v Principles of Hemodialysis
Series Editor: William R. Clark
Properties of Membranes Used for Hemodialysis Therapy
William R. Clark*² and Dayong Gao³
*Renal Division, Baxter Healthcare Corp., McGaw Park, Illinois, ²Nephrology Division, Indiana University School
of Medicine, Indianapolis, Indiana, and ³Center for Biomedical Engineering, Department of Mechanical
Engineering and Membrane Science Center, University of Kentucky, Lexington, Kentucky
ABSTRACT
Recent trends show a progressive increase in the use of modi®ed
cellulosic and synthetic dialyzers and a corresponding decrease
in the utilization rate of unmodi®ed cellulosic dialyzers. The
purpose of this article is to describe current membrane and
dialyzer technology, with the focus almost entirely on modi®ed
As discussed earlier in this series (1), the ®rst hollow
®ber arti®cial kidney used clinically in the 1960s consisted
of a 1.0 m2 unmodi®ed cellulosic membrane. Hollow
®ber dialyzers with highly permeable polyacrylonitrile (2)
and polysulfone membranes (3) were subsequently
developed, as were dialyzers with modi®ed cellulosic
membranes. Over time there has been a progressive
increase in the use of modi®ed cellulosic and synthetic
dialyzers, predominantly in the high-eciency and high-
¯ux segments, respectively, and a corresponding decrease
in the utilization rate of unmodi®ed cellulosic dialyzers
(4). In fact, these latter dialyzers play a relatively limited
role in the current global hemodialysis (HD) market, for
which approximately 90 million units are now manufac-
tured annually. The movement away from unmodi®ed
cellulosic dialyzers has been driven largely by the desire to
extend the molecular weight spectrum of solute removal
and to minimize complement activation. In addition,
retrospective data suggest outcomes of patients treated
with these types of dialyzers are inferior to those achieved
with modi®ed cellulosic and synthetic dialyzers (5,6).
The purpose of this article is to describe current
membrane and dialyzer technology. A general overview
of membrane-related determinants of dialyzer perform-
ance is ®rst presented, followed by a discussion of speci®c
characteristics of some of the more commonly used
dialyzers.
Address correspondence to: William R. Clark, MD, Hemodi-
alysis Research Laboratory, Renal Division, Baxter Healthcare
Corp., Wishard Hospital/Myers Building D711, West 10th St.,
Indianapolis, IN 46202, or e-mail: bill_clark@baxter.com.
Seminars in DialysisÐVol 15, No 1 (January±February) 2002
pp. 191±195
191
cellulosic and synthetic membranes. A general overview of
membrane-related determinants of dialyzer performance is
®rst presented, followed by a discussion of speci®c characteris-
tics of some of the more commonly used membranes and
dialyzers.
Hollow Fiber Membrane Characteristics
In assessing the clinical e€ects of a particular dialyzer,
the membrane justi®ably receives the most scrutiny. In
this section several important characteristics determining
membrane performance are discussed. These include
hollow ®ber dimensions, surface area, porosity, and
water permeability.
Hollow Fiber Dimensions
An individual hollow ®ber can be viewed as a solid
cylinder in which the central region has been removed
(``cored out'') to form the blood compartment. The
process of manufacturing (``spinning'') a hollow ®ber
membrane is a complex one incorporating aspects of a
broad array of scienti®c disciplines, including polymer
chemistry, thermodynamics, reaction kinetics, and chem-
ical engineering (7). Although clear di€erences exist
among the various types of membranes (see below), a
number of common features are evident. From a
structural perspective, most hollow ®bers have a relat-
ively standard inner (blood compartment) diameter
(approximately 180±220 lm) and length (approximately
20±24 cm). These parameters are dictated essentially by
the operating conditions used during hemodialysis (HD)
and are the result of a compromise between opposing
forces. On one hand, a relatively small hollow ®ber inner
diameter is desirable because it provides a short di€usive
distance for solute mass transfer. At a given blood ¯ow
rate, a lower inner diameter also provides a higher shear
rate, resulting in greater attenuation of blood-side
boundary layer e€ects (8). However, a decrease in hollow
®ber inner diameter also has undesirable e€ects. Fluid
192 Clark and Gao
¯ow along the length of a cylinder (i.e., the axial ¯ow) in Afiber ˆ …2p†…10 4
m†…0:24 m†
many situations is governed by the Hagen±Poisseuile 4
equation (9): ˆ 1:51  10 m2 :

QB ˆ DP=…8lL=pr4 †: …1†
In this equation, QB is blood ¯ow rate, DP is axial
pressure drop, l is blood viscosity, L is ®ber length, and r
is hollow ®ber radius. A speci®c application of this
equation is axial blood ¯ow (i.e., from the arterial to the
venous end) in a hollow ®ber membrane during HD. A
more general form of equation 1 is
QB ˆ DP=R: …2†
From equations 1 and 2, the resistance to blood ¯ow
(R) is
4 related parameters for a hollow ®ber membrane used in
R ˆ 8lL=pr : …3†
Due to the inverse relationship between R and r4, a
small decrease in hollow ®ber inner diameter induces a
large increase in ¯ow resistance. Equation 3 also
demonstrates that increases in ®ber length and hemat-
ocrit (l) are associated with an increase in ¯ow resistance.
In turn, as indicated by equation 2, an increase in ¯ow
resistance results in an increase in axial pressure drop at a
constant blood ¯ow rate.
In contemporary HD practice, patients with pro-
gressively rising hematocrits are commonly treated
with large surface area dialyzers of high water
permeability. These dialyzers require relatively high
blood ¯ow rates (at least 350 ml/min) to derive
maximum bene®t from a solute removal perspective.
The high ¯ow resistance and associated large axial
pressure drop in this speci®c scenario result in
signi®cant back®ltration of dialysate under normal
HD operating conditions (10). The combination of
signi®cant back®ltration and contaminated dialysate
increases the likelihood of cytokine-inducing substance
transfer, as has been discussed recently (11). Modi®-
cations in hollow ®ber dimensions are constrained by
these considerations.
For the large surface area dialyzers routinely used
now, the total number of ®bers (N) typically used is
approximately 12,000. Therefore
Adialyzer ˆ …Afiber †…N†
4
ˆ …1:51  10 m2 †…12; 000†
ˆ 1:81 m2 : …5†
Membrane Pore-Related Characteristics
To provide rough quantitative estimates of pore-
HD, the straight cylindrical pore model can be used (12).
As shown in Fig. 1, this model assumes a membrane's
pores all have the same radius (rp), which is larger than
the radius (rs) of the hypothetical solute shown. In
addition, the directional orientation of the cylinders is
assumed to be perpendicular to the ¯ow of blood and
dialysate. As noted above, the Hagen±Poisseuile equa-
tion governs ¯uid ¯ow through cylinders in many
situations, applying also to transmembrane ultra®ltrate
¯ow through the pores in this membrane model. As such,
the rate of ultra®ltrate ¯ow is directly related to the
fourth-power of the pore radius (i.e., r4) at a constant
transmembrane pressure. Thus, although the number of
pores also in¯uences water permeability, the membrane
characteristic that most directly in¯uences water per-
meability is mean pore size.

Surface Area
For a particular hollow ®ber, the inner annular surface
represents the nominal blood compartment surface area
and is the theoretically maximal area available for blood
contact. For the entire group of ®bers comprising a
dialyzer, total nominal surface area then depends on ®ber
length, inner diameter, and overall number, the latter of
which varies generally from approximately 7000 to
14,000.
A frequently asked question relates to the manner in
which membrane surface area is calculated. For the inner
annular region of a single hollow ®ber described above,
the surface area (A) is given by the equation de®ning the
surface area of a cylinder:
Afiber ˆ 2prL: …4†
)4
FIG. 1. Pictorial representation of idealized, equal-sized pore
Based on assumed values of r ˆ 100 lm (10 m) and membrane model (lower panel) and the associated relationship
L ˆ 24 cm (0.24 m), the surface area of an individual between pore size and solute permeability (upper panel). Reprinted
hollow ®ber can be calculated as: with permission from Takeyama and Sakai (12).
 HEMODIALYSIS MEMBRANES 193
On the other hand, the di€usive properties of a
dialysis membrane are determined mainly by the
porosity (pore density) and, to some extent, the pore
size (13). Based on the cylindrical pore model described
above, membrane porosity is directly proportional to
both the number of pores and the square of the pore
radius (r2). Therefore di€usive permeability is also
strongly dependent on pore size, but not as strongly as
is water permeability. The major pore-related determi-
nants of ¯ux (r4) and di€usive permeability (number of
pores, r2) di€er suciently that the two properties can
be independent of one another for a particular
hemodialysis membrane. Speci®cally, cellulosic high-
eciency dialyzers typically have high di€usive per-
meability values for small solutes but low water
permeability. On the other hand, there are examples
of high-¯ux dialyzers that have signi®cantly lower small
solute di€usive permeabilities than comparably sized
dialyzers of much lower water permeability.
It should be noted that HD membranes used in actual
clinical practice demonstrate pores having a distribution
of radii and tortuous (noncylindrical) structures.
However, the cylindrical pore model is useful for a ®rst
approximation. The degree to which actual HD mem-
branes deviate from this ideal model and the clinical
implications with respect to solute removal will be
discussed in subsequent editions of this series.
FIG. 2. Sequence of steps in the conversion of a hollow ®ber to a
Non-Membrane-Related Determinants dialyzer for PMMA. Reprinted with permission from Sugaya and
of Dialyzer Performance Sakai (14).

rates. On the other hand, values greater than approxi-

In assessing the clinical e€ects of a particular dialyzer,
the membrane justi®ably receives the most scrutiny.
Although the membrane itself is a key determinant of
overall dialyzer function, the manner in which the
membrane interacts with other components of the
dialyzer is also very important. In Fig. 2, the sequence
of events resulting in the conversion of polymethylmeth-
acrylate (PMMA) hollow ®bers to a dialyzer is shown
(14). After removal of glycerin (used in the hollow ®ber
preparation), ®bers are covered with spacer yarns, which
are ®laments designed to create optimal spacing between
®bers (15). Subsequently the ®bers that eventually serve
as the collective membrane in the dialyzer are assembled
(``bundled'') and inserted in the dialyzer casing. The ®ber
bundle is then ``potted'' (encapsulated) at both ends with
silicone rubber and cut. Finally, the dialyzer is placed in a
pouch and the entire unit is sterilized, usually by ethylene
oxide, gamma rays, or steam.
Several of these manufacturing steps may have a direct
e€ect on dialyzer function and performance. Fiber
bundle con®guration and spacing have a major impact
on mass transfer, as has been demonstrated recently
(16,17). One consideration is the spacing of ®bers within
the bundle. However, of equal or greater importance is
the degree to which the dialyzer jacket is ``packed'' with
®bers. A dialyzer's packing density is the ratio of the area
comprised of ®bers to the total area, based on a
transverse cut through the dialyzer. Empirically, packing
densities less than approximately 50% imply insucient
membrane surface area for an appropriate set of ¯ow
mately 60% are associated with a high risk of dialysate
¯ow maldistribution in which dialysate is ``channeled'' to
the peripheral aspect of the ®ber bundle, at the expense of
¯ow to the inner bundle area. Finally, sterilization
technique may in¯uence the dialyzer performance
through an e€ect on mean membrane pore size.
Dialyzer Classi®cation by Membrane
Composition (Table 1)
Unmodi®ed Cellulosic Dialyzers
The constituent component of cellulosic membranes is
cellobiose, a saccharide found in a number of naturally
occurring substances (18). From the perspective of
blood's interaction with a cellulosic membrane, the most
important characteristic of cellobiose is its high density of
hydroxyl groups. Although the contact of blood with any
arti®cial surface elicits activation of the alternative
complement pathway, the abundance of hydroxyl
groups makes this phenomenon particularly pronounced
for unmodi®ed cellulosic dialyzers. This cellulosic char-
acteristic was deemed clinically undesirable when ®rst
reported and has contributed to the progressive decline in
unmodi®ed cellulosic use over the years. However, the
relatively long duration of popularity of cellulosic
membranes can be explained largely by their particular
suitability for a di€usion-based procedure like hemo-
dialysis. The underlying hydrogel structure of these
194 Clark and Gao
TABLE 1. Hemodialysis membranes
Unmodi®ed Modi®ed cellulosic
cellulosic (substance group) Synthetic
Cuprophan Cellulose (di) acetate Polysulfone
(acetate)
Cuprammonium Cellulose triacetate Polyamide
rayon (acetate)
SCE Hemophan Polyethersulfone
(tertiary amine)
SMC (benzyl) PAN
Vitamin E-bonded PMMA
membranes and their tensile strength allow the combi-
nation of low wall thickness (see below) and high
porosity to be attained in the ®ber spinning process
(19). These characteristics allow the attainment of high
rates of di€usive membrane transport and ecient
removal of small, water-soluble uremic solutes, such as
urea and creatinine. Another characteristic feature of
these membranes is symmetry with respect to composi-
tion, implying an essentially uniform resistance to mass
transfer over the entire wall thickness. On the other hand,
these membranes are characterized by low mean pore size
and pronounced hydrophilicity, such that neither trans-
membrane nor adsorptive removal of middle and larger
size uremic toxins is signi®cant (20,21).
Modi®ed Cellulosic Dialyzers
Similar to regenerated cellulose membranes, modi®ed
cellulosic membranes are characterized by low wall
thickness values, typically in the 6±15 lm range, and
symmetric structures. However, dialyzers composed of
these membranes, ®rst used for HD in the 1980s, cause
less pronounced complement activation and generally
have larger mean pore size (22) than their unmodi®ed
cellulosic counterparts. This latter characteristic results
in higher water permeability and middle molecule
clearances relative to the unmodi®ed cellulosic class.
The two most commonly used modi®ed cellulosic
dialyzers contain membranes in which the hydroxyl
replacement mechanisms are quite di€erent. For cellu-
lose acetate membranes (rigorously cellulose diacetate)
(23), approximately 75% of the hydroxyl groups on the
cellulosic backbone are replaced with an acetate group.
As opposed to a hydroxyl group, an acetate group does
not bind avidly to a C3 molecule to initiate activation of
the complement cascade. Consequently complement
activation is attenuated, as is the leukopenic response,
in which the white blood cell (WBC) count decrease from
baseline is usually in the 35±40% range. Because
production of cellulose triacetate membranes involves
complete hydroxyl substitution replacement, further
attenuation of complement activation and leukopenia
is achieved (22).
Along with cellulose acetate dialyzers, Hemophan
dialyzers are the most commonly used products contain-
ing modi®ed cellulosic membranes (24). However, the
substitution approach is completely di€erent from that
used for cellulose acetate. For Hemophan, only a small
percentage (less than 5%) of the hydroxyl groups are
actually replaced. However, the tertiary amine replace-
ment group is bulky and e€ectively shields a signi®cantly
greater percentage of hydroxyl groups by a steric
mechanism. The attenuation in the degree of comple-
ment activation and leukopenia with Hemophan dialyz-
ers is similar to that observed with cellulose acetate
dialyzers. This same approach of providing a low degree
of hydroxyl substitution with a relatively bulky moiety is
employed for synthetically modi®ed cellulose (SMC), a
more recently developed membrane for which the
substitution group is a benzyl moiety (25).
Synthetic Dialyzers
Synthetic membranes were developed essentially in
response to concerns related to the narrow scope of
solute removal and the pronounced complement activa-
tion associated with unmodi®ed cellulosic dialyzers. The
AN69 membrane, a copolymer of acrylonitrile and an
anionic sulfonate group, was ®rst employed in ¯at sheet
form in a closed-loop dialysate system in the early 1970s
(2). Since that time a number of other synthetic
membranes have been developed, including polysulfone
(3), polyamide (26), PMMA (27), polyethersulfone (28),
and polyarylethersulfone/polyamide (29). Largely rela-
ted to the interest in hemo®ltration (HF) as an ESRD
therapy in the late 1970s and early 1980s, along with the
inability to use low-¯ux unmodi®ed cellulosic dialyzers
for this therapy, these membranes were initially formu-
lated with high water permeability (3,30). The large mean
pore size and thick wall structure of these membranes
allowed the high ultra®ltration rates necessary in HF to
be achieved at relatively low transmembrane pressures.
However, with the waning of interest in HF as a chronic
dialysis therapy in the late 1970s and early 1980s,
dialyzers with these highly permeable membranes were
used subsequently in the di€usive mode as high-¯ux
dialyzers. This latter mode continues to be the most
common application of these membranes, although they
are increasingly being employed for chronic hemodia®l-
tration (HDF) (31). Synthetic dialyzers with relatively
low water permeability (32) also are now utilized in
certain markets.
An obvious di€erence between synthetic and cellulosic
membranes is chemical composition. As opposed to
naturally occurring cellulose, synthetic membranes are
manufactured polymers that are classi®ed as thermo-
plastics. In fact, for most of the synthetic membranes, the
hemodialysis market represents only a small fraction of
their entire industrial utilization. As noted above,
another feature di€erentiating cellulosic and synthetic
membranes is wall thickness. Synthetic membranes have
wall thickness values of at least 20 lm and may be
structurally symmetric (e.g., AN69, pPMMA) or asym-
metric (e.g., polysulfone, polyamide, polyethersulfone,
polyamide/polyarylethersulfone). In the latter category,
a very thin ``skin'' (approximately 1 lm) contacting the
blood compartment lumen acts primarily as the mem-
brane's separative element with regard to solute removal.
The structure of the remaining wall thickness (``stroma''),
which determines a synthetic membrane's thermal,
chemical, and mechanical properties, varies considerably
 HEMODIALYSIS MEMBRANES
among the various synthetic membranes (14,33). For
example, the stroma has a relatively homogeneous,
spongelike consistency in the Fresenius polysulfone
membrane. On the other hand, the Gambro Poly¯ux
membrane, which is actually a blend of polyamide
and polyarylethersulfone, has three distinct layers.
Similar to the Fresenius polysulfone membrane, one
layer is a thin, blood-contacting inner lumen, composed
of polyarylethersulfone enriched with polyvinylpyrolli-
done (PVP), while the outer surface is composed of
relatively PVP-free polyamide (see below for a discussion
of PVP). Interspersed between these two layers is a
polyarylethersulfone stroma (33). Finally, the DiaPES
polyethersulfone membrane, developed by Membrana
GmbH, contains both inner and outer skin layers
surrounding a spongelike stroma (34). For this mem-
brane, the average pore radii of the inner and outer skin
layers are approximately 5 and 10 nm, respectively.
Takeyama and Sakai (12; Fig. 1) have suggested an
e€ective mean pore radius of 5±8 nm achieves the
appropriate balance between b2-microglobulin removal
and albumin loss.
Many of the synthetic polymers used in the manufac-
turing of the above membranes are hydrophobic and
require the addition of a hydrophilic agent (PVP) to
avoid excessive protein adsorption upon blood exposure.
During membrane preparation, water-soluble PVP is
blended into the hydrophobic base polymer through the
formation of hydrogen bonds (26). This hydrogen
bonding provides miscibility for the hydrophilic±hydro-
phobic mixture and prevents leaching of PVP during
blood contact. In addition to imparting hydrophilicity,
PVP also in¯uences membrane pore size distribution
through its e€ects on pore surface tension, and its content
may vary considerably across a synthetic membrane's
wall thickness.
Conclusion
A general overview of membrane-related determinants
of dialyzer performance has been provided, along with a
speci®c discussion of some of the more commonly used
membranes and dialyzers used in HD. Future editions of
this series will provide additional information regarding
speci®c membrane and dialyzer properties in¯uencing
small solute removal, middle molecule removal, and
biocompatibility.
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