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Article history: In this study, barrier membranes were prepared from poly(vinyl alcohol) (PVOH) with different amounts
Received 22 February 2008 of cellulose nanocrystals (CNXLs) as ller. Poly(acrylic acid) (PAA) was used as a crosslinking agent to
Received in revised form 4 April 2008 provide water resistance to PVOH. The membranes were heat treated at various temperatures to optimize
Accepted 5 April 2008
the crosslinking density. Heat treatment at 170 C for 45 min resulted in membranes with improved water
Available online 12 April 2008
resistance without polymer degradation. Infrared spectroscopy indicated ester bond formation with heat
treatment. Mechanical tests showed that membranes with 10% CNXLs/10% PAA/80% PVOH were syner-
Keywords:
gistic and had the highest tensile strength, tensile modulus and toughness of all the membranes studied.
Cellulose
Nanocrystal
Polarized optical microscopy showed agglomeration of CNXLs at ller loadings greater than 10%. Differ-
Poly(vinyl alcohol) ential thermogravimetric analysis (DTGA) showed a highly synergistic effect with 10% CNXL/10% PAA/80%
Poly(acrylic acid) PVOH and supported the tensile test results.
Barrier Transport properties were studied, including water vapor transport rate and the transport of
trichloroethylene, a representative industrial toxic material. Water vapor transmission indicated that all
the membranes allowed moisture to pass. However, moisture transport was reduced by the presence of
both CNXLs and PAA crosslinking agent. A standard time lag diffusion test utilizing permeation cups was
used to study the chemical barrier properties. The membranes containing 10% CNXLs or PAA showed
signicantly reduced ux compared to the control. The CNXLs were then modied by surface carboxy-
lation in order to better understand the mechanism of transport reduction. While barrier performance
improvements were minimal, the chemical modication improved the dispersion of the modied CNXLs
which led to improved performance. Of special note was an increase in the initial degradation tempera-
tures of both modied and unmodied systems, with the modied system showing an initial degradation
temperature >100 C higher than the cellulose alone. This may reect more extensive crosslinking in the
modied composite.
2008 Elsevier B.V. All rights reserved.
0376-7388/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2008.04.009
S.A. Paralikar et al. / Journal of Membrane Science 320 (2008) 248258 249
system remained constant throughout the experiment. (3) After 2.4. Surface modication of cellulose nanocrystals
a sufcient time interval, a semi-steady state mass transfer was
attained and the ux became constant. (4) The permeant was a A dispersion of 200 mL of 1% CNXLs was mixed with 0.2 g of
liquid with concentration c0 at the upstream surface of the mem- TEMPO and 2 g of NaBr. The oxidation reaction was initiated with
brane and a concentration of zero at the downstream surface of the the addition of 10 mL of NaClO solution. Then 10 mL NaClO solu-
membrane. tion was subsequently added after 2 and 4 h. The overall reaction
There are generally three different parameters that characterize time was 15 h and a pH of 10 was maintained throughout with
the diffusion of a permeant through a polymer membrane in this the addition of 1N NaOH as necessary. The oxidation reaction
type of experiment [29]: (1) The time from initial exposure until was terminated by the addition of 30 mL of ethanol. The suspen-
the permeant is rst detected, i.e. the breakthrough time. (2) The sion was ultraltered thrice (Ultrasette tangential ow UF device,
ux (Q), which is obtained from the slope of the line of cumulative pore size = 50 nm, Pall Corp., Ann Arbor, MI) to remove unreacted
ow through the membrane vs. time. (3) The time lag (tlag ), which reagents. A calculated amount of 1 M HCl was added to convert the
is the x-axis intercept of the same plot. carboxylates to free acid. The solution was again ultraltered until
Under the conditions of this experiment, assuming the diffusion a permeate conductivity of <5 S/cm was obtained. A dispersion of
coefcient (D) is constant and the solubility of the permeant in the 1% carboxylated CNXLs (C.CNXLs) was obtained by concentrating
polymer membrane is uniform, Ficks law may be used to derive in a rotavaporizer R110 (Buchi, Flawil, Switzerland). Carboxylated
the time dependence of Q as content (mmols of acid group/g CNXL) of the dispersion was deter-
mined by potentiometric titration using 0.01N NaOH.
Pc0 L2
Q = t (1)
L 6D 2.5. Preparation of the membranes
toughness was obtained as the area under the load vs. elongation attached to an Eclipse E400 Nikon microscope (Nikon Company,
curve from zero load to failure. Melville, NY) using crossed polarizers.
Atomic force microscope (AFM) imaging was performed using a
2.8. Water vapor transmission rate (WVTR) Dimension 3100 series Scanning Probe Microscope (Veeco Metrol-
ogy Inc., Santa Barbara, CA). The AFM was operated in tapping
The prepared heat-treated membranes were glued onto glass mode using a rectangular silicon cantilever NSC 15/AIBS (Mikro-
jars half lled with water. The initial weights of the assemblies were Mash Wilsonville OR) with a tip radius <10 nm, typical resonance
noted. Three replicates of each sample were placed in a controlled frequency of 325 kHz and force constant of 46 N/m.
environmental chamber at 30 C and 30% relative humidity. The
weight change was noted as a function of time until a constant ux 3. Results and discussion
was obtained for three consecutive days. The water vapor trans-
mission rate was calculated from the steady state weight loss as 3.1. Crosslinking
2.12. Imaging
Fig. 4. Total % water sorption, after 72 h of soaking time, for membranes with heat
treatment at 170 C/45 min.
3.2. Agglomeration
Fig. 5. Polarized optical microscopy pictures of (A) 5 wt% CNXL/10 wt% PAA, (B) 10 wt% CNXL/10 wt% PAA and (C) 15 wt% CNXL/10 wt% PAA. PVOH makes up the remaining
content of the membranes.
S.A. Paralikar et al. / Journal of Membrane Science 320 (2008) 248258 253
Fig. 6. Mechanical properties as a function of CNXL and PAA content. Coefcient of variability for the samples ranged from 3 to 10%. The error bars represent 1 standard
deviation of the data.
from further consideration as commercially interesting composi- ates (Fig. 8B), but their well-dispersed pattern argues against this.
tions. Higher magnications gave no further elucidation of these fea-
The tensile modulus increased with the addition of CNXLs from tures on our equipment. Once again, the 20% CNXL/10% PAA sample
0 to 10%, but then dropped (Fig. 6). We believe that the drop in showed a much rougher texture (Fig. 8C) indicative of agglomera-
modulus with CNXL content was due to agglomeration. Modulus tion and poor fracture resistance.
increased with PAA content from 0 to 10% then leveled off. This Supporting the optical microscopy results, CNXLs were found
suggested that either there was no additional crosslinking in the to be agglomerated in the 20% samples. Within these agglomer-
20% PAA sample compared to the 10%, (although the reduction in ates the CNXL surfaces are probably not fully wetted by the matrix.
water sorption argues against this explanation), or that the 10% This results in void spaces and weak interactions between particles
already had sufcient crosslinking to maximize the modulus. Again, and between particles and the matrix, hence crack propagation is
we see a signicant synergy for the 10% CNXL/10% PAA sample. enhanced in these regions, lowering the mechanical properties of
The energy to break is the area under the stress strain curve, the membrane.
which is one measure of the toughness of a material. A signi-
cant synergy was observed once again with the 10% CNXL/10% PAA
3.5. Thermal properties
sample (Fig. 6). With an increase in the PAA content to 20% the brit-
tleness in the membranes increased, the % elongation decreased
Pure PAA and pure PVOH degraded thermally in three steps at
and as a result toughness decreased. Again, 10% PAA with 10% CNXLs
similar temperatures. Pure CNXL degraded in a complicated pattern
showed excellent toughness, an improvement of 2.5 times in UTS
with an initial degradation temperature of 220 C and the maxi-
and twice the tensile modulus compared to pure PVOH.
mum at 273 C (Fig. 9A). For pure PVOH, the maxima occurred at
290, 347 and 454 C. The maxima for pure PAA occurred at 300,
3.4. Electron microscopy 360 and 454 C. When PVOH and PAA were blended together only
two maxima were observed and they shifted to higher tempera-
SEM images of fractured membrane surfaces showed a smooth tures at 374 and 463 C. The presence of CNXLs had little effect
surface for 100% PVOH (Fig. 7A). A rough texture with small cracks on the degradation temperatures (Fig. 9B). In fact, CNXL in PVOH
was observed in the presence of CNXLs and PAA (Fig. 7B). The without PAA showed little change in its degradation pattern from
fracture initiated crack formation, but well-dispersed CNXLs and pure PVOH. This suggests that it is the crosslinking with PAA that
good bonding between the components evidently prevented fur- alters the thermal degradation of these composites. Various blends
ther crack proliferation. The rough texture could be attributed to of PAA, CNXL and PVOH with 1020% PAA or CNXL were observed
the addition of PAA which added to the stiffness and brittleness of to be similar to the DTGA graph of 10% PAA/10% CNXL and are not
the membranes. Membranes with CNXL contents >10 wt% showed shown.
more cracks which were deeper, wider and longer (Fig. 7C). Overall, the membrane with 10% PAA/10% CNXL/80% PVOH does
At higher magnication, similar results were observed (Fig. 8). not loose its integrity as a composite material and this combi-
The 100% PVOH appeared to be smooth (Fig. 8A). The 10% CNXL/10% nation holds promise for its further development as a barrier
PAA sample showed raised areas that could be CNXL agglomer- membrane.
254 S.A. Paralikar et al. / Journal of Membrane Science 320 (2008) 248258
Fig. 8. Higher magnication SEM fracture surface images of (A) 100% PVOH, (B) 10% PAA/10% CNXL/80% PVOH and (C) 10% PAA/20% CNXL/70% PVOH.
S.A. Paralikar et al. / Journal of Membrane Science 320 (2008) 248258 255
Fig. 9. DTGA graphs comparing the thermal degradation of (A) the pure components (PVOH, PAA and CNXLs), (B) the effect of PAA and CNXL and (C) C.CNXL to CNXL-lled
membranes.
Fig. 10. WVTR with varying weight% of either CNXLs or C.CNXLs and varying weight% of PAA. PVOH makes up the remaining content of the membranes. The error bars
represent 1 standard deviation of the data.
256 S.A. Paralikar et al. / Journal of Membrane Science 320 (2008) 248258
Fig. 14. AFM tapping mode images of (A) dried dispersion of CNXLs and (B) dried dispersion of C.CNXLs.
Carboxylating the CNXLs showed a consistent, but small, the degree of crosslinking (assumed to be proportional to the con-
decrease in WVTR for the C.CNXL samples (Fig. 10). This is in centration of CO2 H groups) that is important, and not whether the
accord with our contention that the C.CNXLs provide for additional crosslinking is to a nanocrystal or to the PAA. Since the unmodied
crosslinking between the nanoparticle ller and the matrix. CNXLs are suspected to also form ester groups with the PAA, it is not
C.CNXLs in PVOH showed insignicant changes in CVTR time surprising that mechanical properties have not changed. It is per-
lag compared to unmodied CNXLs (Fig. 12). However, the ux of haps more informative that the transport properties do not change.
the 15% C.CNXL was markedly lower than that of the corresponding One might expect that any change in the interphase would alter
15% CNXL sample (Fig. 13). We attribute this to agglomeration in the transport properties if surface ow along the percolating nanopar-
case of the unmodied CNXLs, while the C.CNXLs were observed to ticles governs diffusion through the membrane. However, these
be easier to disperse and gave a more stable dispersion in all cases. data suggest that the diffusion chemistry of the interphase is not
Thermogravimetric analysis showed that the incorporation of that sensitive to its composition and that PAACNXL ester bonds
C.CNXLs gave an increase in initial degradation temperature and and C.CNXLPVOH ester bonds yield similar interphases and there-
peak rate of degradation of approximately 40 C compared to fore similar nal composite properties. An alternative explanation
unmodied CNXLs in the same matrix (Fig. 9C). We conclude would be that the transport of the TCE through the membrane
from this that the C.CNXLs are more highly crosslinked to the is not related to particle surface ow and occurs primarily in the
PVOH matrix than unmodied CNXLs. However, this large effect matrix, with the CNXLs providing a more tortuous path up to con-
observed in the TGA did not result in correspondingly large centrations where they begin to agglomerate. Additional research
effects in either mechanical properties or transport properties. is required to determine which hypothesis predominates in this
When we compare the number of carboxylate groups on the system.
CNXL surface in the 10% C.CNXL/10% PAA/80% PVOH membrane to
those on the PAA backbone in the same membrane, we see that 4. Conclusions
CO2 H(C.CNXL)/CO2 H(PAA) = 10.6%. Furthermore, the total number
of carboxyl groups in the membrane was kept constant. So we con- Heat treatment improved the crosslinking density within the
clude that in terms of mechanical and transport properties, it is membranes made of varying contents of CNXL, PAA and PVOH. Sol-
258 S.A. Paralikar et al. / Journal of Membrane Science 320 (2008) 248258
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