Results
Surface Characterization of Commercially Available
Membranes (PP, PTFE, PVDF)
Before OMD Process
Surface properties have a great impact on the membrane per-
formance. For this reason, wide characterization of the phys-
icochemical properties of the surface was done.
The morphology of the applied membranes is presented in
Fig.
2
. Based on these SEM images, it can be seen that all
membranes are characterized by different morphologies. PP
and PVDF membranes possessed higher porosity and thick-
ness. PTFE membranes with a smaller pore size were charac-
terized by lower values of thickness (65
μ
m) and porosity
(62 %) (Table
1
). The porosity and thickness for 0.45-
μ
m
PTFE membranes were equal to 80 % and 80
μ
m, respective-
ly. Polypropylene (PP) membrane has a fiber-like structure as
it can be observed in the cross section image (Fig.
2
(I)).
PTFE membranes are expanded-film membranes made of
polytetrafluoroethylene by the uniaxial or biaxial stretching
process resulting in an interconnected pore structure
(Kujawski et al.
2013
; Warczok et al.
2007b
). SEM images
of the PTFE membranes shown in Fig.
2
(II and III) indicated a
very similar skin structure of the 0.20- and 0.45-
μ
mmem-
branes. However, it is possible to observe a relatively more
open pore structure of the 0.45-
μ
m membrane than that of the
0.20-
μ
m membrane. These observations are consistent with
the pore size distribution obtained by the capillary flow
porometry technique (Fig.
3
). The polyvinylidenedifluoride
(PVDF) membrane was characterized by a sponge-like struc-
ture (Fig.
2
(IV)). Additionally, compared to the rest of the
membranes, PVDF 0.45 has a very broad PSD (ranging from
0.8 to 0.25
μ
m) and the largest BP (0.800 ± 0.002
μ
m) that
represented quite a large amount of the total pores (
∼
3%).
PTFE membranes showed both narrower PSDs (both with a
span of
∼
0.2
μ
m) and different BPs, being that of the PTFE
0.2 (0.40
μ
m) almost half of the PTFE 0.45
(0.729 ± 0.014
μ
m). PP had the narrowest PSD and the
smallest BP (0.088 ± 0.001
μ
m). A summary of the membrane
characterization prior to the OMD process is shown in Table
2
.
All investigated membranes were characterized by contact
angle values higher than 90°, which corresponds to their hy-
drophobic behavior (Table
2
). Membrane materials have a
clear impact on the hydrophobicity. The most hydrophobic
membranes were made from PTFE. However, the lowest hy-
drophobicity level was observed for PP membranes (i.e.,
CA
∼
113°). HCA values were strongly associated with mem-
brane materials and pore size of the tested membranes. It can
be seen (Table
2
) that for a more smooth material (PVDF),
characterized by a lower value of RMS (50 ± 2 nm), the
contact angle hysteresis is lower (28° ± 1°). SFE values were
in the range of 38.0 × 10
−
3
to 51.2 × 10
−
3
Nm
−
1
. This param-
eter (SFE) is directly related to the hydrophobicity. For that
reason, the lowest value of SFE was noticed for the membrane
characterized by the highest CA value (PTFE 0.45). Surface
free energy for the examined membranes depends on the
membrane materials as well as on the pore size. The highest
value of SFE was observed for the PP membrane (i.e., RMS
125 ± 3 nm) and was associated with the morphology of the
membrane, a fiber-like structure (Fig.
2
.I). On the other hand,
the lowest SFE value was determined for the 0.45-
μ
mPTFE
membrane (i.e., RMS 65 ± 2 nm). Roughness of the mem-
brane surface (RMS) was associated with the HCA value, and
for more rough samples, a higher value of contact angle hys-
teresis was observed (Table
2
). Furthermore, it should be
highlighted that the roughness correlates well with the mem-
brane materials. According to that, the utilized membranes
should be classified into three groups and considered as PP,
PTFE, and PVDF membranes. Based on that assumption, it
can be stated that for more rough samples, higher values of
SFE are observed. The RMS values are well correlated with
CA and SFE values.
After the OMD Process
In order to investigate the impact of the OMD process on the
membrane properties, an extensive characterization of the
membrane was done. During the OMD, different membranes
(PP 0.10
μ
m, PTFE 0.2 and 0.45
μ
m, PVDF 0.45
μ
m) and
stripping solutions (NaCl and CaCl
2
) as well as feed solutions
(water, beet and apple juices) were applied. After the OMD
process, differences in physicochemical properties of the
membranes were observed.
The hydrophobicity level of the polymeric membranes was
changed. It was associated with the organic layer created on
the membrane surface remaining after cleaning the mem-
branes. Depending on the experimental conditions and applied
juices, it was possible to notice a layer on the whole surface or
on only a part of the membrane (Fig.
4
).
The obtained values of the contact angle for the membranes
after the OMD process were lower than those for native sam-
ples (Table
2
). The differences between CA values before and
after the OMD processes were equal to about 8°
–
13°. The
largest difference was observed for the 0.45-
μ
mPTFEmem-
brane from 133° ± 1° to 120° ± 1°, however the smallest for
PVDF and PP membranes from 120° ± 1° to 112° ± 1° and
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from 113° ± 1° to 105° ± 1°, respectively (Table
2
). Membranes
utilized in the OMD process demonstrated a higher value of
HCAandweremorerough(RMS)comparingwiththeunused
membranes. This behavior is
related to the deposition of
Fig. 2
SEM images of used
polymeric membranes: PP
0.10
μ
m(
I
), PTFE 0.20
μ
m(
II
)
and 0.45
μ
m(
III
), and PVDF
(
IV
).
O
obverse and
R
reverse
sidesofthemembranes.
Magnitude 200×, 2000×, and
10000×
Fig. 3
Pore size distribution
(PSD) of the studied membranes
Food Bioprocess Technol (2015) 8:2146
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2158
2151
organic residues from the juices on the membrane surfaces
(Fig.
4
). Taking into consideration the SFE, it can be seen that
after the membrane application in the OMD process, these
values slightly increased (Table
2
). This fact can be associated
with the small changes in the membrane resistance and me-
chanical strength after the OMD process, especially in the case
of the 0.45-
μ
m PTFE membrane. For this sample, changes with
mechanical strength were the most visible.
Porosity and mechanical strength (Mullen burst test) results
for the membranes before and after the OMD concentration
process have been represented in Fig.
5
.
Regarding the porosity values, PTFE membranes showed
higher values (60.3 and 51 % for PTFE 0.45 and PTFE 0.2,
respectively) followed by PVDF 0.45 (50 %). PTFE mem-
branes due to their open structure show high porosities in
general; as for the PVDF 0.45, its relatively big and broad
PSD is also reflected in big porosity values. PP showed a
remarkably lower porosity (21 %), most probably due to its
relatively smaller PSD. Also, as revealed by the SEM images,
the PP membrane showed a much less porous surface wher-
ever the imprints of its particular backer material were located.
However, it was related to the fact that the PP membrane
possesses a support on the backer side (Fig.
2
(I)). After the
OMD process, a general reduction of the porosity in the tested
membranes was observed (Fig.
5
). The PVDF 0.45 seemed to
be the least affected (7 % reduction) while the PP showed the
biggest decrease (37 %). The other two membranes, PTFE
0.45 and PTFE 0.2, showed a porosity reduction of 26 and
15 %, respectively. Most probably, the bigger thickness and
more open structure of the PVDF membrane result from a
sponge-like structure, when compared to its counterparts. This
could prevent the porosity reduction after the OMD process.
Mullen burst tests did not reveal an important influence of the
fouled condition in the mechanical strength of the studied
membranes (Fig.
5
). Amongst the studied membranes, PP
showed the highest burst pressure probably due to its support
(27.8 PSI). In general, all the membranes had similar or slight-
ly smaller burst pressure post OMD application with the only
exception of the PTFE 45 which showed a higher value, and
that might have been due to a comparatively greater fouling
layer accumulated in that particular sample. The fouled mem-
branes were also studied under SEM (Fig.
6
).
The PVDF membrane has a sponge-like structure with a
very high surface porosity consisting of big pores (>1
μ
m)
randomly distributed on the surface (Fig.
3
) combined with
the less hydrophobic nature of the PVDF comparing with
Table 2
Surface properties of membranes before and after application
in the OMD process (feed solutions: apple and beet juices; stripping
solution: CaCl
2
)
Membrane CA (°) HCA (°) SFE (10
−
3
Nm
−
1
)RMS(nm)
Pristine membranes
PP 0.10
μ
m 113 ± 1 36 ± 1 51.2 ± 0.4 125 ± 3
PTFE 0.20
μ
m 121 ± 1 34 ± 1 42.3 ± 0.3 70 ± 2
PTFE 0.45
μ
m 133 ± 1 33 ± 1 38.0 ± 0.3 65 ± 2
PVDF 0.45
μ
m 120 ± 1 28 ± 1 41.6 ± 0.3 50 ± 2
Membrane after the OMD process
PP 0.10
μ
m 105 ± 1 54 ± 1 59.3 ± 0.4 150 ± 4
PTFE 0.20
μ
m 111 ± 1 52 ± 1 57.9 ± 0.4 120 ± 3
PTFE 0.45
μ
m 120 ± 1 40 ± 1 43.7 ± 0.3 103 ± 3
PVDF 0.45
μ
m 112 ± 1 50 ± 1 55.0 ± 0.4 60 ± 2
Fig. 4
The 0.45-
μ
m PTFE membrane after the OMD processes in the
following systems:
1a
NaCl/apple juice,
1b
CaCl
2
/apple juice,
2a
NaCl/
beet juice,
2b
CaCl
2
/beet juice
Fig. 5
Porosity and mechanical strength (Mullen burst test) results for
the studied membranes before and after their application in the OMD
process (feed solutions: apple and beet juices; stripping solution: CaCl
2
)
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2158
PTFE that makes this membrane prone to fouling. The SEM
images showed an almost continuous fouling layer on top of
the PVDF membrane. Moreover, the cross section images
(Fig.
6
b) revealed the presence of scattered internal deposits.
However, the depth (