materials

Article
Effect of Slurry Thickness on the Quality of
Aluminized Coatings
Zhuoyue Li 1 , Cheng Wang 1, *, Xiangyu Ding 1,2 , Xin Li 1 , Jiabo Yu 1 , Qiuliang Li 1 and Yi Qu 1

1 Fundamental Department, Air Force Engineering University, Xi’an 710051, China

2 College of Aircraft Engineering, Nanchang Hangkong University, Nanchang 330063, China
* Correspondence: valid_01@163.com

Abstract: Diffusion aluminum coating is crucial to protect aero-engine turbine blades from high-
temperature oxidation. Slurry aluminizing, as a commonly-used coating preparation technology, has
variations in the process parameters that directly affect the quality of the coating. Therefore, this
paper investigates the effect of slurry thickness on coating quality. Different forms of aluminized
coatings were obtained by coating nine DZ22B nickel-based superalloy plates of the same size with
different slurry thicknesses while keeping other parameters constant. These aluminized coatings were
characterized using a scanning electron microscope (SEM) with an energy dispersive spectrometer
(EDS), an X-ray diffractometer (XRD), and a surface gauge. The results show that the AlNi phase
dominates the matrix of the aluminized coating, and the outer layer of the coating has white dotted
precipitates of Cr. As the slurry thickness increases, the coating thickness increases, and the proportion
of the outer layer in the overall coating increases. In contrast, the thickness of the interdiffusion layer
does not change significantly. The thicker the slurry, the higher the Al content of the coating surface.
A medium-thickness slurry can form a smooth aluminizing coating with a roughness Ra < 4.5 µm
surface. The combined results show that a medium-thick slurry can produce a high-quality coating.

Keywords: aluminized coating; coating thickness; diffusion; roughness; slurry thickness

Citation: Li, Z.; Wang, C.; Ding, X.;
Li, X.; Yu, J.; Li, Q.; Qu, Y. Effect of
Slurry Thickness on the Quality of
Aluminized Coatings. Materials 2022,
15, 6758. https://doi.org/10.3390/ 1. Introduction
ma15196758 The core parameter of an aircraft engine thrust increase is the pre-turbine gas tem-
Academic Editors: Andriy Burbelko
perature. The limiting factor for increasing pre-turbine gas temperatures is the material’s
and Daniel Gurgul
high-temperature resistance (1300–2000 K) [1]. Nickel-based superalloys have excellent
mechanical properties at high temperatures (900–1600 K), which is why they are most
Received: 6 September 2022 widely accepted in manufacturing engine turbine blades [2,3]. The adjustment of alloy
Accepted: 26 September 2022 composition can improve the alloy properties to some extent. For example, adding Cr, Al,
Published: 29 September 2022
and Y can confer oxidation resistance; B, Zr, C, and H can refine grain boundaries; B and Ta
Publisher’s Note: MDPI stays neutral can improve creep properties; and Co, Cr, and Si can provide anti-sulfuration properties [4].
with regard to jurisdictional claims in The high-temperature oxidation resistance of superalloys is positively correlated with
published maps and institutional affil- the content of the corresponding alloying elements, but simply increasing the content of
iations. antioxidant elements can significantly reduce the mechanical properties of the alloy. The
coating’s application balances the material’s mechanical properties and high-temperature
oxidation resistance [1,5–7]. Aluminide coatings or modified aluminide coatings (AlSi [8],
PtAl [9], AlSiY [10]) are commonly used to provide high-temperature oxidation resistance
Copyright: © 2022 by the authors.
to the blades.
Licensee MDPI, Basel, Switzerland.
The relatively mature methods for preparing aluminide coatings include thermal
This article is an open access article
spraying [11], pack cementation [12,13], slurry cementation [14], and hot-dipping [8]. The
distributed under the terms and
slurry method has several advantages over other methods: 1. shorter thermal cycle time
conditions of the Creative Commons
for preparing the coating; 2. the possibility of localized coating, for example, avoiding the
Attribution (CC BY) license (https://
blade root of the turbine blade to coat the blade body; and 3. the possibility of coating large
creativecommons.org/licenses/by/
4.0/).
parts [15]. Therefore, the slurry method is commonly used to obtain diffusion aluminide

Materials 2022, 15, 6758. https://doi.org/10.3390/ma15196758 https://www.mdpi.com/journal/materials

 for preparing the coating; 2. the possibility of localized coating, for example, avoiding the
blade root of the turbine blade to coat the blade body; and 3. the possibility of coating
large parts [15]. Therefore, the slurry method is commonly used to obtain diffusion alu-
Materials 2022, 15, 6758 minide coatings for turbine blades and fans [16–18]. The slurry is a suspension formed 2 of 12 by
mixing the aluminum powder with a binder. The slurry is sprayed on the substrate, dried
and cured, and then heat-treated to obtain a diffused aluminum coating [19]. Therefore,
parameters
coatings forsuch as slurry
turbine bladescomposition, deposition
and fans [16–18]. The slurry thickness, temperature,
is a suspension formed and heat treat-
by mixing
ment
thetime can influence
aluminum powder withthe organization
a binder. The andslurry properties
is sprayedofon diffused aluminum
the substrate, dried coatings.
and
cured, and
Montero et al.then
[20]heat-treated
investigated to obtain a diffused
the effects aluminum
of exposure coating [19].substrate
atmosphere, Therefore, param-
composition,
andeters such treatment
surface as slurry composition,
on aluminum deposition
coatings thickness,
on steeltemperature,
surfaces. The andresults
heat treatment
showed that
time can influence the organization and properties of diffused
the Ar atmosphere protects against oxidation to obtain intact coatings, that analuminum coatings. Montero
increase in
et al. [20] investigated the effects of exposure atmosphere, substrate composition, and
Cr content reduces coating coverage, and that higher roughness and smaller particle size
surface treatment on aluminum coatings on steel surfaces. The results showed that the
facilitate the formation of thick and uniform aluminum coatings. Rasmussen et al. [21]
Ar atmosphere protects against oxidation to obtain intact coatings, that an increase in Cr
investigated
content reducesthe microstructure
coating coverage, of and
aluminide
that higher coatings formed
roughness andby coating
smaller the surface
particle size of
nickel-based high-temperature alloys with two different thicknesses
facilitate the formation of thick and uniform aluminum coatings. Rasmussen et al. [21] of slurry. The results
show that slurry
investigated thethickness significantly
microstructure affects
of aluminide the morphology
coatings and composition
formed by coating the surface ofof the
nickel-based high-temperature alloys with two different
coatings. The mechanism of aluminide coating formation on pure nickel or thicknesses of slurry. Thenickel-based
results
show that slurry thickness significantly affects the morphology
alloy surfaces is well understood [22], but the optimization of slurry aluminizing and composition of the
process
coatings. The mechanism of aluminide
parameters is under continuous research [13,19,20]. coating formation on pure nickel or nickel-based
alloy surfaces is well understood [22], but the optimization of slurry aluminizing process
In the present paper, nine specimens were sprayed with different thicknesses of
parameters is under continuous research [13,19,20].
slurry to investigate the effect of slurry thickness on the quality of aluminized coatings.
In the present paper, nine specimens were sprayed with different thicknesses of
Theslurry
variation of coating
to investigate thequality
effect ofwith slurry
slurry thickness
thickness was
on the obtained
quality by microstructure
of aluminized coatings. ob-
servation, coating
The variation thickness
of coating measurement,
quality with slurryphysical
thicknessphase analysis,byand
was obtained coating surface
microstructure
roughness inspection.
observation, The investigation
coating thickness measurement,results can be
physical usedanalysis,
phase as a reference for the
and coating selection
surface
of slurry aluminizing process parameters.
roughness inspection. The investigation results can be used as a reference for the selection
of slurry aluminizing process parameters.
2. Materials and Methods
2. Materials and Methods
WeWe carried
carriedout
outdifferent thicknessesofofslurry
different thicknesses slurry aluminizing
aluminizing on the
on the surface
surface of DZ22B
of DZ22B
nickel-based, high-temperature alloy to study the effect of slurry thickness on the coat-
nickel-based, high-temperature alloy to study the effect of slurry thickness on the coating’s
ing’s thickness,
thickness, morphology,
morphology, and composition.
and composition. The experimental
The experimental flow is dividedflow is divided into
into preparation
preparation and characterization, as shown
and characterization, as shown in Figure 1. in Figure 1.

Figure 1. Flow chart of specimen preparation and characterization.

Figure 1. Flow chart of specimen preparation and characterization.

2.1.2.1. Aluminized
Aluminized SpecimensPreparation
Specimens Preparation
TheThe DZ22Balloy
DZ22B alloy with
withgood
goodhigh-temperature mechanical
high-temperature properties
mechanical and stability
properties and was
stability
chosen as the substrate, and its nominal composition and EDS analysis composition are
was chosen as the substrate, and its nominal composition and EDS analysis composition
shown in Table 1 [23]. The DZ22B alloy bar with a diameter of 32 mm was cut into 9 flat
are shown in Table 1 [23]. The DZ22B alloy bar with a diameter of 32 mm was cut into 9
pieces of the same size (80 mm× 20 mm × 5 mm) using a wire cutting machine (DK7725H,
ZHCF, Suzhou, China). The flat surfaces were abraded using a grinding and polishing
 Materials 2022, 15, x FOR PEER REVIEW 3 of 13

Materials 2022, 15, 6758

flat pieces of the same size (80 mm× 20 mm × 5 mm) using a wire cutting machine 3 of 12
(DK7725H, ZHCF, Suzhou, China). The flat surfaces were abraded using a grinding and
polishing machine (EcoMet 30, Buehler, Lake Bluff, IL, USA). The speed of the chassis was
set at 300 rpm, the sandpapers P240/P800 were used, and the grinding and polishing time
machine (EcoMetby
was determined 30,the
Buehler, Lake
polishing Bluff, Due
results. IL, USA).
to the The
size speed of the
limitation of chassis was set at
the flat specimens,
300 rpm, the sandpapers P240/P800 were used, and the grinding and polishing time was
it was impossible to mount the specimens in the fixture, so manual grinding and polishing
determined by the polishing results. Due to the size limitation of the flat specimens, it was
was used. The surface roughness to meet the aluminizing conditions is 0.044 μm [24].
impossible to mount the specimens in the fixture, so manual grinding and polishing was
used.
TableThe surface
1. Mass roughness
fraction to meet the
of main elements aluminizing
of DZ22B conditions is 0.044 µm [24].
alloy (wt.%).
Table 1. Mass fraction of main elements of DZ22B alloy (wt.%).
Element Cr Co W Al Ti Fe Nb Hf Ni
Nominal
Element 8.0–10.0
Cr 9.0–11.0
Co 11.5–12.5
W 4.75–5.25
Al 1.75–2.25
Ti <0.25
Fe 0.75–1.25
Nb 0.8–1.1
Hf Bal
Ni
EDS 9.25–9.95 9.03–9.97 11.1–12.9 5.41–5.86 1.95–2.40 0.26–0.37 0.95–1.13 0.74–1.77 56.4–58.9
Nominal 8.0–10.0 9.0–11.0 11.5–12.5 4.75–5.25 1.75–2.25 <0.25 0.75–1.25 0.8–1.1 Bal
EDS 9.25–9.95 9.03–9.97 11.1–12.9 5.41–5.86 1.95–2.40 0.26–0.37 0.95–1.13 0.74–1.77 56.4–58.9
The slurry aluminizing procedure is shown in Figure 2. After the plate specimens
wereThe ground
slurryand polished procedure
aluminizing smooth, they were cleaned
is shown in Figurein2.acetone
After theusing
plateanspecimens
ultrasonic
cleaner (KM-410C, KJM, Guangzhou, China) for 5 min, dried, and set
were ground and polished smooth, they were cleaned in acetone using an ultrasonic cleaner aside. Pure alumi-
num powder was used as the permeate, and fully ground in
(KM-410C, KJM, Guangzhou, China) for 5 min, dried, and set aside. Pure aluminum a mortar and pestle for two
hours. The binder consisted of isoamyl acetate, diethyl oxalate, and
powder was used as the permeate, and fully ground in a mortar and pestle for two hours. nitrocellulose. The
ground
The permeate
binder andofbinder
consisted isoamylwere mixeddiethyl
acetate, to formoxalate,
a slurry.and
Thenitrocellulose.
next step was slurry spray-
The ground
ing, and and
permeate ninebinder
specimenswerewere
mixedsprayed
to formwith different
a slurry. thicknesses
The next step wasofslurry
slurry, as shown
spraying, andin
Table
nine 2. After the
specimens were slurry curing,
sprayed withwe conducted
different two stages
thicknesses of high-temperature
of slurry, as shown in Tablediffusion
2. After
treatment
the in an argon
slurry curing, atmosphere
we conducted twoon the specimens:
stages Ⅰ. 950 ± 10diffusion
of high-temperature min; Ⅱ. 1000
°C, 1 h 10treatment in an±
10 °C, 2 h 20 min. This parameter is consistent ◦ with the typical surface
argon atmosphere on the specimens: I. 950 ± 10 C, 1 h 10 min; II. 1000 ± 10 C, 2 h 20 min. ◦
aluminizing of
turbine
This blades.isFinally,
parameter the with
consistent aluminized specimens
the typical surfacewere cleanedof
aluminizing toturbine
removeblades.
surfaceFinally,
impu-
rities
the and residual
aluminized slurry. were
specimens After cleaned
obtainingto the aluminized
remove surface specimens,
impurities and eachresidual
specimen was
slurry.
cut into
After 32 slicesthe
obtaining with the same specimens,
aluminized dimensionseach (10 mm × 5 mmwas
specimen × 4 cut
mm) for32
into subsequent
slices withchar-
the
same dimensions
acterization (10 mm × 5 mm × 4 mm) for subsequent characterization experiments.
experiments.

Figure2.2.Slurry
Figure Slurryaluminizing
aluminizingprocess.
process.

Table2.2.Slurry
Table Slurrythickness
thicknessvalues
valueson
ondifferent
differentspecimens
specimens(µm).
(μm).

Specimen
Specimen No.No. 1 1 2 33 44 55 66 77 8 8 99
Slurry
Slurry thickness
thickness 26 26 38
38 42
42 59
59 6060 7676 8181 9898 107
107

2.2.Aluminized
2.2. AluminizedCoating
CoatingCharacterization
Characterization
Theslices
The slicesobtained
obtainedby
bythe
thepreparation
preparationprocess
processwere
weremounted,
mounted,and
andthe
thecross-sections
cross-sections
were polished using an automatic grinding and polishing machine (EcoMet30,
were polished using an automatic grinding and polishing machine (EcoMet30, Buehler, Buehler,
Lake Bluff, IL, USA). After taking out the slices from the mounts, they were cleaned
Lake Bluff, IL, USA). After taking out the slices from the mounts, they were cleaned and and
dried in an ultrasonic cleaner (KM-410C, KJM, Guangzhou, China). The thickness and
morphology of the coating on the cross-section of the slices were observed using an SEM
(VEGA-3 XMU, TESCAN, Brno, Czech Republic). The parameters of the SEM were set
Materials 2022, 15, 6758 4 of 12

as follows: accelerating voltage 20 kV, current 3 nA, working distance 20 mm, Image
resolution 768 × 665 px, magnification 500×, SE detector for morphology observation,
and BSE detector for coating thickness measurement. Elemental composition analysis was
performed using the EDS accompanying the SEM. Each slice gives the coating thickness
on both sides so that each specimen can get 64 coating thickness values, and 9 specimens
can get 576 sets of data in total. The coating thickness values were measured using Image J
software developed by the National Institutes of Health. These data were used to determine
the relationship between slurry thickness and coating thickness. A physical phase analysis
of the coatings was performed using an XRD (XRD6100, SHIMADZU, Kyoto, Japan) with
parameters of Cu Kα radiation, λ = 0.15418 nm, 2θ = 20◦ –80◦ . The coating surface was
analyzed using a surface gauge (4D InSpec, 4D Technology, Tucson, AZ, USA) to investigate
the effect of slurry thickness on coating roughness.

3. Results and Discussion

3.1. Thickness of Aluminized Coating
Each specimen was cut into 32 slices and 64 coating thickness values were obtained. The
slurry thickness applied to each specimen was plotted against its corresponding coating thick-
ness in a box plot, as shown in Figure 3. The box plot was plotted using OriginPro software
(2018C, OriginLab Corporation, Northampton, MA, USA). According to the definition of the
box plot, the lower boundary of the box is the lower quartile (Q1 ), the horizontal line inside
the box is the median of the sample (Q2 ), and the upper boundary of the box is the upper
quartile (Q3 ). The interquartile distance (IQR) is equal to (Q3 − Q1 ). The upper edge of the
whisker line is the upper limit of the normal value, and its value is (Q3 + 1.5IQR). The lower
edge of the whisker line is the lower limit of the normal value, and its value is (Q1 − 1.5IQR).
In this paper, coating thickness values within the interval of [Q1 − 1.5IQR, Q3 + 1.5IQR] are
considered normal values. Otherwise, they are considered abnormal values. From Figure 3a,
it can be found that there are abnormal coating thickness values for specimens #3–6 and
specimen #8. Those cases of thin or even no coating thickness in abnormal values are probably
because the areas are located in the clamping position of the specimen during aluminizing and
are not sprayed with slurry or the sprayed slurry is thin. Those thicker coatings’ abnormal
values are caused by the aggregation of the slurry at the edges during the curing process.
The median coating thickness was slightly above the mean value except for specimen
#7, where the abnormal values influenced the mean value. Therefore, the median line can
more fairly reflect the interval where the coating thickness values are most concentrated.
We made a linear fit curve and a cubic polynomial fit of the median slurry thickness versus
coating thickness in Figure 3b,c, respectively. The goodness-of-fit (R2 ) of the linear fit was
0.93892, while the R2 of the cubic polynomial fit was 0.98346. Furthermore, in Figure 3b, we
can see that the coating thickness values for specimen #1 and specimen #9 deviate far from
the linear fit line. Y. Tamarin [15] proposed a 1:1 relationship between slurry thickness and
coating thickness after diffusion annealing of the cured slurry coating at a high temperature
(1200 ◦ C) for 1–2 h. From our experimental results, this linear relationship can be applied
when the slurry coating is of medium thickness. However, it does not apply when the
slurry thickness is too thin or too thick, which may be related to the diffusion dynamics.
When the slurry layer is thicker, the diffusion dynamics are strong, and the interdiffusion
between Ni and Al is fast, forming a thicker coating, while the opposite is true when the
slurry thickness is thin.
Materials 2022,
Materials 15, 6758
2022, 15, x FOR PEER REVIEW 5 of
5 12
of 13

(a) 160 25%~75%

Within 1.5 IQR
140 141
Median line 134
Coatings thickness(μm)

127
120 Average value 118
111 110
Abnormal values 102
100 97.5 95.4 98.6
90.5 87.8
84.7
80 77.2 79.1
72.7 72.7
67.1
60 60 60.6
56.2
52.4 50.6
40 42.1

25
20 20.5
14.2
0
26 38 42 59 60 76 81 98 107
Slurry thickness(μm)

y = 0.984 x + 16.981 y = 3.9×10-4 x3−0.1x2+6.6x−101.2

Median value of coating thickness (μm)

Median value of coating thickness (μm)

(b) 140 (c) 140

120 120

100 100

80 80

60 60

40 40

20 20
20 40 60 80 100 120 20 40 60 80 100 120
Slurry thickness (μm) Slurry thickness (μm)

Figure 3. Relationship
Figure between
3. Relationship slurry
between thickness
slurry and coating
thickness thickness.
and coating (a) Box
thickness. (a)plot
Boxofplot
slurry thickness
of slurry thick-
vs. ness vs. thickness;
coating coating thickness;
(b) linear(b) linear
fitting fitting
curve of curve
slurry of slurry thickness
thickness andthickness;
and coating coating thickness; and (c)
and (c) cubic
cubic polynomial
polynomial fitting
fitting curve curve thickness
of slurry of slurry thickness
and coatingandthickness.
coating thickness.

3.2.3.2.
Microstructure
Microstructure andand
Element
ElementDistribution
Distribution
Typical slices
Typical fromfrom
slices nine nine
specimens were were
specimens selected to observe
selected the microstructure
to observe of their of
the microstructure
cross-sections. The coating thickness and the distribution of elements on the cross-sections
their cross-sections. The coating thickness and the distribution of elements on the cross-
were obtained,
sections wereas obtained,
shown in as Figure
shown4. For brevity,4.only
in Figure For the BSE images
brevity, only theofBSE
the six samples
images #1,six
of the
#3, samples
#5, #6, #8, and #9 and the distribution of the major elements are shown in Figure
#1, #3, #5, #6, #8, and #9 and the distribution of the major elements are shown in 4.
For specimen
Figure 4. #1, the coating formed at a slurry thickness of only 26 µm was dis-
continuous, showing high and low undulations. As the slurry thickness increases, the
boundary between the coating and the substrate becomes flat and straight, and the coating
becomes thick. The top of the thicker aluminized layer is porous [25]. Overall, the slice
cross-section can be divided into four regions, as shown by the markers in Figure 4. Zone
I shows the same dark gray color as zone II under the BSE detector. However, there are
dense white spots in zone I, which are produced by Cr elements precipitated from the
substrate forming Crx Aly compounds with Al [22]. In Figure 5, the elemental content of
Cr fluctuates significantly from high to low in zone I, decreases in amplitude in zone II,
increases abruptly to a higher level in zone III, and plateaus in zone IV. It further proves that
the small white dots in zone I are Cr compounds. The Ni element shows a slow increase in
zone I and II, while the Al element, on the contrary, is slowly decreasing. Therefore, the
matrix in zone I may be an Al-rich AlNi phase, while zone II is a Ni-rich AlNi phase [21],
Materials 2022, 15, 6758 6 of 12

which needs to be verified after XRD testing. Zone III is the zone of the sharp decline of Al
elements and the enrichment of alloying elements in the substrate. It is noteworthy that
the content of Ni in zone III is lower than its content in the other zones. Zone III is often
referred to as the interdiffusion zone (IDZ) [26], while zone IV is the DZ22B alloy substrate.
Materials 2022, 15, x FOR PEER REVIEW 6 of 13
Based on the EDS map attached next to the BSE image of each sample, it is clear that the
larger white spots shown on the substrate and coating are compounds of Ti.

Figure 4. BSE cross-sectional images of different thicknesses of aluminized coatings on the surface of
Figure
DZ22B BSE (a)
4. alloy. cross-sectional
23 ± 9 μm, (b) images
60 ± 5 μm,of(c)
different thicknesses
85 ± 5 μm, of aluminized
(d) 89 ± 6 μm, coatings
(e) 109 ± 12 μm, (f) 136 ±on
13 the
μm.surface
of DZ22B alloy. (a) 23 ± 9 µm, (b) 60 ± 5 µm, (c) 85 ± 5 µm, (d) 89 ± 6 µm, (e) 109 ± 12 µm,
(f) 136 ±For13 specimen
µm. #1, the coating formed at a slurry thickness of only 26 μm was discon-
tinuous, showing high and low undulations. As the slurry thickness increases, the bound-
aryFigure
between4a the coating
shows the and the substrate
coating formed becomes
by the thin flat slurry,
and straight, and the
with zone coating
I only be-
sporadically
comes thick.
distributed at The
thetop of the thicker
edges. As thealuminized
thickness layerof theis porous
slurry[25]. Overall,zone
increases, the slice cross- up an
I takes
section can
increasing be divided
proportion of into four regions,
the coating systemas and
shown by the markers
gradually overtakes in Figure
zone II.4.ItZone I
is probably
shows the same dark gray color as zone II under the BSE detector.
due to the incomplete diffusion of Ni in the slurry with increasing slurry thickness that However, there are
dense white spots in zone I, which are produced by Cr elements precipitated from the
leads to a slight increase of Al content in the coating. At the same time, Cr solubility in the
substrate forming CrxAly compounds with Al [22]. In Figure 5, the elemental content of Cr
AlNi phase decreases with increasing Al content [27], forming more white dot precipitates.
fluctuates significantly from high to low in zone I, decreases in amplitude in zone II, in-
As creases
shownabruptly
in Figureto4,a the thickness of the IDZ layer does not vary with the slurry thickness
higher level in zone III, and plateaus in zone IV. It further proves
andthat
always
the small white dots in 15
remains around µm.
zone This
I are Criscompounds.
because theThe thickness
Ni elementof the IDZalayer
shows slow is in-mainly
affected
crease in zone I and II, while the Al element, on the contrary, is slowly decreasing. There- heat
by the temperature and time of high-temperature diffusion [28]. The same
treatment
fore, themethod
matrix inwaszone used
I mayforbeallanspecimens
Al-rich AlNi in this
phase, work and
while therefore
zone did notAlNi
II is a Ni-rich affect the
IDZ layer.
phase [21], which needs to be verified after XRD testing. Zone III is the zone of the sharp
decline of Al elements and the enrichment of alloying elements in the substrate. It is note-
worthy that the content of Ni in zone III is lower than its content in the other zones. Zone III
is often referred to as the interdiffusion zone (IDZ) [26], while zone IV is the DZ22B alloy
substrate. Based on the EDS map attached next to the BSE image of each sample, it is clear
that the larger white spots shown on the substrate and coating are compounds of Ti.
Materials
Materials2022,
2022,15,
15,x6758
FOR PEER REVIEW 7 7ofof13
12

Figure 5. The elements’ content variation along the coating depth direction. (a–i) represent speci-
Figure 5. The elements’ content variation along the coating depth direction. (a–i) represent specimens
mens #1–9, respectively.
#1–9, respectively.
Figure 4a
3.3. Physical shows
Phase the coating formed by the thin slurry, with zone I only sporadically
Analysis
distributed at the edges. As the thickness of the slurry increases, zone I takes up an in-
Slurry aluminizing coatings are usually divided into high-temperature (850–1100 ◦ C)
creasing proportion of the coating system and gradually overtakes zone II. It is probably
low-activity and low-temperature (700–850 ◦ C) high-activity coatings [15]. The former is
due to the incomplete diffusion of Ni in the slurry with increasing slurry thickness that
dominated by the AlNi phase [29], while the latter is dominated by the Al3 Ni, Al3 Ni2 , and
leads to a slight increase of Al content in the coating. At the same time, Cr solubility in the
AlNi phase from the surface to the interior [30]. Figure 6 shows the XRD patterns for the
AlNi phase decreases with increasing Al content [27], forming more white dot precipi-
surfaces of nine slurry aluminized specimens. The main peak of each specimen is the AlNi
tates. As shown
compound, in Figure
which is due 4,
to the
the thickness of the IDZ
high-temperature layer does coating
low-activity not varygenerated
with the slurry
by the
thickness and always
heat treatment of allremains
specimens around 15 μm. This isgreater
at temperatures because the 950
than thickness of the IDZ
◦ C. However, layeris
there
isa mainly affected by the temperature and time of high-temperature diffusion
slight change in the molecular formula of the AlNi compound as the slurry thickness [28]. The
same heat treatment method was used for all specimens in this work and
increases. From specimen #1 to specimen #9, the molecular formula changes as follows: therefore did
not affect the IDZ layer.
Al Ni (#1) → Al Ni (#2–#6) → Al Ni (#7) → AlNi(#8, #9). The Ni-rich AlNi
0.42 0.58 0.9 1.1 0.96 1.04
phase dominates the coating matrix when the slurry thickness is thin. With the increase of
3.3.
the Physical Phase Analysis
slurry thickness, the Al element content of the outermost layer of the coating gradually
Slurry aluminizing
increased, the Ni element coatings
content aregradually
usually divided
decreasedinto(Figure
high-temperature
7), and the (850–1100
AlNi phase °C)
of
low-activity
the matrix was andno low-temperature
longer Ni-rich, (700–850
and a 1:1 °C) high-activity
molecular formulacoatings [15]. TheInformer
was obtained. Figureis7,
dominated
the atomic by the AlNi phase
percentages of Al [29], while the
are higher thanlatter
thoseis dominated
of Ni exceptbyforthespecimen
Al3Ni, Al#1,
3Niwhich
2, and

AlNi
may phase
be duefromto thethe surface toofthe
formation interior [30].
compounds Figure
of Al with6other
shows the XRDFor
elements. patterns for the
example, the
Al2 O3 phase
surfaces of ninemarked
slurryinaluminized
Figure 6 is specimens.
generated by Thethemain
oxidation
peak ofofeach
Al inspecimen
the AlNi isphase. This
the AlNi
oxidation reaction
compound, which produces
is due to the the Al 2 O3 film, which is
high-temperature the essence coating
low-activity of the oxidation
generated resistance
by the
of the
heat aluminized
treatment coating.
of all specimensIn addition, the Al84.6greater
at temperatures Cr15.4 phase was°C.
than 950 marked in specimen
However, there is#6,a
whichchange
slight is consistent with the statement
in the molecular formula of that
theAlCr
AlNicompounds
compound as were
the formed in zone I,in-
slurry thickness as
mentioned
creases. Fromin the previous
specimen #1section. For the#9,
to specimen TiCthe
andmolecular
Ti8 C5 phases, it corresponds
formula changes as to follows:
the large
white
Al 0.42Nispots in→Figure
0.58(#1) Al0.9Ni4.1.1(#2–#6) → Al0.96Ni1.04(#7) → AlNi(#8, #9). The Ni-rich AlNi phase
dominates the coating matrix when the slurry thickness is thin. With the increase of the
slurry thickness, the Al element content of the outermost layer of the coating gradually
increased, the Ni element content gradually decreased (Figure 7), and the AlNi phase of
the matrix was no longer Ni-rich, and a 1:1 molecular formula was obtained. In Figure 7,
 Al2O3 phase marked in Figure 6 is generated by the oxidation of Al in the AlNi phase. This
oxidation reaction produces the Al2O3 film, which is the essence of the oxidation resistance
of the aluminized coating. In addition, the Al84.6Cr15.4 phase was marked in specimen #6
which is consistent with the statement that AlCr compounds were formed in zone I, as
Materials 2022, 15, 6758 8 of 12
mentioned in the previous section. For the TiC and Ti8C5 phases, it corresponds to the
large white spots in Figure 4.

Figure6.6. XRD
Figure XRDpatterns
patternsfor
foraluminized specimens.
aluminized (a) (a)
specimens. #1–3#1–3
specimens, (b) #4–6
specimens, specimens,
(b) #4–6 and and (c
specimens,
(c)
#7–9#7–9 specimens.
specimens.
Materials 2022, 15, 6758 9 of 12
Materials 2022, 15, x FOR PEER REVIEW 9 of 13

100

Al
80
Ni

Content (at.%)
60

40

20

0
1 2 3 4 5 6 7 8 9
Specimen number
Figure The
7. The
Figure 7. variation
variation pattern
pattern of Al of
andAlNiand Ni elements
elements in the aluminized
in the aluminized specimens’
specimens’ outermost outermost
layer
(zone(zone
layer I). I).

3.4.
3.4. Surface Roughness
Surface Roughness
Figure 88shows
Figure showsthe thesurface
surfacemorphology
morphology [31] [31]
and roughness valuesvalues
and roughness of the aluminized
of the aluminized
specimens. In
specimens. InFigure
Figure8,8,
PVPVindicates the the
indicates difference between
difference peak and
between peak valley
and values,
valley and
values, and
RMS and
RMS and Ra
Ra are
are roughness
roughness parameters.
parameters.InInaddition,
addition,there
thereare
aresurface
surfacestats parameters
stats parameters such
such
as as skewness
skewness (Ssk),(Ssk), kurtosis
kurtosis (Sku),(Sku), maximum
maximum valley
valley depth
depth (Sv),
(Sv), andandthethe maximumheight of
maximum
height of the surface (Sq) in Table 3. We assume that the roughness of the DZ22B speci-
the surface (Sq) in Table 3. We assume that the roughness of the DZ22B specimens before
mens before aluminizing is the same due to using the same sanding method (P800sand-
aluminizing is the same due to using the same sanding method (P800sandpaper). However,
paper). However, in Figure 8, the coating surface morphology and roughness changed
in Figure 8, the
considerably withcoating surface
the change morphology
in slurry thickness. and roughness
As the changed
slurry’s thickness considerably
increases, the with
the change in slurry thickness. As the slurry’s thickness increases,
coating surface’s roughness first decreases and then increases. From the three-dimen- the coating surface’s
roughness first decreases
sional morphology,
Materials 2022, 15, x FOR PEER REVIEW
and thenofincreases.
the unevenness specimensFrom#1–7 the three-dimensional
is caused morphology,
by tiny needle-like
10 of 13
the unevenness of specimens #1–7 is caused by tiny needle-like bumps,
bumps, while the coating surfaces of specimens #8 and #9 are islands or patches of bumps while the coating
surfaces
or pits. of specimens #8 and #9 are islands or patches of bumps or pits.

Table 3. Coating surface stats parameters.

Surface Stats #1 #2 #3 #4 #5 #6 #7 #8 #9
Ssk 0.182 −0.202 −0.0418 −0.00552 0.144 0.154 0.104 −0.0864 −0.390
Sku 3.08 3.35 4.15 4.23 3.59 3.66 4.06 4.40 3.12
Sv (μm) 26.1 29.6 54.6 36.8 27.0 23.2 31.0 55.8 74.3
Sq (μm) 39.5 25.4 53.3 43.2 36.4 36.4 37.7 83.2 70.8

Figure
Figure 8. Surface
8. Surface macromorphology and
macromorphology and roughness
roughnessofof
aluminized specimens.
aluminized (a–i) (a–i)
specimens. are specimens
are specimens
#1–9 in order.
#1–9 in order.
The relatively rough macroscopic surface of specimen #1’s aluminized coating corre-
sponds to the undulating coating in Figure 4a. We have two guesses as to the cause of this
rough surface. One possibility is related to the particle size of the Al powder. Although
the diffusion heat treatment temperature has exceeded the melting point of Al, the Al
powder particles may still slightly retain their paste shape. This shape causes undulations
at the interface between the coating and the substrate, thus affecting the surface rough-
Materials 2022, 15, 6758 10 of 12

Table 3. Coating surface stats parameters.

Surface Stats #1 #2 #3 #4 #5 #6 #7 #8 #9
Ssk 0.182 −0.202 −0.0418 −0.00552 0.144 0.154 0.104 −0.0864 −0.390
Sku 3.08 3.35 4.15 4.23 3.59 3.66 4.06 4.40 3.12
Sv (µm) 26.1 29.6 54.6 36.8 27.0 23.2 31.0 55.8 74.3
Sq (µm) 39.5 25.4 53.3 43.2 36.4 36.4 37.7 83.2 70.8

The relatively rough macroscopic surface of specimen #1’s aluminized coating corre-
sponds to the undulating coating in Figure 4a. We have two guesses as to the cause of this
rough surface. One possibility is related to the particle size of the Al powder. Although
the diffusion heat treatment temperature has exceeded the melting point of Al, the Al
powder particles may still slightly retain their paste shape. This shape causes undulations
at the interface between the coating and the substrate, thus affecting the surface rough-
ness. Another possibility is the overproliferation of Ni. Due to the thin thickness of the
slurry, after the complete diffusion of Al and Ni, the Ni in some positions continues to
diffuse outward, forming a Ni-rich NiAl phase and an uneven surface. The medium slurry
thickness formed a relatively smooth surface (Ra < 4.5 µm), which is consistent with the
findings of the literature [32] that found that the low-aluminum activity coating formed a
coarse crystalline smooth surface. For the thicker slurry (samples #8 and #9), corresponding
to Figure 4e,f, it can be seen that the interface between the coating and the substrate is
relatively flat. The oxidation of particles at the top of the slurry, the lower temperature at the
top of the coating due to argon flow, and the incomplete diffusion of nickel all contribute to
the coating’s loose and porous outer layer [25].

4. Conclusions
To investigate the effect of slurry thickness on the coating, we analyzed the coating
thickness, microstructure, element distribution, physical phase, and surface roughness
Materials 2022, 15, x FOR PEER REVIEW
formed by different slurry thicknesses. Figure 9 shows a schematic11diagram
of 13
of three
different thicknesses of slurry aluminized in thin, medium, and thick.

Figure 9. Schematic diagram of slurry aluminization for (a) thin, (b) medium, and (c) thick slurry
Figure 9. Schematic diagram of slurry aluminization for (a) thin, (b) medium, and (c) thick
thickness.
slurry thickness.
Combining Figure 9 and the experimental results, we obtain the following conclu-
sions.
1. The coating thickness increases with increasing slurry thickness. The relationship be-
tween coating and slurry thickness is approximately linear in the medium thickness
interval, but not when it is too thick or too thin, which may be related to the diffusion
Materials 2022, 15, 6758 11 of 12

Combining Figure 9 and the experimental results, we obtain the following conclusions.
1. The coating thickness increases with increasing slurry thickness. The relationship
between coating and slurry thickness is approximately linear in the medium thick-
ness interval, but not when it is too thick or too thin, which may be related to the
diffusion dynamics.
2. The aluminized coating can be divided into an outer layer containing Cr precipitates
(Zone I), an inner layer of AlNi phase (Zone II), and an IDZ layer (Zone III). When the
slurry is thin, zone I can hardly be observed, and with the increase of slurry thickness,
the thickness of zone I gradually increases and exceeds that of zone II. The thickness
of zone III does not change with the slurry thickness. When the slurry is relatively
thick, a porous aluminized layer will be formed on the outer surface, which will affect
the surface roughness of the coating.
3. As the thickness of the slurry increases, the Al content in the coating gradually
increases, and the matrix of the aluminized coating gradually becomes an AlNi phase
of molecular formula 1:1 from the Ni-rich AlNi phase.
4. The coating surface formed by medium-thickness slurry is smoother than that of
thinner or thicker slurry.
Summing up the above conclusions, we found that aluminizing treatment using a
medium-thick slurry can obtain coatings with high Al reserves (good oxidation resistance),
stable AlNi phases, and smooth surfaces. As for the other performance parameters of
the coating, such as fatigue, creep, and experimental verification of oxidation properties,
further studies are needed.

Author Contributions: Conceptualization, Z.L. and C.W.; methodology, C.W., Z.L. and X.D.; software,
Z.L. and X.L.; validation, Q.L., J.Y. and Y.Q.; formal analysis, C.W.; investigation, X.D.; resources,
C.W.; data curation, X.L.; writing—original draft preparation, Z.L.; writing—review and editing,
C.W.; visualization, Z.L.; supervision, C.W.; project administration, Q.L.; funding acquisition, C.W.
All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China, grant number
92060202, and the Innovation Fund of Air Force Engineering University, grant number CXJ2021115.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: We are grateful to Xiangyang Hangtai Power Machine Factory for providing the
aluminizing slurry support.
Conflicts of Interest: The authors declare no conflict of interest.

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