke, A.; Stöver, D. Recent Developments in the
Field of Thermal Barrier Coatings. J. Therm. Spray Technol. 2009, 18,
181.
(10) Fauchais, P.; Vardelle, A. Solution and Suspension Plasma
Spraying of Nanostructure Coatings. In Advanced Plasma Spray
Applications; Hamid, J., Ed.; InTech, 2012; pp 149−188.
(11) Noppakun, S. Solution Precursor Plasma Spray System; Springer,
2014.
(12) Chen, D.; Jordan, E. H.; Gell, M. The Solution Precursor
Plasma Spray Coatings: Influence of Solvent Type. Plasma Chem.
Plasma Process. 2010, 30, 111.
(13) Govindarajan, S.; Dusane, R. O.; Joshi, S. V. In Situ Particle
Generation and Splat Formation during Solution Precursor Plasma
Spraying of Yttria-Stabilized Zirconia Coatings. J. Am. Ceram. Soc.
2011, 94, 4191.
(14) Basu, S.; Jordan, E. H.; Cetegen, B. M. Fluid Mechanics and
Heat Transfer of Liquid Precursor Droplets Injected into High-
Temperature Plasmas. J. Therm. Spray Technol. 2008, 17, 60.
(15) Basu, S.; Cetegen, B. M. Modeling of Thermo-Physical
Processes in Liquid Ceramic Precursor Droplets Injected into a
Plasma Jet. Int. J. Heat Mass Transfer 2007, 50, 3278.
(16) Ozturk, A.; Cetegen, B. M. Experiments on Ceramic Formation
from Liquid Precursor Spray Axially Injected into an Oxy-Acetylene
Flame. Acta Mater. 2005, 53, 5203.
(17) Basu, S.; Cetegen, B. M. Modeling of Liquid Ceramic Precursor
Droplets in a High-Velocity Oxy-Fuel Flame Jet. Acta Mater. 2008, 56,
2750.
(18) Dobbins, T. A.; Knight, R.; Mayo, M. J. HVOF Thermal Spray
Deposited Y2O3-Stabilized ZrO2 Coatings for Thermal Barrier
Applications. J. Therm. Spray Technol. 2003, 12, 214.
(19) Cetegen, B. M.; Basu, S. Review of Modeling of Liquid
Precursor Droplets and Particles Injected into Plasmas and High-
Velocity Oxy-Fuel (HVOF) Flame Jets for Thermal Spray Deposition
Applications. J. Therm. Spray Technol. 2009, 18, 769.
(20) Marchal, J.; John, T.; Baranwal, R.; Hinklin, T.; Laine, R. M.
Yttrium Aluminum Garnet Nanopowders Produced by Liquid-Feed
Flame Spray Pyrolysis (LF-FSP) of Metalloorganic Precursors. Chem.
Mater. 2004, 16, 822.
(21) Jain, S.; Skamser, D. J.; Kodas, T. T. Morphology of Single-
Component Particles Produced by Spray Pyrolysis. Aerosol Sci.
Technol. 1997, 27, 575.
(22) Hinklin, T.; Toury, B.; Gervais, C.; Babonneau, F.; Gislason, J.
J.; Morton, R. W.; Laine, R. M. Liquid-Feed Flame Spray Pyrolysis of
Metalloorganic and Inorganic Alumina Sources in the Production of
Nanoalumina Powders. Chem. Mater. 2004, 16, 21.
(23) Mahadevan, R.; Lee, D.; Sakurai, H.; Zachariah, M. R.
Measurement of Condensed-Phase Reaction Kinetics in the Aerosol
DOI: 10.1021/acs.iecr.6b04857
Ind. Eng. Chem. Res. 2017, 56, 4957−4969
Industrial & Engineering Chemistry Research Article

Phase Using Single Particle Mass Spectrometry. J. Phys. Chem. A 2002, (48) Shannon, K. S.; Butler, B. W. A Review of Error Associated with
106, 11083. Thermocouple Temperature Measurement in Fire Environments. Int.
(24) Mädler, L.; Pratsinis, S. E. Bismuth Oxide Nanoparticles by Wildl. Fire Ecol. 2003, 7.
Flame Spray Pyrolysis. J. Am. Ceram. Soc. 2002, 85, 1713. (49) Suryanarayana, C.; Prabhu, B. Synthesis of Nanostructured
(25) Rudin, T.; Wegner, K.; Pratsinis, S. E. Towards Carbon-Free Materials by Inert-Gas Condensation Methods. In Nanostructured
Flame Spray Synthesis of Homogeneous Oxide Nanoparticles from Materials: Processing, Properties, and Applications; Carl, C. K., Ed.;
Aqueous Solutions. Adv. Powder Technol. 2013, 24, 632. William Andrew, 2007; pp 47−90.
(26) Rudin, T. Towards Scalable Carbon-Free Synthesis of Sophisticated (50) Mahrukh, M.; Kumar, A.; Gu, S.; Kamnis, S. Computational
Nanoparticles. Dissertation, Doctor of Sciences, ETH Zurich, 2012. Development of a Novel Aerosol Synthesis Technique for Production
(27) Fauchais, P.; Montavon, G.; Lima, R. S.; Marple, B. R. of Dense and Nanostructured Zirconia Coating. Ind. Eng. Chem. Res.
Engineering a New Class of Thermal Spray Nano-Based Micro- 2016, 55 (28), 7679.
structures from Agglomerated Nanostructured Particles, Suspensions (51) Gröhn, A. J.; Pratsinis, S. E.; Antoni, S.-F.; Raffaele, M.; Wegner,
and Solutions: An Invited Review. J. Phys. D: Appl. Phys. 2011, 44, K. Scale-up for Nanoparticle Synthesis by Flame Spray Pyrolysis: The
93001. High-Temperature Particle Residence Time. Ind. Eng. Chem. Res. 2014,
(28) Gadow, R.; Killinger, A.; Rauch, J. New Results in High-Velocity 53, 10734.
Suspension Flame Spraying (HVSFS). Surf. Coat. Technol. 2008, 202, (52) Gröhn, A. J.; Pratsinis, S. E.; Wegner, K. Fluid-Particle
4329. Dynamics during Combustion Spray Aerosol Synthesis of ZrO2.
(29) Puranen, J.; Laakso, J.; Kylmälahti, M.; Vuoristo, P. Character- Chem. Eng. J. 2012, 191, 491.
ization of High-Velocity Solution Precursor Flame-Sprayed Manganese (53) Dongmo, E.; Wenzelburger, M.; Gadow, R. Analysis and
Cobalt Oxide Spinel Coatings for Metallic Sofc Interconnectors. J. Optimization of the HVOF Process by Combined Experimental and
Therm. Spray Technol. 2013, 22, 622. Numerical Approaches. Surf. Coat. Technol. 2008, 202, 4470.
(30) Li, M.; Shi, D.; Christofides, P. D. Diamond Jet Hybrid HVOF (54) Gu, S.; Eastwick, C. N.; Simmons, K. A.; McCartney, D. G.;
Thermal Spray: Gas-Phase and Particle Behavior Modeling and McCartney, G.; McCartney, D. G. Computational Fluid Dynamic
Feedback Control Design. Ind. Eng. Chem. Res. 2004, 43, 3632. Modelling of Gas Flow Characteristics in a High-Velocity Oxy-Fuel
(31) Li, C.; Yang, H.; Li, H. Effect of Gas Conditions on HVOF Thermal Spray System. J. Therm. Spray Technol. 2001, 10, 461.
Flame and Properties of WC-Co Coatings. Mater. Manuf. Processes (55) Kruis, F. E.; Kusters, K. A.; Pratsinis, S. E.; Scarlett, B. A Simple
1999, 14, 383−395. Model for the Evolution of the Characteristics of Aggregate Particles
(32) Li, C.; Wang, Y. Effect of Particle State on the Adhesive Undergoing Coagulation and Sintering. Aerosol Sci. Technol. 1993, 19,
Strength of HVOF Sprayed Metallic Coating. J. Therm. Spray Technol. 514.
2002, 11, 523. (56) Gozali, E.; Mahrukh, M.; Gu, S.; Kamnis, S. Numerical
(33) Wang, Y.; Li, C.; Yang, G. Effect of Flame Conditions on Investigation on Effects of Nanoparticles on Liquid Feedstock
Abrasive Wear Performance of HVOF Sprayed Nanostructured WC- Behavior in High-Velocity Oxygen Fuel (HVOF) Suspension
12Co Coatings. Trans. Nonferrous Met. Soc. China 2004, 14, 72. Spraying. Surf. Coat. Technol. 2015, 280, 370.
(34) Li, C.; Yang, G.; Wang, Z. Formation of Nanostructured TiO2 (57) Chen, D.; Jordan, E. H.; Gell, M. Effect of Solution
by Flame Spraying with Liquid Feedstock. Mater. Lett. 2003, 57, 2130. Concentration on Splat Formation and Coating Microstructure
(35) Mahrukh, M.; Kumar, A.; Gu, S. Effects of Angular Injection, Using the Solution Precursor Plasma Spray Process. Surf. Coat.
and Effervescent Atomization on High-Velocity Suspension Flame Technol. 2008, 202, 2132.
Spray Process. Surf. Coat. Technol. 2016, 302, 368. (58) Gozali, E.; Mahrukh, M.; Gu, S.; Kamnis, S. Numerical Analysis
(36) Liu, L.; Fu, M.; Wu, J. The Distribution of SMD Downstream of Multicomponent Suspension Droplets in High-Velocity Flame
the Discharge Orifices of Effervescent Atomizers. J. Eng. Thermophys. Spray Process. J. Therm. Spray Technol. 2014, 23, 940.
2001, 22, 653.
(37) Qian, L.; Lin, J.; Xiong, H. A Fitting Formula for Predicting
Droplet Mean Diameter for Various Liquid in Effervescent Atom-
ization Spray. J. Therm. Spray Technol. 2010, 19, 586.
(38) Lefebvre, A. H.; Wang, X. F.; Martin, C. A. Spray Characteristics
of Aerated-Liquid Pressure Atomizers. J. Propul. Power 1988, 4, 293.
(39) Roesler, T. C.; Lefebvre, A. H. Studies on Aerated-Liquid
Atomization. Int. J. Turbo Jet Engines 1989, 6, 221−230.
(40) Qian, L.; Lin, J.; Xiong, H. Simulation of Droplet-Gas Flow in
the Effervescent Atomization Spray with an Impinging Plate. Chin. J.
Chem. Eng. 2009, 17, 8.
(41) Sovani, S. D.; Sojka, P. E.; Lefebvre, A. H. Effervescent
Atomization. Prog. Energy Combust. Sci. 2001, 27, 483.
(42) Qian, L.; Lin, J. Modeling on Effervescent Atomization: A
Review. Sci. China: Phys., Mech. Astron. 2011, 54, 2109.
(43) Jedelsky, J.; Jicha, M.; Slama, J.; Otahal, J. Development of an
Effervescent Atomizer for Industrial Burners. Energy Fuels 2009, 23,
6121.
(44) Whitlow, J. D.; Lefevbre, A. H. Effervescent Atomizer Operation
and Spray Characteristics. Atomization Sprays 1993, 3, 137.
(45) Joshi, N. G.; Garg, A. N. Gamma-Radiolysis of Solid Zirconium
Nitrate and Its Binary Mixtures with Potassium Halides. J. Radioanal.
Nucl. Chem. 1990, 142, 515.
(46) Askestad, I. Ceramic Thermal Barrier Coatings of Yttria Stabilized
Zirconia Made by Spray Pyrolysis. Master’s thesis, Norwegian University
of Science and Technology, 2011.
(47) Biswas, M.; Ojha, P. K.; Jayasingh, E. M.; Prasad, C. D. Synthesis
of Nanocrystalline Yttria Stabilized Zirconia for SOFC. Nanomater.
Nanotechnol. 2011, 1, 55.

4969 DOI: 10.1021/acs.iecr.6b04857

Ind. Eng. Chem. Res. 2017, 56, 4957−4969