Slurry Spray Coating Technology with the Aid of Sintering Additive

R. Verma1, N.M. Suri3, S. Kant2,

1
Assistant Prof., Production & Industrial Engg, PEC University of Technology, Chandigarh
E-mail: rajeev.pec123@gmail.com
2
Associate Prof. Production & Industrial Engg, PEC University of Technology, Chandigarh
3
Assistant Prof. Production & Industrial Engg, PEC University of Technology, Chandigarh

Abstract
Slurry spray technique (SST) usually known by its low fabrication cost, is a relatively un-
utilized coating fabrication method which can be used for a variety of sinterable feedstock
materials. It utilizes thermal energy corresponding to the sintering temperature for
consolidation of the powder constituents, which is substantially lower than their melting
temperature. To further lower the fabrication temperatures, use of TiO2 as liquid phase sintering
additive is investigated in the present work. Furthermore, the article reports the effect of SST
process parameters on response parameters of the produced mullite based environmental
barrier coatings. Coating thickness and coating density were measured as the response
parameters. The results revealed that coating thickness and coating density increases
substantially with increase in sintering time. Moreover, change in sintering temperature
drastically affect coating thickness and coating density with incorporation of sintering additive.
Keywords: Slurry spray technique, environmental barrier coatings, coating thickness, coating
density.
1. INTRODUCTION
Ceramics are preferable choice and used customarily as environmental barrier coatings (EBCs)
which represent a comparatively thin film of impervious material bonded to the substrate. EBC
materials are chosen so that they can to protect the metal substrate at elevated temperatures and
chemically harsh conditions. Application of EBCs can thus reduce thermal shocks acting on
the load carrying structures ranging from the gas turbine, boilers, internal combustion engines
and many more. Use of partially stabilised zirconia (PSZ) is prevalent in manufacturing EBCs;
however, research efforts have continually been made towards making use of monolithic
mullite (3Al2O32SiO2), which is comparatively better alternative and economically viable
material in such applications. Functional gradation in the coating structure can help reduce the
thermal mismatch between the ceramic and metal when subjected to temperature excursions.
This can be done by making use of nickel which closely resembles the thermo-mechanical
properties of mullite and ASTM 1018 low carbon steel substrate chosen for the study. These
properties are determined by the coefficient of thermal expansion (CTE) and thermal
conductivity of these materials.

In this present work, SST a novel and unutilized technique was used for manufacturing mullite-
nickel based functionally graded coatings on ASTM 1018 low carbon/mild steel substrate. The
overall aim was to expand the understanding of the mechanism of various fabrication stages
and investigate the effect of process deposition parameters of SST on coating compliance. Fly
ash emerges as the primary waste generated by combustion of pulverized coal largely in
thermal power plants. It comprises of oxides like -quartz (SiO2), mullite (3Al2O32SiO2),
hematite (Fe2O3), magnetite (Fe3O4), lime (CaO) and other minor constituents as the loss on
ignition (LOI) (White et al., 1990). An effort has been made in the present investigation, to
explore the coating potential of class F fly ash using SST, to develop EBCs on low carbon
steel.

Sintering of the green powder compact to form sturdy structure is the critical stage of SST.
However, sintering of powdered mullite in its purest form exhibits difficulties due to poor inter-
diffusions of Si4+ and Al3+ in mullite lattice (Tenzuka et al., 2009). Moreover, sintering at high
temperature up to 1600C poses the threat of defects in the coating as well as the substrate. In
response to this, attempts have been made to sinter mullite at lower temperatures with the aid
of titanium dioxide (TiO2) as liquid phase sintering (LPS) additive in the present research. It
envisages the processing and characterization of series of slurry sprayed mullitenickel coating
premixed with fly ash and LPS in different proportions.

In this research article, SST was studied through one-factor-at-a-time approach. Four control
parameters namely fly ash composition, sintering additive, sintering time, and sintering
temperature were selected for the study. The experimentation was performed using ASTM
1018 low carbon steel substrate material. Based on extensive review of the literature survey,
coating thickness and coating density were chosen as the result of experimentation and
analysed to determine the individual effects of the process parameters within the selected range.
2. SLURRY SPRAY TECHNIQUE
The slurry spray technique utilises conventional wet powder spraying method to deposit
sinterable slurry materials onto target substrate. The process involves slurry preparation which
involves suspending the coating powders within a fluid that can be applied to a surface using
conventional gravity feed air pressurised spray gun. Tera sodium pyrophosphate (TSPP) as
dispersing agent (Greenwood et al., 1999), hydrosoluble polyvinyl alcohol (PVA) as binder (Roy
et al., 2005) and distilled water as solvent was utilized for slurry preparation. Successive layers
are then sprayed onto the substrate and dried using varying slurry compositions to produce a
functional coating. The multi-layered coatings is left to dry for approximately and hour,
depending on ambient conditions (Nguyen, 2007). The loosely held green coating is
compressively loaded to form a densified layer. The applied pressure varies depending on the
coating thickness and typically ranges between 20 and 40 MPa. Stamping pressure of 30 MPa
was held constant throughout the experimentation in this study. The dried green coating layers
are subsequently fired in a furnace to the sintering temperature corresponding to the highest
melting ingredient which is ceramic. The fabrication in the SST consists of the principle stages
as explained in Figure 1.

(1) Slurry preparation (2) Multilayer spraying

Load

(5) Debinding & sintering (4) Pressure stamping (3) Solvent drying
 Figure 1: Stages in slurry spray technique (Verma et al., 2015)

One-factor-at-a-time approach
For the pilot experimentation on the development of mullite-nickel based EBCs, the selected
experimental design was according to one-factor-at-a-time (OFAT) approach. This method
consists of selecting a starting point or baseline set of levels, for each factor and then
successively varying each factor over its ranges with all other factors held constant at the
baseline level. After performing all the tests, a series of graphs are usually constructed showing
how the response variable is affected by varying each factor with the other factors held constant
(Montgomery, 2013). Using these OFAT graphs, one could select the optimal combination of
the certain set of considered conditions. However, OFAT is unable to consider any interaction
between the variable, which is the major limitation of this method. This is the main reason the
OFAT approach is widely used for preliminary experimentations in order to screen out the
main process parameters and to decide the range of factors for subsequent detailed and
extensive experimentation. The composition of the slurry mixture used for the experimentation
is given in Table 1. The selected process parameters and their range for the pilot
experimentation are given in Table 2.
Table 1: Composition of slurry mixture, (125g)
Ceramic to Mullite Fly-ash Nickel Additive: TiO2 Binder Dispersant Mix agent
Metal (1%) 1% 2.5% 0.5% 52%
75-25 40.8375 0.413 13.75 1.25 3.125 0.625 65
50-50 27.225 0.275 27.5 1.25 3.125 0.625 65
25-75 13.6125 0.138 41.25 1.25 3.125 0.625 65

Table 2: Process parameters and their chosen levels considered for the pilot experiments
Labels Process Parameter Range Units Level 1 Level 2 Level 3 Level 4
A Fly-ash composition 1-15 wt.% 1 5 10 15
B Sintering additive 1-7 wt.% 1 3 5 7
C Sintering time 15-45 Minutes 15 25 35 45
D Sintering temperature 800-1100 C 800 900 1000 1100
Stamping pressure, 30MPa; Spraying pressure: 4 bar

Coating thickness (m) and coating density (kg/m3) were selected as quality characteristics
under consideration for pilot experimentation. Coating thickness of each ASTM 1018 low
carbon/mild steel coating coupons after the carrier drying stage, and eventually after the
sintering stage was carefully noted. For coating density, the weight of the each coating coupons
before and after the coating was carefully measured. Each dimension of the uncoated coupons
was noted for volume measurement. These measurements were used for calculating coating
density as;
( )
= (Eqn. 1)

The coating coupons were coated via the procedure as per Figure 1. Each experiment was
repeated three times, and the responses of respective experiments were recorded (Table 3).
3. RESULTS AND DISCUSSION
Effect of fly-ash composition on CT and CD
The randomized experiments with process parameters were planned as per Table 3, to study
the effect of the OFAT, i.e. fly-ash composition wt.% on the response parameters of coating
thickness, CT (m) and coating density, CD (kg/m3).

Table 3: Results of experimentation - Fly-ash composition

Response for Coating Thickness, Response for Coating Density,

Parameter
Exp No. CT (m) CD (kg/m3)
A
R1 R2 R3 Mean CT R1 R2 R3 Mean CD
1 1 227 236 221 228 2598 2648 2612 2619
2 5 243 238 261 247 2115 2128 2132 2125
3 10 256 267 253 259 1768 1875 1892 1845
4 15 192 178 181 184 2828 2847 2869 2848
Stamping pressure, 30MPa; Spraying pressure: 4 bar.
R1, R2, R3 represent response value for three repetitions of each trial.

The main effect of the process parameter, fly-ash composition (A) on coating thickness, CT
and coating density, CD was determined based on the average of the raw response data. The
main effect of the Fly-ash composition with all other factors held constant at the baseline level
is plotted in Figure 2.
300 3000

Coating Density CD, (kg/m3)

Coating Thickness CT, (m)

250 2500
200 2000
150 1500
100 1000
50 500
CT CD
0 0
1 5 10 15
Fly-ash composition (wt.%)
Figure 2: Effect of Fly-ash composition on Coating thickness and Coating density in pilot experimentation

The main effect of fly-ash composition shows increasing trend for coating thickness up to 10
wt.%. However, at 15 wt.% there is a drop being noted in coating thickness. This initial
increasing trend in coating thickness may be attributed to the liquid phase sintering effect of
the fly-ash particles (Dong et al. 2010). The opposite trend of coating thickness and coating
density was observed throughout the pilot experimentation for Fly-ash composition studied
from 1 15 wt.%.

Effect of sintering additive on CT and CD

To study the effect of the OFAT, i.e. sintering additive (wt.%) on the response parameters of
coating thickness, CT and coating density, CD, the randomized experiments with process
parameters were planned as per Table 4.
 Table 4: Results of experimentation Sintering additive (TiO2)
Response for Coating Thickness, Response for Coating Density,
Parameter
Exp No. CT (m) CD (kg/m3)
B
R1 R2 R3 Mean CT R1 R2 R3 Mean CD
1 1 317 321 338 325 2837 2857 2846 2847
2 3 267 291 276 278 3735 3745 2315 3265
3 5 147 168 159 158 2115 2128 2132 2125
4 7 256 244 253 251 1528 1516 1531 1525
Stamping pressure, 30MPa; Spraying pressure: 4 bar.
R1, R2, R3 represent response value for three repetitions of each trial.

The main effect of the sintering additive on coating thickness and coating density with all other
factors held constant at the baseline level is plotted in Figure 3. The main effect shows a
decrease in coating thickness with an increase in sintering additive upto 5wt.%, thereafter there
is increase in coating thickness being observed. The decline in coating thickness may be
attributed to the increased effect of the low temperature, rapid densification due to liquid phase
sintering additive i.e. TiO2 (Rajeswari et al., 2010). Coating density, however, showed an initial
increase from 1 to 3 wt.%, and beyond 3 wt.% there is a decreasing trend.

Coating Density CD, (kg/m3)

350 3500
Coating Thickness CT, (m)

300 3000
250 2500
200 2000
150 1500
100 1000
50 500
CT CD
0 0
1 3 5 7
Sintering additive, TiO2 (wt.%)
Figure 3: Effect of Sintering additive on Coating thickness and Coating density

Effect of sintering time on CT and CD

The main effect of the sintering time on coating thickness and coating density (Table 5), with
all other factors held constant at the baseline level is plotted in Figure 4.

Table 5: Results of experimentation Sintering time

Response for Coating Thickness, Response for Coating Density,

Parameter
Exp No. CT (m) CD (kg/m3)
C
R1 R2 R3 Mean CT R1 R2 R3 Mean CD
1 15 185 209 201 198 1965 1922 1864 1917
2 25 308 278 292 293 2512 2654 2594 2587
3 35 352 368 376 365 2825 3088 2874 2929
4 45 275 292 288 285 3190 3344 3288 3274
Stamping pressure, 30MPa; Spraying pressure: 4 bar.
R1, R2, R3 represent response value for three repetitions of each trial.
 400 3500

Coating Thickness CT, (m)

Coating Density CD, (kg/m3)

350 3000
300 2500
250
2000
200
1500
150
100 1000
50 500
CT CD
0 0
15 25 35 45
Sintering Time, (Minutes)
Figure 4: Effect of Sintering time on Coating thickness and Coating density

It was observed during the study, that increase in sintering time increases coating thickness and
coating density almost linearly showing the similar trend as shown in figure 4. However, there
is a slight decrease in coating thickness being observed from sintering time level 3 to 4 i.e. 35
to 45 minutes. Thus sintering time corresponding to 35 minutes may be considered optimal for
the given set of experimental conditions, which suggests decreased sintering time required for
coating densification with the introduction of applied stamping pressure before sintering.

Effect of sintering temperature on CT and CD

The main effect of the sintering temperature on coating thickness and coating density (Table
6) deduced from the experiments, with all other factors held constant at the baseline level is
plotted in Figure 5.
Table 6: Results of experimentation Sintering temperature
Response for Coating Thickness, Response for Coating Density,
Parameter
Exp No. CT (m) CD (kg/m3)
D
R1 R2 R3 Mean CT R1 R2 R3 Mean CD
1 800 302 288 296 295 1822 1918 1865 1868
2 900 358 372 380 370 3190 3328 3282 3267
3 1000 224 230 218 224 2895 2820 2892 2869
4 1100 198 182 204 195 2038 2078 1981 2032
Stamping pressure, 30MPa; Spraying pressure: 4 bar.
R1, R2, R3 represent response value for three repetitions of each trial.
Coating Density CD, (kg/m3)

400 3500
Coating Thickness CT, (m)

350 3000
300 2500
250
2000
200
1500
150
100 1000
50 500
CT CD
0 0
800 900 1000 1100
Sintering Temperature, (C)
Figure 5: Effect of Sintering temperature on Coating thickness and Coating density
It has been observed that coating thickness initially increases with increase in sintering
temperature upto 900C, and afterwards downfall trend has been observed at the higher
temperatures (beyond 900C). A similar trend is also observed for coating density for the
selected range of sintering temperature (i.e. 800 1100C). Increased coating thickness and
coating density at 900C suggest the improved sintering activity, lowering the secondary
mullitization temperature, due to TiO2 as well as fly ash. The observed decrease in coating
thickness and coating density beyond 900C may be attributed to the increased shrinkage of
mullite due to crystallization of amorphous mullite, which is also observed in mullite coatings
by Withey et al., 2007.
Surface macrographs of some of the sintered sample during the experiments are shown in
Figure 6. Defect free surface of these specimens suggests that the above design settings yielded
good results concerning coating integrity and coating thickness obtained. These sintered
specimens were ground at one end, showing a clearly distinct substrate and multilayer coating
with thickness as shown in Figure 7. Moreover, fly-ash as an alternative to ceramic was tested
which showed promising results with intensified coating deposition. So these design
parameters can be implemented and could be used for further detailed experiments.

3mm 3mm 3mm

Figure 6: Surface macrographs of mullite-nickel based coated specimens

3mm 3mm
3mm

Figure 7: Surface macrographs after grinding of coated specimen shows multilayer coatings

4. SEM ANALYSIS

The surface micrograph and the cross-sectional morphology of the as-deposited coating
specimen (Table 4: Trial 2 - sintering additive: 3 wt.%) has been shown in Figure 8a & 8b
respectively. The fabricated coatings have been deposited by moving the slurry spray gun onto
stationary substrates, and the desired coating thickness is due to varying the number of passes
of the distinct functionally graded composition layers (as per Table 1). The as-sprayed splat
morphology with the continuous interface is evident from the coating microstructure and
suggest a good coating-substrate adherence. Dense inter-splat coating with coarser grain
structure has been observed along with the characteristic microstructure features of a thermal
spray coating like discontinuities, pores, microcracks, and voids, etc. Inclusions in the form of
globular and interlamellar pores, oriented parallel to the substrate surface have been observed
in the coatings structure. It can be noted from the cross-section micrographs that the specimen
exhibit a little porosity and hence densified structure. The reduced porosity was caused by the
sintering mechanism driven by the deduction of surface energies and increased grain boundary
areas of constituent particles by fusing to create a continuous medium (Bernard-Granger et al.,
2007, Masoumi et al., 2014). Moreover, liquid phase sintering effect imparted by TiO2 caused
the constituents to drawn into closer proximity thereby reducing the coating volume.

Figure 8: SEM micrographs of the slurry sprayed mullite-nickel coating on mild steel specimen using SST
(a) Surface micrograph, (b) Along the cross-section
(Trial 2, Table 4 - Sintering additive: 3 wt.%; Mean coating thickness: 278m, Mean coating density:
3265 kg/m3)

CONCLUSION
SST which is being identified as new avenue to utilize fly ash as coating ingredient and its low
fabrication cost, makes it a suitable choice for further investigation and work towards its large
scale use as part of governments make in India campaign. Pilot experimentation based on
OFAT was performed with a focus on experimental studies of the effect of identified control
parameters of SST. The selected parameter setting provided a substantial range of coating
thickness and coating density, which can be considered as a measure of deposition efficiency
of SST. For manufacturing mullite-nickel based EBCs on mild steel substrate, optimum
parameters setting (fly ash composition 1-wt.%, sintering additive 3-wt.%, sintering time 35
minutes, and sintering temperature 900C) was obtained by this experimentation. These
parameter setting provided higher coating thickness and coating density values, and delineated
good surface integrity free from any visible defects.

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