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Abstract
The previous report of this work has demonstrated the fabrication and properties of porous yttria-stabilized zirconia (YSZ) ceramics with unidi-
rectionally aligned pore channels. As a follow-up study, the present work aims at lowering the thermal conductivity of the porous YSZ ceramics
by silica aerogels impregnation. The porous YSZ ceramics were immersed in an about-to-gel silica sol. Both the unidirectionally aligned pore
channels and the inter-grain pores by grain stacking in the channel-pore wall of the porous YSZ ceramics were impregnated with the silica sol. After
aging and supercritical drying, silica aerogels formed in the macroporous network of the porous YSZ ceramics with unidirectionally aligned pore
channels. The influences of silica aerogel impregnation on the microstructure and properties of porous YSZ ceramics with unidirectional aligned
pore channels were investigated. The porosity decreased after impregnation with silica aerogels. Both microstructure observation and pore size
distribution indicated that both channel-pore size and inter-grain pore-size decreased significantly after impregnation with silica aerogels. Impreg-
nating porous YSZ ceramics with silica aerogels remarkably lowered the room-temperature thermal conductivity and enhanced the compressive
strength. The as-fabricated materials are thus suitable for applications in bulk thermal isolators.
© 2011 Elsevier Ltd. All rights reserved.
0955-2219/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jeurceramsoc.2011.07.014
2916 L. Hu et al. / Journal of the European Ceramic Society 31 (2011) 2915–2922
Fig. 3. SEM images of the porous YSZ ceramics with unidirectionally aligned pore channels before impregnation (a), after impregnation (b), silica aerogels (the
former pore channel) (c) and ceramic wall impregnated with silica aerogels (d).
the cooled plate. The microstructure was taken at four randomly surement System (PPMS, Model 6000, Quantum Design, USA).
selected locations on each sample (two samples per condition). The TTO system measured thermal conductivity λ by applying
Pore size distribution of the porous YSZ ceramics with uni- heat from the heater shoe in order to create a user-specified tem-
directionally aligned pore channels was analyzed by a mercury perature differential (T) between the two thermometer shoes,
intrusion porosimetry (AutoPore-IV9510, Micromeritics Instru- which were connected to the two sides of sample using epox-
ment Corp., United States). The mesopores of the silica aerogels ies (including silver-filled H20E and nonconductive tra-bond
are hardly detectable with mercury intrusion method due to 816H01). TTO dynamically modeled the thermal response of
crushing of the silica aerogels during intrusion of mercury into the sample to the low-frequency, square-wave heat pulse, thus
the silica aerogels. For this reason, the average pore size dis- expediting data acquisition. TTO then calculated thermal con-
tribution of silica aerogels was determined by N2 adsorption at ductivity directly from the applied heat power, resulting T, and
77 K instead of mercury intrusion. Bulk density of the sintered sample geometry. The compressive strength was measured by
samples before infiltration was measured from sample mass and using a CSS-2220 testing machine with cylindrical specimens
dimension, and relative density, thus porosity were determined with a diameter of 20 mm and a height of 20 mm. Three speci-
from the ratio of the measured bulk density to the theoretical mens were used to determine the average compressive strength.
one of the YSZ material, which was taken as 6.0 g/cm3 . Three
samples were examined to determine the average porosity. The 3. Results and discussion
mass of the silica aerogel impregnated into the sample was cal-
culated by subtracting the mass of the sample after impregnation 3.1. Microstructure
by the corresponding mass before impregnation. The volume of
the incorporated silica was obtained through dividing the mass Fig. 3 shows the microstructure of the porous YSZ ceramics
by the density of the silica aerogel which was measured sepa- with unidirectionally aligned pore channels before impregna-
rately. The porosity of the sample after impregnation was then tion (a), after impregnation (b), silica aerogels (the former pore
calculated through subtracting the original volume fraction of channel) (c) and ceramic wall impregnated with silica aero-
pores by the volume fraction that was occupied by the silica gels (d). The architectures were observed in the same section
aerogel. Thermal conductivity at room temperature was mea- area parallel to the pore channels before and after impregnation
sured on 5 mm × 5 mm × 3 mm machined specimens, using a (Fig. 3(a) and (b)), respectively. Compared to Fig. 3(a), impreg-
Thermal Transport Option (TTO) of Physical Properties Mea- nation with silica aerogels in the unidirectionally aligned pore
2918 L. Hu et al. / Journal of the European Ceramic Society 31 (2011) 2915–2922
Fig. 4. Porosity of the porous YSZ ceramics with unidirectionally aligned pore
channels before and after impregnation with silica aerogels. The porous YSZ
ceramics were fabricated using three freezing agents: chilled alcohol (CAH),
solidified carbon dioxide (SCD) and liquid nitrogen (LN2).
3.2. Porosity
Fig. 6. (a) Room-temperature thermal conductivity of the porous YSZ ceramics with unidirectionally aligned pore channels before and after impregnation with silica
aerogels. The thermal conductivity was tested along two directions: parallel direction (λ ) and perpendicular direction (λ⊥ ). (b) Thermal conductivity of the porous
YSZ ceramics with unidirectionally aligned pore channels: comparison of experimental data with calculated values derived from Rayleigh expression (perpendicular
direction), parallel model (parallel direction) and EMT model (the fine interconnected pore structure).
in the channel-pore wall, of the porous YSZ ceramics. Both pore of the silica aerogels occurred when measurements were per-
sizes of porous YSZ ceramics before and after impregnation formed using the mercury intrusion method. Typically, aerogels
revealed a similar decreasing trend as the freezing temperature can easily be compressed, in particular by the capillary stresses
decreased. The reasons had been demonstrated in the previous during adsorption or desorption in mercury porosimetry.24
report.7 Because the mesopores of the silica aerogels are hardly
Fig. 5(b) shows a typical pore size distribution determined by detectable with mercury intrusion method, the pore size dis-
mercury intrusion method for porous YSZ ceramics with unidi- tribution of silica aerogels was determined by N2 adsorption at
rectionally aligned pore channels before and after impregnation 77 K and then calculated using the KJS method.25 The results
with silica aerogels. Each case presented a bimodal pore size were shown in Fig. 5(c), in which a single peak near 50 nm was
distribution with two peaks. One peak had a peak pore size of observed. The single peak represented the mesopores in silica
0.35 m and 0.15 m before and after impregnation, respec- aerogels. It could be concluded that three types of pores were
tively. These pores were created by both burn-out of binders detected by pore size distribution determinations of the porous
and grain stacking in the ceramic wall, as shown in Fig. 3(d). YSZ ceramics impregnated with silica aerogels. The results were
The other peak was located at 23 m and 3 m before and after consistent with the observations in Fig. 3.
impregnation, respectively. These pores dominated most pore
volume in all samples. They represented the unidirectionally 3.4. Room-temperature thermal conductivity
aligned pore channels. Each peak revealed a narrow half-peak
width, signifying a narrow pore size distribution. It could be Fig. 6 shows the room-temperature thermal conductivity
seen in this figure that the pore channel size and the pore size of of porous YSZ ceramics before and after impregnation with
inter-grain pores in the channel-pore wall decreased from 23 m silica aerogels. All the samples had low thermal conductivi-
and 0.35 m to 3 m and 0.15 m, respectively. The result was ties, 0.04–0.27 W/m K, which were much lower than that of
consistent with that of Fig. 5(a). It should be noted that the dense YSZ ceramics (∼1.8 W/m K). The reproducibility of
pore size of the mesoporous silica aerogels was not observed the equipment was checked with a set of control experiments
in this figure. The authors believed that no intrusion of mer- on the same silica aerogel specimen including 3 measure-
cury into the silica aerogels was detected and only a crushing ments of the thermal conductivity. The measured values were
2920 L. Hu et al. / Journal of the European Ceramic Society 31 (2011) 2915–2922
0.018 W/m K, 0.020 W/m K and 0.023 W/m K, respectively. than that predicted by the parallel model. It was consistent with
They had an average value 0.020 W/m K of and a deviation value the experimental data. Although the calculated and experimen-
of ±0.002 W/m K, respectively. tal results were not in exact agreement, the difference between
At a given porosity, the thermal conductivity of porous YSZ the calculated values approached the difference in experimental
ceramics after impregnation was lower than that before impreg- results for the two measured directions. Meanwhile, the exper-
nation. Particularly, after impregnating porous YSZ ceramics imental data were lower than the values predicted from both
with silica aerogels, the thermal conductivities along the parallel Rayleigh expression and parallel model.
direction (λ ) and perpendicular direction (λ⊥ ) decreased from One reason why the experimental data were lower than the
0.24 to 0.28 W/m K and 0.08–0.11 W/m K to 0.18–0.24 W/m K calculated values was that the fine interconnected pores among
and 0.04–0.09 W/m K, respectively. Both thermal conductivities the channel walls took up considerable volume fraction of the
of porous YSZ ceramics before and after impregnation with sil- overall pores. In the fine interconnected pore structure in which
ica aerogels revealed a similar decreasing trend as the porosity the two components are distributed connectively, either compo-
increased. Meanwhile, the thermal conductivity in the perpen- nent may form continuous heat conduction pathways, depending
dicular direction (λ⊥ ) along the pore channel was lower than on the relative amounts of the components. James28 developed
that in the parallel direction (λ ). Landauer’s theory29 and pointed out that the effective conduc-
As a better thermal insulator than air (λ, 0.026 W/m K), silica tivity of this type of structure could be modeled well by the
aerogels replaced the air in both pore channels and the inter- effective medium theory (EMT) model:
particle packing pores in the ceramic wall, which resulted in a
decrease of thermal conductivity. The very low thermal conduc- k1 − k e k2 − k e
(1 − v2 ) + v2 =0 (3)
tivity of the silica aerogel could also be related to the Knudsen k1 + 2ke k2 + 2ke
effect, which means that the gas molecules collide with the pore
walls more frequently than with each other because the pore size where the symbols have same meaning with that in the Rayleigh
(50 nm) in the silica aerogel is smaller than the mean free path expression. Fig. 6(b) shows the calculated results for comparison
of the diffusing gas molecules. The gas molecules within the with the experimental data. The values predicted from the EMT
matrix experienced the Knudsen effect, which virtually elim- model were lower than the experimental data. This indicated
inated exchange of energy in the gas, effectively eliminating that the fine interconnected pores among the channel walls which
convection and lowering overall thermal conductivity. Solid took up considerable volume fraction of the overall pores played
phase conduction was low due to the low density and high surface an important role in lowering further the thermal conductivity,
area of the material. along the parallel and perpendicular direction, of the porous YSZ
The thermal conductivity along the perpendicular direction ceramics with unidirectionally aligned pore channels. Taking
and the parallel direction could be modeled by the Rayleigh both the long pore channels (Rayleigh expression and parallel
expression for two-phase component materials and parallel approaches) and the fine interconnected pores (EMT model)
model, on the basis of the structural characteristics along these into account, the calculated values and the experimental data
two measurement direction, respectively. The effective thermal of thermal conductivity approached an agreement.
conductivity λe of two-phase composite materials could be pre-
dicted by the Rayleigh expression26 :
3.5. Compressive strength
λ2 + λ1 + v2 (λ2 − λ1 )
λe = λ1 (1)
λ2 + λ1 − v2 (λ2 − λ1 ) Fig. 7 shows the compressive strength of porous YSZ ceram-
ics with unidirectionally aligned pore channels before and after
where λ1 and λ2 are the thermal conductivity of the two phases, impregnation with silica aerogels. Due to the high porosity
1 and 2, in the composite materials, and v2 is the volume fraction (>70%) which led to an exponential decrease of strength, the
of phase 2. Meanwhile, the Parallel model predicts the effective compressive strength of the porous YSZ ceramics in the present
thermal conductivity of two-phase materials27 : work, 0.3–8.6 MPa, was much lower than the corresponding
λe = (1 − v2 )λ1 + v2 λ2 (2) value (2068 MPa)c of dense zirconia ceramics. The compres-
sive strength of porous YSZ ceramics after impregnation with
where the symbols have same meaning with that in the Rayleigh silica aerogels was much higher than that before impregna-
expression. tion. Particularly, after impregnating porous YSZ ceramics with
On the basis of the two-phase parallel model (parallel direc- silica aerogels, the compressive strength along the parallel direc-
tion) and the Rayleigh model (perpendicular direction), the tion (σ ) and perpendicular direction (σ ⊥ ) increased from 0.9
calculated thermal conductivity values were given in Fig. 6(b) to 3.9 MPa and 0.3–1.7 MPa to 7.4–8.6 MPa and 1.8–2.7 MPa,
for comparison with the experimental data. The calculation respectively. Decreased porosity and pore size, as well as stiff-
used 1.8 Wm−1 K−1 as λ1 for the YSZ solid phase and ened network by impregnation with silica aerogels contributed
0.026 Wm−1 K−1 as λ2 as for the pores, resulting in calculated to the increased compressive strength of porous YSZ ceramics
thermal conductivity values of porous YSZ sample with different impregnated with silica aerogels. Meanwhile, the compressive
porosities before impregnation. At a given porosity, the thermal strength tested along the parallel direction (σ ) was higher than
conductivity predicted by the Rayleigh expression was lower that along the perpendicular direction (σ ⊥ ).
L. Hu et al. / Journal of the European Ceramic Society 31 (2011) 2915–2922 2921
Fig. 7. Compressive strength of the porous YSZ ceramics with unidirectionally aligned pore channels before and after impregnation with silica aerogels. The
compressive strength was tested along two directions: parallel direction (σ ) and perpendicular direction (σ ⊥ ).
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