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Arab J ournal of Nuclear Science and Applications, 45(4), 344-353 (2012



Effect of Heat Treatment on Electrical Properties Of Plasma Sprayed YSZ

R. Abdel Kareem
, A. F. Waheed
, Omar A. A. Abdelal
and Salama. S. Elshikh

Metallurgy Department, Faculty of Engineering, Cairo University Cairo, Egypt
Metallurgy Department, Nuclear Research Center, AEA,Cairo, Egypt.
Received: 4/7/2011 Accepted: 17/10/2011


Impedance spectroscopy (IS) was used to measure the impedance of as
received and heat treated free stand specimens of yttria-stabilized zirconia (YSZ)
coated materials . The atmospheric plasma sprayed (APS) coatings had different t
porosities and microstructures, because of using two spraying machines and
spraying parameters . The coated samples were heat treated. The changes in pore
percentage after heat treatment were determined from both, the geometrical and
theoretical densities of the coat material, and by impedance spectroscopy. The
results showed that the increase in heat treatment time decreased the porosity and
consequently increased the electrical conductivity for all tested APS samples

Key Words: APS, YSZ, TBC's , Heat Treatment, Impedance spectroscopy.


Thermal Barrier Coatings (TBC’s) are widely used in gas turbines for propulsion in power
generation plants
TBC’s are deposited on transition pieces, combustion lines, first-stage blades and
vanes and other hot-path components of gas turbines either to increase the inlet temperature with a
consequent improvement of the efficiency or reduce the requirements for cooling system. Thermal
Barrier Coatings (TBC’s) can reduce the surface temperature of metallic structure by 50°C-200°C.
These coatings allow increased operating temperature of the engine and therefore enhanced efficiency,
increased durability, and extended life of metallic components, typical service temperature range for
these coatings is from 800
C to 1300
. In general thermal barrier coatings (TBC’s) are used as an
application for thermal insulation, corrosion and oxidation and wear resistances. However, both
microstructure and phase composition of these coatings are dynamic during service. At these high
temperatures densification, decrease in porosity and cracks, as well as phase transformation was
currently occurred, which lower the tolerance against thermal stresses. The impedance spectroscopy
(IS) has been frequently used to get information about the electrical properties of zirconia's-based
materials. Impedance spectroscopy technique has the ability to separate the bulk resistance of the
measured material from that of the microstructure resistance as grain boundaries, pores and micro
. The impedance spectroscopy (IS) can accommodate the microstructure differences and
measure the desired TBC parameters which are important for ensuring the long-term reliable operation
of advanced, high-efficiency

The aim of this research is to study the effect of heat treatment at 1200
C on the electrical
properties of yttria stabilized zirconia’s(YSZ ) prepared by air plasma spraying with different
spraying parameters and different powder size to get different microstructure and pores and
differentiate between the different spraying parameters which have the least reduction in pore
percentages. A part of the sprayed YSZ specimens with different porosity and microstructure were
heat treated at 1200
C for different times namely 1hr, 5hr, 10hr, 100hr, 500hr and 1000hr.
Arab J ournal of Nuclear Science and Applications, 45(4), 344-353 (2012)


The as-sprayed and heat treated specimens were tested by impedance spectroscopy technique to
examine the change in electrical properties (resistivity and electrical impedance) as indication of
microstructure changes.

3.1. Sample preparation:

A commercial 8% yttria stabilized zirconia's (8Y
) powder (CERAC- USA) with a mean
particle size 0.45 - 1.0 µm was used as feed stock material for the plasma spray process. Two different
processing regimes with different spraying parameters were used and studied their effect on
microstructure and percentage pores and electrical properties of 8 wt %Y
(8YSZ). The
powder was deposited by conducting in a Sulzer Metco (Ementron -Germany), atmospheric plasma
spraying facility with Metco 204 NS power, using a F-4 gun 64kw class for the first 3 groups and
using a Triplex” gun 80kw class for the second 3 groups , the main working gas was argon and
helium was used as auxiliary gas. The spraying parameters were described in Table.1. All coatings
were sprayed on steel sheet substrate. Prior to spraying, the substrates were roughened with Al
particles by shooting machine. During spraying the substrate was cooled with high pressure air at the
back of substrates.
To obtain free-standing of plasma sprayed 8 wt %Y
(8YSZ) coated samples were
immersed in20% HCI, a low-speed (lubricated) diamond saw was used to section the samples. Six
groups free standing of plasma sprayed 8 wt %Y
(YSZ) samples with different thickness,
pores, and micro crack densities were produced and tested.

Table (1): Parameter of plasma spraying
Spraying Apparatus F-4 gun 64 kw Triplex” gun 80kw
Gun speed, mm/s 55 100
No. of group A B C D E F
Spraying distance (mm) 300 250 150 120 100 90
Gun Current(A) 520 500 500 245 305 520
Plasma gas (Ar) (NLPM) 40 4 20 20 20 30
Auxiliary gas (He)(NLPM) 50 50 10 13 13 20
Thick(µm) 460 540 560 600 620 640

Free standing samples have been annealed at 1200ºC in air annealing furnace, for different
times namely (1hr, 5hr, 10hr, 100hr, 500hr and 1000hr). The as-sprayed and annealed free–standing
samples were painted with platinum paint (Ementron – Germany), to form electrodes on the two sides
of the free standing samples. The painted samples were heated in a furnace at 900ºC/1hr., to support
the painted platinum electrodes. The electrical conductivity of the free–standing (YSZ) samples as
sprayed and heat treated were measured by using AC- Impedance analyzer HP-4129A-LF ,
interfaced with computer , at frequency range 5hz to 13Mhz. at temperature 300 -500
C.As shown in
Fig.(1). The comparison between absolute values of electrical properties of the samples can be carried
out from electrical properties values measured at 500
C both before and after heat treatments.
Arab J ournal of Nuclear Science and Applications, 45(4), 344-353 (2012)


Fig (1): Experimental Setup for A-C Impedance analyzer


4.1. Microstructure of plasma-sprayed YSZ coating:

The microstructure of six free standing coating specimens was characterized by optical
microscopy. There are different from each other.The micro-cracks (pores, cracks) were clearly present
in all samples that are inherent in plasma –sprayed coating ceramic. Figures (2) show the optical
photos of cross sectional of free standing coating specimens as sprayed and after heat treatment for
different times (1h,5h,10h,100h and 500h) at 1200
C. It can be seen that there are differences in
microstructure of the free standing specimens as sprayed owing to the difference in particle size (0.45
- 1.0 µm) of starting powder and the use of two different plasma spaying Apparatus (F-4 gun 64 kw
and Triplex” gun- 80kw) and different spraying distance (300mm,250 mm,150 mm,120mm,100mm
and 90mm). (Fig.2) revealed the lamellar morphology, with each lamellae compressed of columnar
grains and submicron porosity between adjacent lamellae, and micro-cracks appeared. It can clearly
observed that YSZ coatings deposited with Triplex” gun- 80kw can produce higher particle velocity
than F-4 gun 64 kw and increased particle velocity causes enhanced flattening and spreading of the
droplet. Presented a dense microstructure (low porosity), where plasma spraying sufficient melting and
high velocity of spray particles to deposited a dense coatings, while YSZ coatings deposited with F-4
gun 64 kw presented more porous microstructure than YSZ coatings deposited with Triplex” gun-
80kw. Fig. (2) shows the optical photos of cross sectional free standing coating specimens after heat
treatment for (1h, 5h, 10h, 100h and 500h) at 1200
C. The photos show that the microstructure of the
samples greatly improved from the wide pore size distribution (high porosity) of the as-sprayed
sample to a narrow pore size distribution (low porosity) of the sample after heat -treatment at 1200 ?C
for different times.
It is noted that, the lamellar morphology largely transformed to a granular microstructure and
reduced in the porosity. Heat treatment changed the pores morphology and closed cracks, which lead
to the decrease the porosity content
. Quantitative analysis on total porosity (pores and micro crack)
was carried out using geometric method, the porosity-property relationships. This analysis is also
being used to develop a predictive capability of the microstructural property correlations. The change
in microstructure reflects itself as changes in porosity.The results show that the porosity of the samples
is significantly decreased after heat treatment at 1200 ?C for (1h.5h, 10h, 100h and 500h, as shown in
Table. 2.
Arab J ournal of Nuclear Science and Applications, 45(4), 344-353 (2012)


Table (2): Total porosity percent of Samples A, B, C, D, E, and F measured by geometric

As Heat Treated At 1200
1 hour 5 hour 10 hour 100 hour 500 hour
A 25 23.7 22 20.6 18.6 15.4
B 23 21 19.5 17.8 16.4 13.5
C 20 18.3 16.6 15.2 14 12
D 18 16 14.5 13 11.5 10
E 17 13.8 12.5 11 9.5 8
F 15 12.3 10.4 9 7.8 6.5

4.2. Electrical properties (impedance, conductivity):

The electrical impedance measurements were carried out to detect the change in the fraction of the
porosity were in the surface coatings (connected porosity). After heat treatment, the samples as
sprayed and heat treatment were contacted by sputtered platinum electrodes and the complex
impedance (Z) measurements of samples were performed at temperature of 500°C in air, using the
two-point probe AC impedance spectroscopy technique over a frequency range of 5 Hz to 13 MHz.
EIS measurements were done for all the specimens to record the variation in the impedance with the
heat treatment time. Figures (3-7) show the impedance diagrams of free standing (YSZ) as Spraying
and heat treated at 1200
C measured at 500
C under air. Fig. (3) shows impedance diagrams of free
standing samples (A, B, C, D, E and F) as sprayed, which show a difference between these six types of
coatings It was found that the coating of the samples (D, E, and F) which were deposited with a
plasma spraying machine (Triplex” gun 80kw) were about 25% less than the coating samples (A, B
and C) deposited with a plasma spraying machine (F-4 gun 64kw).

The observed difference in electrical impedance between these two types spraying machines
might be a result of the difference in the power, spraying parameters (particles speed, spraying
distances). Figures (4-7) show impedance diagrams of free standing (YSZ) sample as heat treated at
C for different times(1h,5h,10h,100h and 500hrs),. The impedance of the coatings changed
significantly with the heat treatment time (between 1 h and 500 h). A decrease in the impedance was
observed, which could be related to the densification of the coating and the consequent decrease in the

Samlpe(A) heat treated /5hr Samlpe(A) heat treated /1hr Sample(A) as Sprayed at
Arab J ournal of Nuclear Science and Applications, 45(4), 344-353 (2012)


Samlpe (B) heat treated /5hr Samlpe (B) heat treated /1hr Sample(B) as Sprayed at

Samlpe (C) heat treated /5hr Samlpe (C) heat treated /1hr Sample(C) as Sprayed at

Sample(D) heat treated /5hr Sample(D) heat treated /1hr Sample(D) as Sprayed at

Sample(E) heat treated /5hr Sample(E) heat treated /1hr Sample(E) as Sprayed at

Sample(F) heat treated /5hr Sample(F) heat treated /1hr Sample(F) as Sprayed at
Arab J ournal of Nuclear Science and Applications, 45(4), 344-353 (2012)


Figure (2): Optical photos of specimens A, B, C, D, E and F as sprayed at different distances
and after heat treatment at 1200
C for : 1, 5, 10, 100, 500 hrs.

Samlpe (A) heat treated /500hr Samlpe (A) heat treated /100hr Samlpe (A) heat treated/10hr

Samlpe (B) heat treated /500hr
Samlpe (C) heat treated /500hr

Samlpe (D) heat treated /500hr
Samlpe (B) heat treated /100hr

Samlpe (C) heat treated /100hr

Samlpe (D) heat treated /100hr
Sample(B) heat treated/10hr
Samlpe (C) heat treated/10hr
Samlpe (D) heat treated/10hr

Samlpe (E) heat treated /500hr Samlpe (E) heat treated /100hr Samlpe (E) heat treated/10hr

Samlpe (F) heat treated /500hr Samlpe (F) heat treated /100hr Samlpe (F) heat treated /10hr
Arab J ournal of Nuclear Science and Applications, 45(4), 344-353 (2012)


Fig (3): Impedance Spectrum for Samples A, B, C, E, F, as sprayed, measured at 500

Fig (4): Impedance Spectrum for Samples A, B, C, E, F,(H.T at 1200
C/1h), measured at 500

Fig(5): Impedance Spectrum for Samples A, B, C, E, F (H.T at 1200
C/5h)measured at 500

Arab J ournal of Nuclear Science and Applications, 45(4), 344-353 (2012)


Fig (6): Impedance Spectrum for Samples A, B, C, E, F, (H.T at 1200
C/10h) measured at 500

Fig (7): Impedance Spectrum for Samples A, B, C,E, F, (H.T at 1200
C/100h)measuredat 500

N.Q.Wu et al.
, studied the microstructure evolution of thermal barrier coatings, (TBC),
consisting of an yttria stabilized zirconia (YSZ) top coating and an intermediate McrAlY,
(M=Ni,Co,Fe) bond coating, by electrochemical impedance spectroscopy [using Solartron 1260
Impedance Analyzer]. They observed that impedance spectroscopy measurements can fit to an
idealized model circuits, which represent the physical behavior of the thermal barrier coatings. They
concluded that the impedance spectroscopy was sensitive to defects such as cracks, within yttria
stabilized zirconia coatings and the results provide a basis for its application as a non – destructive
evaluation of TBCs.
T.Hilpert et al.
, investigated the electrical properties of free-standing plasma sprayed thermal
barrier coatings after 1250 ºC annealing up to 1000 hrs, by the impedance spectroscopy measurements
in the temperature range from 200 to 350 ºC. They concluded that the electrical impedance of the
coatings is sensitive to changes in microstructure like densification, reduced micro crack density and
phase transformation. They added that these effects can be separated from each other since they affect
different elements in the used equivalent circuit model. The activation energies obtained from bulk
and interlayer conductivities are affected by the annealing process. So, they summarized that this
method can be used to monitor changes in the top coat due to long terms operation at high
temperatures as well as in quality control applications.
Arab J ournal of Nuclear Science and Applications, 45(4), 344-353 (2012)


B.Jayaraj et al.
, also developed the electrochemical impedance spectroscopy as a non-
destructive evaluation technique for life-remain assessment and quality control of thermal barrier
coatings-TBCs. They examine impedance and capacitance behavior of monolithic 8YSZ with open
pores as a function of thickness and density, and found that with 8YSZ thickness increase, the
resistance and the capacitance increased and decreased respectively. For similar thickness, higher
capacitance was observed with lower density.

J.Zhang and V.Desai
used the electrochemical impedance spectroscopy to study the
thermal conductivity
and porosity
of free standing air plasma sprayed (APS) thermal barrier
coatings (TBCs) after exposure at temperatures of 1100, 1200 and 1350 ºC for 3,10,17, 24 and 120
hrs. They found that high temperature exposure of TBCs increases the thermal conductivity as well as
the electrochemical conductance with an increase in exposure temperature and exposure time
. They
found a linear relation ship between the thermal conductivity K, and the electrochemical conductance
They also found for the same porosity: a linear relation ship between TBCs, topcoat thickness and the
ceramic impedance resistance R. But for constant ceramic thickness, the porosity shows a proportional
relation ship with the ceramic impedance capacitance
. Their results indicated that electrochemical
impedance spectroscopy can be used for quality assurance of TBC to evaluate thickness, porosity and
kind of defects
, besides monitoring the thermal conductivity

S.H.Song, et al.
evaluated the number of thermal cycles in air up to 1030 ºC, effect on air
plasma Sprayed YSZ and concluded that impedance measurements showed the affect of alumina scale
formation after 100 to 250 cycles which was not detected for cycles less than 15, and they found that
the resistance of the alumina scale (thermally grown oxide, TGO) increased and the capacitance
decreased with increasing cycles, and their response to the continuous TGO vanishes after 400 cycles
due to TGO degradation.

Ping Xiao, Junfa Mei, Xin Wang
. used Impedance spectroscopy (IS) to characterize the
degradation of thermal barrier coatings (TBCs) due to thermal treatments at 1100oC for a period up to
200 hrs. They examined The growth of the oxide layer at the yttira stablised zirconia (YSZ)/bond coat
interface in TBCs by measuring the impedance diagrams. From the analysis of the impedance
diagrams of TBCs, the electrical properties of YSZ were found to be nearly constant during the
thermal treatments, indicating there was little change in the microstructure and composition of YSZ.
However, there was a clear change in the electrical properties of the oxide layer in the TBCs after
thermal treatments, suggesting both microstructure and composition changes occurred in the oxide
layer. They concluded that the IS is a very useful method in non-destructive characterization of the
degradation of TBCs.

Based on the results obtained, it can be deduced, that the heat treatment at 1200
C effect on the
plasma sprayed YSZ coating is decreased the porosity ratio in all samples. This decrease in porosity
was detected clearly through the impedance spectroscopy measurements which gave good indication
of the porosity decrease by electrical resistance and capacitance decrease. The electrical conductivity
of plasma-sprayed YSZ coating increased with the increase of plasma power, these tendencies of the
electrical conductivity on plasma power and spray distance were consistent with that of the lamellar
bonding ratio. This fact suggested that the lamellar structure feature with the limited interface bonding
dominates the electrical conductivity. It can be considered that the effect of spray parameters on the
electrical conductivity will be realized through the effect on lamellar structure, especially, the lamellar
bonding condition.

Arab J ournal of Nuclear Science and Applications, 45(4), 344-353 (2012)



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