Electron tomography reveals details of the internal
microstructure of desalination membranes
Tyler E. Culpa,1, Yue-xiao Shena,1, Michael Geitnera, Mou Paulb, Abhishek Royc, Michael J. Behrd, Steve Rosenberge,
Junsi Guf, Manish Kumara,2, and Enrique D. Gomeza,g,h,2
a
Department of Chemical Engineering, The Pennsylvania State University, University Park, PA 16802; bThe Dow Chemical Company, Lake Jackson, TX 77566;
c
The Dow Chemical Company, Freeport, TX 77541; dAnalytical Science, The Dow Chemical Company, Midland, MI 48667; eWater Solutions, DowDuPont, Edina,
MN 55439; fAnalytical Science, The Dow Chemical Company, Collegeville, PA 19426; gDepartment of Materials Science and Engineering, The Pennsylvania State
University, University Park, PA 16802; and hMaterials Research Institute, The Pennsylvania State University, University Park, PA 16802
Edited by Monica Olvera de la Cruz, Northwestern University, Evanston, IL, and approved July 23, 2018 (received for review March 18, 2018)
As water availability becomes a growing challenge in various regions
throughout the world, desalination and wastewater reclamation
through technologies such as reverse osmosis (RO) are becoming
more important. Nevertheless, many open questions remain re-
garding the internal structure of thin-film composite RO membranes.
In this work, fully aromatic polyamide films that serve as the active
layer of state-of-the-art water filtration membranes were investi-
gated using high-angle annular dark-field scanning transmission
electron microscopy tomography. Reconstructions of the 3D mor-
phology reveal intricate aspects of the complex microstructure not
visible from 2D projections. We find that internal voids of the active
layer of compressed commercial membranes account for less than
0.2% of the total polymer volume, contrary to previously reported
values that are two orders of magnitude higher. Measurements of
the local variation in polyamide density from electron tomography
reveal that the polymer density is highest at the permeable surface
for the two membranes tested and establish the significance of
surface area on RO membrane transport properties. The same type
of analyses could provide explanations for different flux variations
with surface area for other types of membranes where the density is
distributed differently. Thus, 3D reconstructions and quantitative
analyses will be crucial to characterize the complex morphology of
polymeric membranes used in next-generation water-purification
membranes.
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reverse osmosis polyamide | transmission electron microscopy |
|
tomography voids
M embrane microstructure plays a key role in determining
transport properties, such as rejection or permeability of a
specific component. As a consequence, characterization of the
nanoscale morphology has been of intense interest across several
areas of membrane research. Most of these studies are focused on
measuring the pore size and density, void structure, and spatial
locations of component rejection. Nevertheless, resolving the in-
terplay between the 3D nanostructure and transport properties
remains challenging, despite notable advances (1). Developing
approaches to resolve and analyze the 3D structure of membrane
materials at scales approaching molecular dimensions will likely
be crucial in applications such as ultrafiltration (2), nanofiltration
(3), virus filtration membranes (4), gas separations (5), filtration
for pharmaceuticals (6, 7), and reverse osmosis (RO) (1, 8).
Of the various available technologies, RO has become the most
widely used approach for desalination and wastewater reuse due to
its economic benefits, high permeability, and selectivity (9–14). RO
systems rely on a semipermeable membrane to enable water pas-
sage while rejecting ions. Commercial RO membranes are typically
thin-film composite membranes that incorporate an ultrathin
polyamide top selective layer, a porous 20- to 50-μm polysulfone
support layer, and a nonwoven 50- to 150-μm polyester backing
(10, 15). Polyamide films are synthesized directly on the poly-
sulfone support via an interfacial polymerization reaction between
m-phenylenediamine and trimesoyl chloride (16), resulting in a
8694–8699 | PNAS | August 28, 2018 | vol. 115 | no. 35
fully aromatic, highly cross-linked polymer film with a thickness of
100–200 nm and a root-mean-squared roughness of 50–130 nm
(1, 17, 18).
Because of their critical role in the separation of salt and water,
the properties of polyamide films are pivotal to understanding
transport mechanisms and performance in overall modules. The
polyamide active layer has been labeled with a “ridge and valley”
structure, characterized by techniques such as atomic force mi-
croscopy (AFM), scanning electron microscopy (SEM), and trans-
mission electron microscopy (TEM) (15, 18–23). Nevertheless,
these characterization techniques are largely limited to 2D quali-
tative analyses mostly at the micrometer scale (23, 24). Polymer
materials with low electron density hamper direct high-resolution
electron microscope observation, such that measurements using
quartz crystal microbalance, spectroscopic ellipsometry, electron
microscopy of thin cross-sections, and other techniques were
employed to characterize polymer voids and thicknesses (25,
26). Another limitation is the focus of most studies on pristine
membranes (1, 8, 15, 21, 23–25, 27–35) that cannot account for
the influence of membrane compression during operations; such
compression could result in swelling, collapsing, and rearrangement
of the highly heterogeneous polyamide network. Therefore, little
quantitative information regarding the internal nanostructure of
the active layer exists.
Significance
The development of membrane materials is limited by our lack
of tools to characterize their complex microstructure. We
demonstrate how a combination of careful sample prepara-
tion, electron tomography, and quantitative analysis of 3D
models can provide unique insights into the morphology of
polyamide active layers used in reverse osmosis membranes.
Extracting the 3D morphology is required to obtain accurate
estimates of the top surface area and internal void fraction.
Furthermore, mapping the internal heterogeneity shows that
polymer density is highest near the top surface and suggests
new models of how microstructure and membrane perfor-
mance is connected.
Author contributions: T.E.C., Y.-x.S., M.P., A.R., M.J.B., S.R., J.G., M.K., and E.D.G. designed
research; T.E.C., Y.-x.S., and M.G. performed research; T.E.C., Y.-x.S., M.G., M.P., A.R.,
M.J.B., S.R., J.G., M.K., and E.D.G. analyzed data; and T.E.C., Y.-x.S., M.K., and E.D.G. wrote
the paper.
Conflict of interest statement: M.G., A.R., M.J.B., S.R., and J.G. are all employees of
DowDuPont Inc.
This article is a PNAS Direct Submission.
Published under the PNAS license.
1
T.E.C. and Y.-x.S. contributed equally to this work.
2
To whom correspondence may be addressed. Email: manish.kumar@psu.edu or edg12@
psu.edu.
This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.
1073/pnas.1804708115/-/DCSupplemental.
Published online August 13, 2018.
www.pnas.org/cgi/doi/10.1073/pnas.1804708115
 Recent studies determined the void fraction of fully aromatic
polyamide thin films to be 15–32% (specifically 30% and 31%
for the commercial Dow SW30HR and XLE membranes) for a
range of commercially available RO membranes using water
uptake measurements, spectroscopic ellipsometry, and both
plane-view and cross-sectional TEM image analysis (23–25).
While cross-sectional and plane-view TEM micrographs accurately
display the complex morphology of polyamide films, differentiating
between closed voids and permeable area open to the top surface
is difficult due to the finite thickness of any TEM sample. De-
termining the permeable area open to the surface is important
because of its potential influence on membrane transport prop-
erties. Although TEM tomography results suggest the presence
of closed voids within polyamide films, little quantitative infor-
mation is available to enable comparisons across multiple RO
membrane materials (1, 8, 36–38).
Imaging thick polymer films (>100 nm) using TEM tomog-
raphy at high angles may cause variations in defocus and under/
overexposure artifacts across the image, which increase the dif-
ficulties in posttreatment of data (39–41). More importantly,
quantitative analyses regarding the internal structure were not
readily available from these studies due to challenges with the
application of TEM tomography to these low-electron-density
polymeric materials and image analysis. Scanning TEM
(STEM) imaging, which scans a focused probe across a sample,
has the ability to perform a dynamic focus that can account for
variations in defocus at high tilt angles for thick samples (42).
When employed in high-angle annular dark-field (HAADF) Fig. 1. Electron tomography of isolated polyamide films to reveal 3D mi-
mode, HAADF-STEM imaging relies on contrast from differ- crostructure. (A) Schematic of polyamide isolation protocol. (B) AFM micro-
graphs of the polyamide top surface of the pristine and isolated SWHR-C
ences in mass, thickness, or atomic number (Z-contrast) and is
membrane after cross-flow compression showing minimal surface changes
less prone to image artifacts (42, 43). HAADF-STEM is thus during the polyamide isolation process. (C) Schematic of the HAADF-STEM
ideal to resolve vacuum, carbon-based samples, and gold fidu- tomography tilt series acquisition. Two-dimensional projection images are
ciary markers while mitigating under- and overexposure prob- acquired from ±65°. (D) Volume rendering of the SWHR-C membrane.
lems and improving image quality.
In this work, we applied a combination of cross-flow filtration
for sample compression, a versatile polyamide active layer iso- and after polyamide isolation was characterized by AFM. Minimal
lation method, and HAADF-STEM tomography to reconstruct surface changes in terms of root-mean-squared roughness and sur-
3D models of fully aromatic isolated polyamide films from face area are observed. This is contrary to uncompacted membranes,
commercial RO membranes. Surface characterization of pre- and where the roughness and surface area decrease by ∼50% for both
postisolated films suggests minimal perturbation of the polyamide commercial SWHR and BWXLE membranes after isolation (SI
films during sample preparation. Quantitative analyses of 3D recon- Appendix, Figs. S3 and S4 and Tables S2 and S3). We attribute
structions yield structural parameters such as void volume percentage, these changes in roughness and surface area to collapse of the
surface area, and depth profiles of the polymer density in a manner structure in uncompressed membranes due to the isolation
not otherwise possible. Our approach demonstrates the need for procedure. Thus, compressing all membranes before character-
characterizing the 3D morphology to extract crucial parameters ization simulates conditions and the morphology present during
required for developing transport models connecting the micro- module operation.
structure with membrane performance. To demonstrate the variations between dry and hydrated

ENVIRONMENTAL
polyamide films, we use in situ ellipsometry to determine changes

Results
Polyamide Isolation Process. Fig. 1A shows a schematic of the poly-
amide isolation process; details can be found in SI Appendix. Briefly,
we spin-coat poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)
as a sacrificial layer onto a silicon substrate (44). The RO membrane
top surface is applied to the substrate and organic solvents dissolve
the support layers. After drying in a vacuum oven (SI Appendix, Fig.
S1), the sacrificial layer is dissolved in water and the polyamide film
is removed. Thus, the use of a sacrificial layer enables character-
ization of the top surface of isolated polyamide films.
We compress membranes in a cross-flow system at 150 psi for
12 h to simulate operating conditions in RO modules. SI Ap-
pendix, Fig. S2 and Table S1 show that membrane thicknesses
decrease by 25% and 8% due to compression for brackish water
(BWXLE) and seawater high-rejection (SWHR) membranes,
respectively. We denote membranes that are compressed before
analysis with a “-C” after the membrane abbreviation. We propose
that examining the effects of the isolation procedure is important
to ensure minimal introduction of artifacts. The polyamide top
surface of a compressed membrane (SWHR-C, Fig. 1B) before
SCIENCES
in thickness of isolated polyamide films when the relative humidity
(RH) is changed from 0 RH to 88% RH. We find that the swollen,
hydrated thickness of the SWHR-C and BWXLE-C membranes
increases by 23% and 10% from their dry-state morphologies,
respectively (SI Appendix, Fig. S5). Thus, we focus on character-
ization of dry membranes, as our results suggest significant mor-
phological changes for hydrated membranes are not expected.
HAADF-STEM Tomography and 3D Model Quantification. We obtained
a tilt series by the acquisition of HAADF-STEM images at var-
ious tilt angles (Fig. 1C) up to ±65° (SI Appendix, Figs. S6 and
S7). Tilt series of the polyamide film were aligned and the 3D
volume was reconstructed using FEI Inspect3D software. The
reconstructed grayscale 3D model was segmented using Avizo 3D
software to obtain a binary volumetric model and visualize the
polyamide film (Fig. 1D). Video reconstructions as a function of
z-height for each tomogram are shown in Movies S1 and S2. The
reconstruction is segmented through thresholding individual XY
planes and is therefore dependent on the grayscale intensity of
each voxel (Fig. 2A). Gold nanoparticles, applied to the surface of

Culp et al. PNAS | August 28, 2018 | vol. 115 | no. 35 | 8695
the membrane before tomography, serve as fiduciary markers and
permit high-quality volume reconstructions.
The segmented binary volumetric model separates the selected
tomogram space into three parts: polymer film, closed voids within
the film, and vacuum (in the microscope). Fig. 2A shows an ex-
ample of the resulting 3D reconstruction and corresponding
thresholding for SWHR-C. This segmentation enables analyses of
the 3D volume in terms of multiple microstructural parameters; in
this work, we focus on the closed void fraction (voids within the
membranes), overall surface area, and void fraction along the
depth of the film.
Previous work based on cross-sectional TEM images of 60- to
100-nm-thick ultramicrotomed sections suggests the presence of
closed voids throughout polyamide active layers (25, 45). These
features are subject to the limitations imposed by the projection
of the structure onto 2D images and overlapping features. From
our 3D reconstructions, we can select regions where a close pore
is apparent in the cross-sectional view, such as in Fig. 2B. Fig. 2C
shows a series of images along the y axis (in XZ plane) of three
1-nm-thick cross-sectional slices with a spacing distance of 4 nm
based on the region identified in Fig. 2B. The selected region
(left slice) indicates a closed void. The visualization of the same
region a 4-nm step further along the y axis (middle slice) reveals
this enclosed “pore” becomes larger, and another 4-nm extension
(right slice) shows that the pore opens to the top surface, indicating
it contributes to the surface area of the polyamide film. Further-
more, the polymer volume completely separates vacuum on either
side, indicating that there are no observable pores at the current
resolution (1–5 nm depending on local variations in polyamide
thickness) that percolate through the thickness of the
membrane (46).
If we define the void fraction as the ratio of the volume of the
closed voids to the total polymer volume, we can compute this
measure of the closed porosity for our entire 3D reconstructions.
We find the closed void fraction is 0.12% and 0.04% for SWHR-
C and BWXLE-C membranes, respectively. These results are in
contrast to, and more than two orders of magnitude smaller than,
recent reported values (25). We speculate that overestimation of
void fractions in the literature are from artifacts due to the
thickness of the 2D projection cross-sectional images or from the
use of pristine instead of compressed membranes. A near-zero
void fraction of the SWHR-C and BWXLE-C membranes sug-
gests many features that were interpreted as closed voids in
previous studies (1, 23, 25, 45, 47, 48) are actually accessible to
the top surface and thus contribute to overall filtration surface
area. Further, the small amount of internal voids appears to have
little variance between commercial RO membranes examined
Fig. 2. Analyses of 3D reconstructions reveal that most pores in cross-
sectional images are connected (open) to the top surface of the mem-
brane. (A, Left) Single slices of the XY (Top), XZ (Middle), and YZ (Bottom)
planes. (A, Right) Corresponding thresholding needed for segmentation
procedure. (B) Single-slice cross-section of SWHR-C tomogram near the tilt
axis (XZ). (C) Zoomed-in region of the boxed area in B with subsequent slices
4 nm in depth along the y axis showing that the pore visible in B is open to
the top surface 8 nm further into the film.
8696 | www.pnas.org/cgi/doi/10.1073/pnas.1804708115
Fig. 3. Quantitative analyses of 3D reconstructions are insensitive to
thresholding procedure. (A) Single-slice cross-sections of the SWHR-C to-
mogram for five intensity values used for thresholding (1–5 from top to
bottom; 5 is most aggressive while 1 is least aggressive). (B) Porosity as a
function of film thickness (Z-height) and thresholding intensity value de-
termined from polymer areal fraction at each individual XY plane of the
SWHRC-tomogram. The polyamide thickness is ∼170 nm. (C) Cross-section
TEM micrograph of a ∼70-nm-thick SWHR-C membrane section obtained
from ultramicrotomy. The rough, top surface of the polyamide active layer is
apparent and the underlying layer is the polysulfone support layer.
here and thus seems to have little significance on membrane
transport properties.
We calculate the top surface area of each segmented model
and normalize it by the projected area. The normalized surface
areas for the SWHR-C and BWXLE-C tomograms are 3.48 ± 0.15
and 3.07 ± 0.04, respectively, indicating that the unevenness of the
polyamide surface contributes about three times more surface area
per unit projected area. In contrast, values measured from AFM
are about a factor of two lower, only 1.63 ± 0.08 for SWHR-C
and 1.27 ± 0.05 for BWXLE-C membranes (SI Appendix, Tables
S2 and S3); AFM values agree with previously reported values (18,
21, 49). A possible explanation for the reduced surface area by
AFM measurements is that an AFM tip cannot reach all of the
accessible surface area due to the complex, or “leaf-like,” folding
polyamide morphology formed during interfacial polymerization,
as highlighted in SI Appendix, Fig. S8 (50, 51). The larger surface
area from 3D reconstructions compared with AFM images is
consistent with previous work where nanoparticle filtration and
3D SEM data suggest that top surface nodules contribute to the
permeable area (8).
Analyses along the z axis yields polymer areal fraction as a
function of depth and thus membrane thickness can be defined by
this profile. First, we define a “low-porosity” polyamide region as
when the porosity, denoted as 1-polymer fraction (by volume), is
less than 5% for a given z value. Thus, the first z-slice on the
bottom of the tomogram is defined as z = 0 nm, and we evaluate
the porosity as a function of height within the polymer film (Fig.
3C and SI Appendix, Fig. S9), where a porosity of 1 indicates all
vacuum and 0 indicates all polymer. An initial decrease from 1 to
0 represents the roughness on the polyamide bottom surface (near
the polysulfone interface), and the increase back to 1 is represen-
tative of the polyamide roughness on the top surface. The porosity
profiles indicate a portion of the polyamide film that is completely
free of voids (within the tomographic resolution of about 5 nm)
near the bottom polyamide surface, confirming the results from
other studies (23, 36, 52, 53). By our definition of a low-porosity
region, we can quantify the low-porosity polymer layer thickness for
each polyamide film (SI Appendix, Tables S4 and S5). The low-
porosity layer thicknesses are 21 nm and 62 nm for the SWHR-C
and BWXLE-C membranes, respectively, and are consistent with
apparent dense layers observed in previous electron micrographs
of cross-sections (23, 24). As discussed below, this definition of
a low-porosity layer does not address the possibility of varying
density within polymer regions. The 1-polymer fraction profiles
can also be used to estimate the maximum thickness of the
Culp et al.

Fig. 4. (A) XZ planes of the thresholded volume of SWHR-C and BWXLE-C
tomograms with intensity displayed as a heat map (red corresponds to higher
intensity). (B) Average voxel intensity from tomograms as a function of z-
height for the SWHR-C and BWXLE-C membranes. Each data point repre-
sents the average intensity of each voxel in a given XY plane only where
polyamide is located (i.e., vacuum contributions are neglected). Contributions
from gold fiduciary markers have been removed. The bottom of the tomo-
gram (below the polyamide bottom surface) is defined as z = 0. The poly-
amide top surface is at approximately z = 280 nm for both membranes.
polyamide film, or when the polymer fraction goes to zero. The
thicknesses of the SWHR-C and BWXLE-C films are about 170 nm
and about 190 nm, consistent with previous reports (26). Moreover,
these results present a different way of envisioning RO membranes;
instead of a void-filled, 200-nm-thick active layer, the polyamide thin
film may be a void-absent film of 60 nm or less with a surface area
more than double what was previously measured (18, 21).
HAADF-STEM image intensities are directly proportional to
the density of the sample at a given position, enabling a local
analysis of polymer density within membranes. Thus, if we ex-
amine a cross-section of the tomogram reconstruction such that
only the polymer regions are visible (obtained via thresholding),
we can examine local variations in density within polyamide thin
films. As shown in Fig. 4A and Movies S3 and S4, significant
heterogeneity in polymer density is present throughout both
SWHR-C and BWXLE-C active layers. As shown in Fig. 4B, in-
tegrating the tomogram intensities for only the polymer regions
leads to a polymer density profile as a function of film thickness.
For both the SWHR-C and BWXLE-C membranes, polymer
density is highest near the top surface, and in particular within
protruding features that contribute to the surface roughness, or
“polyps.” The profiles shown in Fig. 4B also demonstrate that the
bottom surface is on average of higher density compared with the
middle of the film. As a consequence, we speculate that limiting
barrier layers of two high-performance, commercial RO mem-
branes are near the polyamide top surface, although bottom layers
may contribute as well. Indeed, the larger increase in density
near the top surface for SWHR-C membranes compared with
BWXLE-C membranes suggests a larger barrier layer, which is
consistent with the lower permeability of SWHR membranes (30,
54). The location of regions of high polymer density may differ for
other commercial and experimental membranes, and we propose
that the density analysis developed here is needed to pinpoint
crucial transport elements and barriers.
Culp et al.
Evaluating Tomogram Reproducibility. The choice of thresholding
values is critical and can have large impact on the segmented
binary models and the final obtained quantitative information
from reconstructed 3D tomograms. Previous work has explored
the thresholding dependence on structural parameters of 3D
reconstructions and in some cases even used an algorithm to
determine the appropriate thresholding (55–57). Nevertheless,
ambiguity could exist in accurately identifying the boundary be-
tween polyamide and vacuum or voids given the complex struc-
ture and modest contrast. As such, we propose to systematically
vary the intensity where thresholding takes place. The different
thresholding procedures create a set of segmented models for a
given tomogram. We controlled the thresholding starting from a
conservative value that retains more of the polymer fraction
(model 1) to a limit where the polymer layer was thin and broken
through (model 5); details of the thresholding procedure can be
found in Materials and Methods. From segmented models 1
through 5, we observe a decreasing polyamide film thickness in
1-nm-thick XZ planes of the segmented models of the SWHR-C
tomogram (Fig. 3A). To verify our segmented models accurately
represent the morphology of polyamide thin films, we compare
with a cross-sectional TEM image of the identical membrane
(Fig. 3B). SI Appendix, Fig. S10 displays the results of a similar
analysis performed for the BWXLE-C tomogram.
We further investigate the dependence of void fraction, surface
area, low-porosity layer thickness, and porosity profile along the
z direction on the subsequent segmented binary models using dif-
ferent thresholding values. The systematic thresholding variations
show only slight variations in low-porosity layer thickness and porosity
profiles that is due to the influence of thresholding on the overall
polyamide film thickness (Fig. 3C and SI Appendix, Fig. S9 and
Tables S4 and S5). Other parameters such as the void fraction and
surface area show negligible dependence on tomogram thresholding,
indicating that our thresholding procedure accurately represents the
structure of the polyamide film (SI Appendix, Tables S4 and S5).
Tomogram reproducibility was analyzed by examining the var-
iability of the polyamide surface area of the SWHR-C tomogram
(SI Appendix, Table S6). We progressively separate each tomo-
gram into smaller tomograms with equivalent projection areas and
examine the resulting variability in surface area. As expected, the
standard deviation of the surface area increases as the subdivision
area is reduced due to the higher variability in the structure.
Nevertheless, when the subdivision area is 3.4 μm2 (four subdivi-
sions) or 1.5 μm2 (nine subdivisions), the standard deviations are
nearly equivalent, suggesting a 1.5-μm2 projected area is sufficient
to statistically capture the heterogeneity in the microstructure; our
ENVIRONMENTAL
SCIENCES
Fig. 5. Schematics of models for location of layers with high polymer
density in polyamide thin films. (A) If a high-density layer is at the poly-
sulfone interface, then the projected area Am is crucial to establish transport
properties. (B) Layer with high polymer density in the middle of the mem-
brane. Again the projected area is the most accurate representation of
membrane area. (C) A layer of high polymer density located at the water
interface, where now the surface area is needed to obtain flow properties.
PNAS | August 28, 2018 | vol. 115 | no. 35 | 8697
projected area of our 3D reconstruction is nearly 10 times larger
(13.4 μm2).
Discussion
The production rate of water from an RO membrane (Qw) is a
function of both the area of the membrane, Am, as well as the
membrane thickness, L, as described by widely used solution
diffusion transport models that simplify to Eqs. 1 and 2 for most
RO applications [see, e.g., Geise et al. (58)]:
Pw M w
Qw = Jw Am = Am ðΔP − ΔπÞ [1]
L RT
Pw Mw
permeance = A = , [2]
L RT
where Jw is the water production rate per unit area, Pw is the pure
water permeability of the membrane, Mw is the molecular weight
of water, R is the gas constant, T is temperature in degrees
kelvin, ΔP is the pressure drop across the membrane, and the
Δπ is the osmotic difference across the membrane.
Despite the apparent simplicity of Eqs. 1 and 2, the challenge
with applying these equations is obtaining values for Am and L
for commercial RO membranes. Thus, the permeance A, com-
monly referred to as the “A value,” is currently used to characterize
membrane performance; but, this lumps multiple parameters to-
gether and prohibits the development of structure–function rela-
tionships. In this work, we demonstrate that the surface area of
membranes is significantly higher than the projected area, and for
any given point on the membrane the effective thickness varies
significantly at the nanoscale. Our work presents a method to
identify and describe the relevant dense-layer thickness of RO
membranes using quantitative analysis of RO tomography data.
We propose that either the projected area or the actual surface
area (that we determine using tomography) should be used to
model flux depending on the distribution and location of the actual
dense layer (that provides the highest resistance to flow) of the
membrane (Fig. 5). If a dense layer is identified close to the in-
terface between the polyamide active layer and polysulfone support
layer, as evidenced by high polymer density that is separated from
the top rough surface (as depicted in Fig. 5 A and B), we hypothesize
that the use of projected area to model transport is appropriate
because the top layers would then provide little resistance to
flow compared with the layer of high density. If, however, there
is evidence that a barrier layer could be adjacent to the top
surface area (Fig. 5C), as based on recent nanoparticle filtration
experiments (32), then the actual surface area would be more
relevant to determine transport correlations. If the density of the
membrane is homogeneous, then membrane properties must be
defined locally (at the nanoscale) to account for different
thicknesses. We propose that detailed tomographic studies on a
wide range of membranes, possibly with higher resolution than
those achieved in this work, will be crucial to unequivocally
establish the location of the dense layer and enable modeling of
transport properties as well as development of robust structure–
function relationships.
In the case of commercial RO membranes examined here, we
hypothesize that the higher polymer density near the top surface
(Fig. 4B) establishes a dense layer and suggest that membrane
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8698 | www.pnas.org/cgi/doi/10.1073/pnas.1804708115
properties should be analyzed and predicted based on the actual
surface area as determined from techniques such as tomography.
Given that this area is much larger than the projected area, reported
flux values are currently significantly overestimated. Additionally,
the length scale for resistance in transport models such as that
represented in Eqs. 1 and 2 will likely correlate with the average
thickness of the high-density layer adjacent to the top surface of the
membrane and could be determined using techniques described in
this study. Qualitatively, we show that the higher increase in polymer
density for SWHR-C membranes near the top surface is consistent
with lower permeability compared with BWXLE-C membranes.
In summary, we demonstrate that compression of RO mem-
branes via cross-flow filtration before characterization is both more
representative of the membrane structure under operational con-
ditions and minimizes structural rearrangement during solvent-
based active layer isolation procedures. We present an active layer
isolation procedure that enables the confirmation of minimal
polyamide structural rearrangements of compressed membranes
using AFM. We establish that HAADF-STEM tomography is an
excellent tool to both visualize and quantify the internal nano-
structure of polyamide films. We find that closed void fractions are
0.12% and 0.04% for the SWHR-C and BWXLE-C membranes,
respectively, and are more than two orders of magnitude lower
than previously reported values. We also find that the surface area
of the polyamide top surface is double what has been conven-
tionally measured with AFM, due to the increase in accessible area
from presence of voids connected to the top surface. We extract a
polymer region on the polyamide bottom surface with a porosity of
less than 5%, which can be calculated by the porosity curves from
the tomograms. The low-porosity layer thicknesses for the SWHR-C
and BWXLE-C membranes were 21 nm and 62 nm, respectively,
and agree with previous studies; nevertheless, we propose that
these values are not the key step in connecting structure to
transport. Instead, we propose that polymer density and its dis-
tribution dictate flow, wherein membranes that show highest
polyamide density near the top surface as shown here will require
measurements of the actual surface area to determine relevant
flux values. Altogether, using RO membranes as an example, our
results demonstrate the importance of 3D characterization at the
nanoscale to elucidate fundamental underpinnings of membrane
properties. We propose that local variations in porosity, density,
and surface area will lead to heterogeneity in flux within membranes,
such that connecting chemistry, microstructure, and performance of
membranes for RO, ultrafiltration, virus and protein filtration, and
gas separations will require 3D reconstructions from techniques such
as electron tomography.
Materials and Methods
Materials and methods for membrane compression in a cross-flow device,
polyamide film isolation, RH ellipsometry data acquisition, AFM data acqui-
sition, cross-section image acquisition, and electron tomography acquisition
and analysis can be found in SI Appendix.
ACKNOWLEDGMENTS. The authors thank Prof. Andrew Zydney and Robert
Cieslinski for educational discussions and Jennifer Grey for assistance with
tomography data acquisition and software support. This work was supported
by Dow Chemical Company Agreement 225559AK/177526 and NSF Grant
DMR-1609417 (to T.E.C. and E.D.G.). Flat-sheet membranes were provided
courtesy of Dow Water & Process Solutions.
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PNAS | August 28, 2018 | vol. 115 | no. 35 | 8699