Emergent Materials (2024) 7:2007–2016

https://doi.org/10.1007/s42247-024-00677-2

ORIGINAL ARTICLE

High temperature infiltration behavior and reaction characteristics

of Colima volcanic ashes on gadolinium zirconate coatings deposited
by atmospheric plasma spraying
Ivan F. Bedoya‑Trujillo1,2 · Aixa I. Gutiérrez‑Pérez2 · Sebastián Pérez2 · Natalia Brizuela‑Colmenares2 ·
Juan Zárate‑Medina1 · Juan Muñoz‑Saldaña2

Received: 30 November 2023 / Accepted: 11 March 2024 / Published online: 23 May 2024
© The Author(s) 2024

Abstract
Volcanic ashes are considered a serious threat to the aircraft industry. At high temperatures, they inflict severe thermo-
chemical damage to the typical 7 wt.% yttria-stabilized zirconia thermal barrier coatings that protect the aircraft turbine.
There is a need to evaluate alternative materials with excellent resistance to infiltration of molten siliceous particles, such
as gadolinium zirconate. In this work, free-standing thermal barrier coatings of gadolinium zirconate were manufactured by
atmospheric plasma spraying, varying deposit parameters to obtain different relative densities to evaluate the infiltration of
molten Colima volcanic ashes for 1 h and 10 h at 1250 °C. The infiltration depth and the reaction products resulting from
each interaction, were studied by different characterization techniques. In general, the coatings show high resistance to the
infiltration of the volcanic ashes, reaching infiltration depths between 50 µm and 80 µm after 10 h of infiltration time. In this
sense, gadolinium zirconate coatings are excellent candidates against the infiltration of Colima volcanic ashes compared to
the typical yttria-stabilized zirconia-based thermal barrier coatings.

Keywords Barrier coatings · Thermal spraying · Rare-earth zirconates · Infiltration resistance · Siliceous debris · Raman
spectroscopy · Apatite

1 Introduction turbine engines [1, 2]. Typically, TBCs are manufactured

using either atmospheric plasma spray (APS) or electron-
Thermal barrier coatings (TBCs) are used to protect aircraft beam physical vapor deposition (EB-PVD) techniques. Each
turbine engines, allowing them to operate at higher tempera- processing technique produces different types and levels of
tures and thus improve their efficiency. TBCs are advanced porosity. EB-PVD coatings have inter-columnar gaps that
materials composed of ceramic oxides with refractory prop- can facilitate infiltration of molten particles. On the other
erties, applied as protective coatings to the hottest part of hand, APS coatings do not display interconnected porosity,
which significantly affects the infiltration kinetics [3].
Yttria-stabilized zirconia (YSZ) has been reported as the
* Juan Zárate‑Medina most widely used ceramic for TBCs in the aircraft industry
jzarate@umich.mx
due to its outstanding features as a thermal barrier material
* Juan Muñoz‑Saldaña [4]. TBCs protect the metallic components of the turbine
jmunoz@cinvestav.mx
against physical degradation from foreign particles such as
1
Instituto de Investigación en Metalurgia y Materiales, volcanic ashes (VAs) and serve as thermal and chemical
Universidad Michoacana de San Nicolás de Hidalgo, C. de insulators [5]. However, operating temperatures are increas-
Santiago Tapia 403, Centro, 58000 Morelia, Michoacán, ing and will reach the point where YSZ is no longer viable
México [6, 7]. Also associated with increasing temperatures, VAs
2
Centro de Investigacion y de Estudios Avanzados del have been reported to infiltrate into the porous YSZ coatings,
Instituto Politecnico Nacional, Laboratorio Nacional de eventually causing the failure of TBCs [8]. This increase
Proyección Térmica, CENAPROT, Libramiento Norponiente
2000, Fracc. Real de Juriquilla, 76230 Queretaro, Qro., in turbine engine temperatures to improve its efficiency
México demands for alternative materials.

Vol.:(0123456789)
2008 Emergent Materials (2024) 7:2007–2016

Materials based on rare-earth zirconates (REZ) with volcanoes exhibiting pyroclastic activity in one of the most
­A 2Zr 2O 7 stoichiometry, where A represents rare-earth densely populated regions of the country, namely Pop-
elements, offer a number of exceptional attributes. These ocatepetl [12] and Colima [13]. In particular, the most recent
include a distinctive lattice structure, exceptional chemical pyroclastic activity has been observed in the Popocatepetl
stability, superior ionic conductivity, elevated coefficients volcano [14]. The continued activity of these volcanic for-
of thermal expansion, low thermal conductivity, high pho- mations poses a consistent threat to the air traffic within the
tocatalytic activity, and superior melting points [9]. These region, an issue of particular significance given Mexico’s
characteristics give them wide applications potential in pivotal role as a transportation corridor connecting North
high-temperature TBCs for ceramic materials. Among and South America. While previous studies have explored
these types of materials, gadolinium zirconate (GZO) the infiltrative impact of VAs in YSZ TBCs deposited via
emerges as an alternative material due to its outstanding APS [5], the influence of Colima VAs on GZO ceramics has
features as a thermal barrier material, such as high melt- only been investigated in the context of ceramic coupons
ing point, high temperature phase stability, low thermal [14].
conductivity, high sintering resistance and, especially, high This study aims to assess the rate at which VAs from
resistance to infiltration of molten Si-based particles. GZO Colima volcano infiltrate into GZO ceramic coatings depos-
presents a pyrochlore structure ­(Gd2Zr2O7), which exhibits ited by atmospheric plasma spraying. Additionally, the for-
a high degree of disorder structure and has been reported mation of re-precipitated apatite-type compounds that hin-
to contain several oxygen vacancies that act as phonon dis- der infiltration at the reaction front is examined. The study
persion points, generating desirable properties for thermal evaluates the formation of stable phases with a composition
isolation material. Additionally, several studies have shown close to the nominal value as a function of the infiltration
that REZ materials exhibit high resistance to infiltration of time and the microstructural characteristics of the coatings,
calcium-magnesium–aluminum-silicates (CMAS) and other including relative density. Furthermore, this work analyzes
siliceous melts such as VAs. Mikulla et al. [10] prepared the microstructure and precipitated phases in the reaction
four GZO microstructures by EB-PVD, manipulating both front. In addition, a comprehensive analysis was carried out
the substrate temperature and the rotational speed. Among using DoE methodology to analyze the components influ-
these microstructures, one exhibited a refined architecture encing the infiltration process and their interrelation. Con-
characterized by diminished intercolumnar gaps and elon- ditions that minimize the deterioration of the GZO coating
gated plume arms, which resulted in a significant reduction while exposed to the high temperatures of the VAs melt were
of CMAS infiltration within a remarkable range of 56% to identified.
72%. The presence of a garnet phase ((Gd,Zr,Ca)3(Mg,Al,
Fe,Ti,Zr)2(Si,Al,Fe)O12), which manifested as a continuous
layer interfacing with apatite ((Gd,Ca)4(Gd,Zr)6(SiO4)6O2) 2 Experimental procedure
and fluorite (Gd,Zr,Ca)O1.x was recognized as a valuable
reaction product that improves CMAS resistance, thus offer- This section describes the processing conditions used for
ing a promising avenue for enhanced material performance. the deposition of the coatings. It includes information on
Furthermore, Chen et al. [11] studied the impact of non- the materials, equipment, and parameters used. In addition,
stoichiometric ­Gd2-xZr2+xO7+0.5× on the mechanical char- the infiltration of the coatings with VAs, the materials and
acteristics and thermal conductivity of GZO. The study the parameters examined in the tests performed are detailed.
employed first-principles calculations and validated the The characterization techniques and equipment used to
findings through solid-state reaction methods. The research evaluate the physicochemical properties of the infiltrated
highlights the directional dependency of the material’s coatings, microstructure, structure, and elemental analysis,
elasticity, which intensifies as the levels of ­Gd3+ and ­Zr4+ including the methods used for sample preparation are also
increase due to lattice distortion from the excessive pres- described. Additionally, a description of the factorial DoE
ence of these elements. A moderate excess of Z ­ r4+ increases analysis parameters used to assess the infiltration test results
the hardness of GZO, while an excessive amount of both is provided.
­Zr4+ and ­Gd3+ decreases it. The disordered occupation of
lattice atoms amplifies the nonlinearity of lattice waves 2.1 Manufacture of free‑standing thermal barrier
and increases phonon scattering with increasing concentra- coatings
­ d3+ and Z
tions of G ­ r4+, resulting in decrease in the thermal
conductivity. For the fabrication of the thermal barrier coatings (TBCs),
These contributions focused on the search of materi- commercial GZO powders (Höganäs, Germany) were used
als to reduce the degradation of TBCs in aircraft engines as feedstock material and deposited on alumina ­(Al2O3)
by CMAS and VAs. Currently, Mexico hosts two active substrates, manufactured by powder pressing and sintering
Emergent Materials (2024) 7:2007–2016 2009

to obtain 2.5 cm diameter round coupons. An APS system across the TBC microstructure and the Ca:(Gd + Zr) ratio,
(9 MB, Oerlikon Metco) was used to manufacture the free- which is associated with the stoichiometry of apatite com-
standing TBC coatings. The powders were sprayed on A ­ l2O3 pound formation at the reaction front. The analysis of vari-
substrates under the following conditions: current of 520 A, ance (ANOVA) was carried out at 95% confidence level
voltage of 75 V, spraying distance of 75 mm, two traverse (α = 0.05), and the responses exhibited a correlation coef-
speeds of 0.75 m/s and 1 m/s, powder feeding rate of 30 g/ ficient ­(R2adj) of > 70%. The analysis included main effect
min, primary hydrogen carrier gas flow of 80 SCFH and plots to examine the influence of the factors at the selected
secondary argon carrier gas flow of 15 SCFH. levels. Contour plots were used to identify trends in the
responses individually, and finally, a simultaneous optimi-
2.2 Infiltration experiments zation approach of the two responses was analyzed using an
overlaid contour plot.
For the infiltration experiments, the geosciences department
of the national autonomous university of Mexico (UNAM)
provided volcanic ashes (VAs) from the Colima volcano. In
3 Results
this process, 20 mg of Colima VAs were applied per square
centimeter of the ceramic surface. Subsequently, the samples
In this section, the results of the sequential characteriza-
were subjected to heat treatment at 1250 °C for 1 h and 10 h,
tion of the investigated materials are presented. Initially, the
with heating and cooling rates set at 10 °C/min. This tem-
description of the microstructural and structural properties
perature was chosen based on previous TGA–DSC analyses
of the feedstock powders and coatings is presented. The next
of these VAs [5], ensuring that the molten VAs infiltrate
subsection provides a detailed description of the microstruc-
through the microstructures of the TBCs.
tural characteristics and a semi-quantitative elemental analy-
sis of the reaction front of the coatings after the infiltration
2.3 Materials characterization
tests. A thorough examination of the phases identified in the
infiltrated samples is included. Finally, an analysis of the
Particle size characterization of the commercial GZO pow-
influence of the TBCs infiltration test characteristics on Ap
der was carried out using a HELOS/BR-OM laser diffrac-
formation and infiltration depth is presented using statisti-
tometer (Sympatec, Germany) under standard dry condi-
cal analysis.
tion. Micrographs of the cross-sections of the free-standing
as-sprayed coatings were recorded with scanning electron
microscope (SEM, JSM-7610F) coupled with secondary 3.1 Feedstock powder and thermal barrier coatings’
electron (SE) and back-scattering electron (BSE) detectors. characterization
Relative densities and TBCs’ thicknesses of the as-sprayed
TBCs were determined using imaging software (ImageJ). Figure 1 shows the microstructural and structural character-
Common metallographic techniques were used to prepare istics of GZO commercial powders. The SEM micrographs
the cross-sections of the infiltrated TBCs, which were then in Fig. 1a and b, show the microstructure of the particles,
used to study the TBC system’s infiltration depths, reac- typical features of agglomerated and sintered feedstock
tion layers, and microstructures using SEM. The chemical powders can be observed. The morphology of most of the
compositions of the reaction products were measured by particles tends to be spherical, which is ideal for improv-
energy dispersive X-ray spectroscopy (EDS) coupled to the ing flowability during the spray process and promoting a
SEM. Micro-Raman spectroscopy measurements (Alpha homogeneous deposition rate. Particles with apple-like mor-
300RA, WiTec, Germany) were performed with a 355 nm phology can also be observed and some fractured agglom-
laser excitation source, a constant laser power of 4.7 mW, erates exhibit a hollow microstructure. The particle size
an integration time of 60 s, and 2 accumulations to identify distribution plot of Fig. 1c is characterized by percentiles
the reaction products and extent of infiltrated samples. The d10 = 45.2 µm, d50 = 99.1 µm and d90 = 135.8 µm, which is
identification of the crystalline phases was performed using in good agreement with the size of the particles observed
X-ray diffraction (XRD) employing a diffractometer Rigaku in the micrographs and represents a suitable distribution
SmartLab with a copper anode (Cu Kα1 = 1.54 Å) operating for the coating fabrication using the APS process [15]. The
at 40 kV and 44 mA, the scanning range in 2θ and scanning XRD pattern for GZO powders is shown in Fig. 1d. The dif-
speed were from 20º to 70º and 10 º/min, respectively. fraction peaks at 2θ = 29.4° (222), 34.0° (400), 48.9° (440),
Statistical analysis of the experiments was conducted 58.0° (622), and 61.0° (444) confirm the presence of the
using Minitab® software to evaluate the influence of pyrochlore phase G ­ d2Zr2O7 (ICSD # 165813). The peak
key input factors in GZO TBCs, such as relative density at 2θ = 37°, diffraction plane (331), is characteristic of the
and infiltration time, on the depth of the melt infiltration pyrochlore superstructure and indicates its ordering degree
2010 Emergent Materials (2024) 7:2007–2016

a) b)

500 µm 100 µm

c) 3.5
x 10=45.26 µm x 50= 99.10 µm x 90= 135.77 µm
d)
100 GZO

(222)
3.0

Cumulative distribution (%)

80
D ensi ty di stri buti on ( l og)

2.5

I ntensi ty ( a. u. )
2.0 60

1.5

(440)
40

(400)

(622)
1.0
20

(444)
0.5

(331)
0.0 0

0 50 100 150 200 20 30 40 50 60 70

Fig. 1  SEM micrographs showing the surface morphology of agglomerated and sintered particles at two magnifications (a, b), particle size dis-
tribution plot (c) and XRD pattern of the commercial GZO powders (d)

[14, 16]. No additional phases were identified in the diffrac- traverse speed of 0.75 m/s and 1 m/s, respectively. Both coat-
tion patterns of the powders. ings exhibit the characteristic layered microstructure usually
The SEM images in Fig. 2a and b show the cross-sec- observed in thermal spray methods, as shown in Fig. 2c and
tional microstructure of the GZO TBCs deposited at a d. This microstructure is formed by the buildup of splats,

Fig. 2  Cross sectional SEM

micrographs recorded at dif- a) b)
ferent magnifications, of the
free-standing GZO coatings
deposited by APS at 0.75 (a, c)
and 1 m/s (b, d) 228.61 µm 168.52 µm

200 µm 200 µm

c) d)

Φ = 91.71 ± 3.2% Φ = 89.83 ± 2.1%

10 µm 10 µm
Emergent Materials (2024) 7:2007–2016 2011

which are produced when particles in a molten state impact These phases, Ap and ­ZrO2, reprecipitate forming a compact
the substrate. In addition, the presence of lamellar and cir- layer that stops infiltration. The reaction layer seals the infil-
cular porosity, and some cracking can be observed in the tration channels of the TBC at different infiltration depths,
microstructure, which is typically observed in TBCs depos- depending on the infiltration time and relative density. As
ited by APS. Porosity plays a key role as a stress concen- infiltration time increases from 60 to 600 min, the infiltration
trator, promoting cracks formation and subsequent fracture depth increases and a thicker reaction layer forms above the
[17, 18]. However, in TBCs it can be beneficial in reducing reaction front. A SEM image at high magnifications of the
thermal conductivity. At high operating temperatures, diffu- reaction layer of the infiltrated TBC with a relative density
sion sintering mechanisms are activated, generating a denser of 89.83% and 60 min, Fig. 3e, shows a closer representation
ceramic that increases mechanical strength, while reducing of the microstructure of the reaction products, revealing the
its thermal insulation capacity [18]. The traverse speed of presence of globular zirconia and needle-like apatite phases.
0.75 m/s and 1 m/s produced coatings with average thickness Figure 4a shows a SEM image of the cross-section of
of 228.61 ± 8.63 µm and 168.52 ± 10.05 µm, respectively. an infiltrated TBC (Fig. 3b, 60 min with 89.93% relative
Higher traverse speed leads to a reduced number of particles density). The volume of the dissolved TBC can be observed.
reaching the substrate, hence yielding a thinner coating. Figure 4b shows a magnified SEM image of the infiltrated
sample, which presents an infiltration depth of 48.48 µm,
3.2 Microstructure of the infiltrated thermal barrier determined by image analysis (ImageJ). EDS mappings,
coatings’ cross sections Fig. 4c, reveal the distribution of the main elements involved
throughout the reaction layer. Si is mainly distributed in the
Figure 3 shows the cross-sectional SEM micrographs of the molten glass of the Colima VA; Zr and Gd elements are
reaction layers of the infiltrated GZO coatings, with rela- mainly observed in the TBC. However, the latter two ele-
tive densities of 91.71% and 89.93%, during 60 min (Fig. 3a ments are also observed in the reprecipitated Z ­ rO2 and Ap
and b) and 600 min (Fig. 3c and d). The infiltrated regions phases [19, 20]. To confirm the presence of these phases,
present different morphologies of the reaction products as a Tables 1 and 2 show the normalized chemical composi-
function of infiltration time and relative density of the TBC. tion of Ap and Z ­ rO2 phases, respectively, measured by EDS.
The infiltrated TBC’s microstructure shows the glass and The Ap phase, C ­ a2(Gd,Zr)8((Si,Al)O4)6O2 can incorporate
the GZO zones. The reaction layers between the GZO and cations of Z­ r4+ and G
­ d3+ in A
­ l3+ and S
­ i4+ sites, respectively
glass zones show the morphology of embedded globular and [20]. For longer infiltration times, from 60 to 600 min, it is
needle-like phases. The observed phase morphologies match observed that TBCs with 91.71% relative density, the con-
those reported for ­ZrO2 and Ap, respectively [5, 14, 19]. tents of Si, Ca and Zr tend to decrease, and meanwhile Gd

Relative density
91.71% 89.93%
a) b)
Melt Melt
ZrO 2
ZrO 2 e)
Ap
60 min

Ap
I nf i l trati on ti me

GZO GZO
10 µm 10 µm

c) d)
Melt Melt
Ap Ap
ZrO 2
ZrO 2
600 min

1 µm

GZO 10 µm GZO 10 µm

Fig. 3  Cross-sectional SEM images of the infiltrated free-standing b, c and d). Enlarged image of (b) showing the microstructure of the
GZO coatings with 91.7% and 89.9% of relative density after 60 min reaction products (e)
and 600 min of infiltration at 1250 °C, showing the reaction front (a,
2012 Emergent Materials (2024) 7:2007–2016

Fig. 4  Cross sectional SEM a) Resin b)

micrographs of an infiltrated
GZO coating sample during
60 min with 89.93% relative
density (a), a magnification of 48.48 µm
the micrograph in the reaction Melt
front zone and the correspond-
ing EDS chemical composi-
tional maps of Si, Zr and Gd (b)

GZO

20 µm

Resin Si Zr Gd

100 µm
30 µm Si 30 µm Zr

Table 1  Elemental compositions of Aps measured by point EDS The graph in Fig. 5, shows the average infiltration depths
of TBCs as a function of time. Two stages of can be seen;
Inf. Time (min) / Si Ca Gd Al Zr
Rel. Density (%)
stage I, which corresponds to time less than 60 min, shows
at. %
fast infiltration rates, 0.30 µm/min and 0.80 µm/min for
60/91.71 61.24 8.12 5.71 22.07 2.83 TBCs with relative densities of 91.71% and 89.83%, respec-
60/89.83 61.07 6.20 8.23 19.06 5.41 tively. For times longer than 60 min, stage II, the infiltra-
600/91.71 56.74 4.31 12.88 25.78 0.27 tion rates decrease to 0.10 µm/min and 0.05 µm/min. At
600/89.83 49.92 6.79 30.53 12.74 - 600 min, TBCs with relative densities of 91.71% and 89.83%
reach infiltration depths around 71 µm and 78 µm, respec-
tively. These differences in the infiltration rates are due to
Table 2  Elemental the kinetic formation of the reaction products. In stage I,
Inf. Time (min) / Gd Zr
compositions of zirconias Rel. Density (%) at.% the melt penetrates along the TBC porosities dissolving the
measured by point EDS TBC components into ­Gd3+ and ­Zr4+, subsequently the melt
60/91.71 11.08 88.91 becomes saturated with these cations and reaction products
60/89.83 10.07 89.92 like Ap and c-ZrO2 begin to reprecipitate and gradually grow
600/91.71 9.27 90.72 to seal the infiltration channels. In stage II, the melt contin-
600/89.83 9.33 90.66 ues to penetrate in the TBCs, but, the infiltration rates, 0.1
µm/min and 0.05 µm/min, decrease considerably due to the
formation of more Ap and c-ZrO2 above the reaction front
amount tends to increase. However, the amount of Si shows which contributes to the sealing of the infiltration channels.
the sharpest decrease, going from 61.24% to 54.74%. On the These phenomena will be discussed in detail later.
other hand, the relative density of the TBC increased from
89.83% to 91.71%. In the TBCs infiltrated during 600 min, 3.3 Phase identification of the thermal barrier
the Si, Ca and Zr contents tend to increase, while ­Gd3+ con- coatings’ reaction layers
tain tends to decrease.
Table 2 exhibits the normalized chemical compositions Figure 6a shows Raman spectra as a function of infiltra-
of the globular phases observed in the reaction layers of the tion depth performed on the reaction layer of an infiltrated
TBC, where it is confirmed that these compositions match GZO TBC, with a relative density of 91.71% for 600 min.
with those reported for cubic zirconia (c-ZrO2) [5, 19, 21]. The Raman spectra shows bands of Ap, c-ZrO2, t-ZrO2, and
It has been reported that the c-ZrO2 phase incorporates up GZO, confirming the presence of these phases along the
to 16% of ­Gd3+ in solid solution [19]. Furthermore, it is reaction layer. At low infiltration depths (15 µm), bands of
observed that as infiltration time increases, the ­Gd3+ con- c-ZrO2, at 247 ­cm−1, 294 ­cm−1, 436 ­cm−1 and 709 ­cm−1;
tained in c-ZrO2 slightly decreases around 3%. t-ZrO2, at 275 ­cm−1, 326 ­cm−1, 408 ­cm−1, 456 ­cm−1; GZO
Emergent Materials (2024) 7:2007–2016 2013

Fig. 5  Plot of the infiltration

depth kinetics of the GZO
coatings with 91.7 and 89.8%
relative density infiltrated
with Colima volcano ashes at
1250 °C

Fig. 6  Raman spectra as a GZO, 91.71%, 600 min

function of infiltration depth of
a) b)
2
t-Z 2

Ap 2

c- O2
ApO2

O
O

O
Zr 2

c- O2

Colima VA with GZO coatings

rO

Zr

Ap
Zr

r
r

t-Z
t-Z

t-Z
c-

0
with 91.7% relative density Exp
Ap
infiltrated after 600 min (a) and 10 GZO calc
band deconvolutions at 30 µm
20

Infiltration depth (mm)

of infiltration depth (b). The t-ZrO 2
R aman i ntensi ty

main vibrational modes of t- 30

ZrO2, c-ZrO2, Ap and GZO are
c-ZrO 2
identified 40

50

60

70

80
200 400 600 800 1000 200 300 400 500 600 700 800 900
-1
Wavenumber (cm ) Wavenumber (cm-1)

at 306 ­cm−1, 335 ­cm−1, 410 ­cm−1, 544 ­cm−1 and 610 ­cm−1 process of the REZ. To understand the interaction of the
are observed [22–24]. However, a slight band of Ap is also reaction products at the infiltration depth, various methodol-
present at 875 ­cm−1, which corresponds to the stretching ogies were used to study the properties of the reaction layer.
vibrational mode of the Si–O tetrahedra in the Ap struc- The performance of GZO TBCs to prevent failure dur-
ture [25]. As infiltration depth increases, from 15 µm to ing infiltration of Colima VAs was evaluated using DoE
50 µm, the Ap band stands out progressively indicating a analysis, considering the relative density (%) of the coating
major amount of this phase. At infiltration depths higher and the infiltration time (min) at 1250 °C as input factors.
than 50 µm, the zirconias and Aps phase bands disappear, The effect of the studied factors on the responses infiltration
with the GZO bands remaining, indicating the maximum depth (µm), and the Ca:(Gd + Zr) ratio related to the forma-
infiltration depth reached. The band deconvolution of the tion of stable apatite compounds during the infiltration tests
Raman spectrum measured at 30 µm of infiltration depth is is discussed. In the main effect plots presented in Fig. 7a
shown in Fig. 6b and exhibits the main vibrational modes of and b, it can be observed that the input factor with the most
t-ZrO2, c-ZrO2, GZO and Ap [14, 22, 24]. significant effect of the two studied responses was the infil-
tration time. Relative density, on the other hand, has the least
3.4 Analysis of the factorial ­22 design of experiment pronounced effect on the infiltration depth, and it can be seen
that the effect of the factors on the responses is the opposite.
This section examines the reaction products observed in Figure 7d and e show, respectively the contour plots of the
the infiltrated ceramics. The distribution and morphologies infiltration depth (µm) and Ca:(Gd + Zr) ratio responses, for
of the precipitated phases were altered by the infiltration the experimental region defined by the infiltration time (min)
2014 Emergent Materials (2024) 7:2007–2016

a) b) c)

d) e) f)

Fig. 7  Main effect plots (a, b) and contour plots (d, e) of the analyzed showing the experimental region, feasible zone, and optimized condi-
responses: Ca:(Gd + Zr) and Infiltration depth as a function of the tion for the input factors, determined with the response optimizer (c)
factors: Infiltration time and relative density. Overlaid contour plot (f)

and the relative density of the coating (%). In the contour overlaid contour plot with the multiple response optimizer
plots the response values can be predicted by a combina- tool, it was predicted that in a TBC with a relative density
tion of the factors; and they can be individually optimized of 89.8%, the most effective Ap to stop infiltration repre-
by setting the tendency to maximize or minimize. For the cipitates at an infiltration depth and time of 66.3 µm and
infiltration depth, the lowest values can be achieved with 338 min, respectively, and exhibits a Ca:(Gd + Zr) of 0.33,
high relative densities and infiltration times, while the oppo- which is closer to the nominal composition of Ap [26]. As
site trend is observed for the Ca:(Gd + Zr) ratio, where the observed in the response optimizer (Fig. 7c), the achieved
range of interest has been reported to be 0.25 to 0.6 [26]. An desirability for single and composed responses was 1, indi-
overlaid contour plot (Fig. 7f) as a function of the studied cating that the defined levels allow achieving the predicted
factors has been obtained to visualize the feasible region responses.
(white) where the two responses are simultaneously ana-
lyzed and defined by setting low and high limits shown by
dashed and solid lines, respectively. The infiltration depth 4 Discussion
and Ca:(Gd + Zr) ratio were optimized in the ranges from
45 μm to 70 μm and μm 0.25 to 0.4 μm, respectively. The In this section, the influence of the reaction products on the
local optima of the input factors that allow mitigating the infiltration kinetics of GZO TBCs is discussed. In Fig. 5, at
degradation of the coating indicate the conditions under stage I (< 60 min), there is a high infiltration rate, compared
which the depth of the melt penetration is restricted, and to stage II, of both manufactured TBCs, presenting infiltra-
the formation of stable apatite phases is promoted. In the tion rates of 0.3 µm/min and 0.8 µm/min for TBCs with
optimizer response of Fig. 7c can be visualized the effects of relative densities of 91.71% and 89.83%, respectively. These
the relative density and infiltration time on the ca:(Gd + Zr) high rates at stage I are due to the dissolution, diffusion, and
ratio and infiltration depth, and the combination of factor reprecipitation reactions taking place [21, 27]. Initially, the
levels that result in the optimal response, which was defined melt dissolves the TBC, and its main constituents, G ­ d3+ and
4+
by setting the objectives of maximizing or minimizing the ­Zr , diffuse away from the reaction into the melt; however,
response variable. By analyzing the feasible region of the as the infiltration continues, the melt becomes saturated and
Emergent Materials (2024) 7:2007–2016 2015

reaches local concentrations to promote the crystallization a stable Ap that effectively stops infiltration. These results
of zirconia and Aps, which gradually and partially seal the indicate that relative density and infiltration time play an
infiltration channel [21, 27, 28]. Therefore, these differ- important role in promoting the crystallization of stable Aps
ences in the relative densities of TBCs directly influence the due to the different amounts of G ­ d3+ cations dissolved in
flowability of the melt through their porous structures, with the melt.
the low relative density (89.83%) penetrating easily com-
pared to high relative density TBCs (91.71%). On average,
a major amount of melt penetrates the low relative density 5 Conclusions
TBCs; however, the local saturation in the melt to promote
the reprecipitation of the reaction products depends on the Free-standing GZO TBCs deposited by APS, showing differ-
amount of dissolved cations in the TBCs, which may vary ent microstructural characteristics such as densification level
due to the relative density of the TBCs and the infiltration and thickness as a function on the deposition rates were used
depth reached. In stage II, the infiltration rates decrease to for infiltration experiments.
0.10 µm/min and 0.05 µm/min for high and low relative den- Compared to YSZ, the GZO TBCs show excellent resist-
sity GZO TBCs, respectively. These changes in infiltration ance to infiltration of molten Colima VAs, and present infil-
rates occur because an significant amount of Ap and zirconia tration depths around 75 µm and 80 µm. On the other hand,
reaction products have already crystallized above the reac- the infiltration kinetics show two infiltration rate regimes,
tion front at the first 60 min; therefore, a large amount of fast infiltration rates during the first 60 min and slow infiltra-
these reaction products prevent high infiltration rates [21] tion rates between 60 to 600 min of infiltration time. These
due to the partial sealing of the reaction front in the TBCs. changes in infiltration rates are attributed to partial sealing
Nonetheless, after 600 min of infiltration time, both samples of the channels due to the formation of stable apatite phases.
present similar values of infiltration depths, around 75 µm Applying a systematic DoE methodology, the impact and
and 80 µm; this indicates that the initial relative density of correlation between key input parameters of the infiltration
the TBC, infiltration depth, and time influence the formation TBCs were investigated to understand their interactions
of reaction products to stop the degradation process. with the Colima VA. The interaction between microstruc-
The Ap phase has been reported to be the main reaction tural characteristics of GZO TBCs and apatite formation was
product stopping infiltration in REZ-based TBCs [14, 27]. studied to identify the best conditions for stopping the infil-
The formation of a stable Ap depends on several factors, tration of molten ash. In the GZO coatings of this work, the
such as ­RE3+ cation size, Ca:(Gd + Zr) ratio, etc. It has been stable Ap phase reprecipitates at infiltration depths around
reported that Aps exhibiting the nominal Ca:Gd around 0.25 66.3 µm after 338 min of Colima volcano ash infiltration
have is the most stable Ap in GZO TBCs [26], representing time.
a defect-free stoichiometry in the Ap structure [29]. In this
sense, understanding the formation of a stable Ap in GZO Data availability No datasets were generated or analysed during the
is relevant to in turn understanding its connection with the current study.
infiltration kinetics. Figure 7 shows the influence of infil-
Declarations
tration time and initial TBC’s relative density on the Ap
stability ratio and infiltration depth. Figure 7a shows that Competing interests The authors declare that they have no known
the reprecipitation of a stable Ap is favorable with longer competing financial interests or personal relationships that could have
infiltration time, while it is unfavorable with TBCs with appeared to influence the work reported in this paper.
The authors declare the following financial interests/personal relation-
higher relative density. On the other hand, the infiltration ships which may be considered as potential competing interests.
depth increases with both longer times and higher relative
densities. Figure 7f shows the optimal region in which sta- Open Access This article is licensed under a Creative Commons Attri-
ble Ap with a Ca:(Gd + Zr) ratio greater than 0.4 at infil- bution 4.0 International License, which permits use, sharing, adapta-
tion, distribution and reproduction in any medium or format, as long
tration depths below 70 µm. The area of this region tends as you give appropriate credit to the original author(s) and the source,
to decrease with increasing relative density and infiltration provide a link to the Creative Commons licence, and indicate if changes
time. Statistical analysis predicts that, in a GZO TBC with were made. The images or other third party material in this article are
a relative density of 89.8%, a stable Ap with a Ca:(Gd + Zr) included in the article’s Creative Commons licence, unless indicated
otherwise in a credit line to the material. If material is not included in
ratio of 0.33 is reprecipitated after 338 min at an infiltration the article’s Creative Commons licence and your intended use is not
depth of 66.3 µm. However, higher relative density TBCs permitted by statutory regulation or exceeds the permitted use, you will
(91.2%—91.7%) require longer infiltration times to reprecip- need to obtain permission directly from the copyright holder. To view a
itate stable Aps with a lower Ca:(Gd + Zr) ratio compared to copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
lower relative density TBCs (89.8%—90.3%), which require
shorter infiltration times to promote the reprecipitation of
2016 Emergent Materials (2024) 7:2007–2016

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