Journal of Saudi Chemical Society (2010) 14, 251256

King Saud University

Journal of Saudi Chemical Society

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Improving the design stresses of high density

polyethylene pipes and vessels used in reverse
osmosis desalination plants
Abdulwahid Al-Hajjaj
a
b

a,*

, Tahseen A. Saki

Chemical Engineering Department, College of Engineering, University of Basrah, Basrah, Iraq

Chemistry Department, College of Science, University of Basrah, Basrah, Iraq

Received 4 November 2009; accepted 8 January 2010

Available online 4 February 2010

KEYWORDS
Nanocomposite materials;
Montmorillonite
nanoparticles;
High density polyethylene;
Mechanical properties;
Reverse osmosis;
Membrane vessels

Abstract Nanocomposite materials have been used on a wide scale in industrial and structural
applications. The present work aims at studying the mechanical properties of high density polyethylene (HDPE) grade TR-401 hexene copolymer reinforced by montmorillonite nanoparticles
(MMT), used to fabricate pipes and membranes vessels for reverse osmosis desalination plants. Different volume fractions and particle sizes of the MMT clay were used to investigate the effect of this
ller on the mechanical properties of the produced composite. Mechanical properties tests were carried out and good improvements of the composite properties were obtained compared to the parent
polymer. The test results showed a signicant enhancement of the mechanical properties at low ller
proportions. Pipe fabricated from these composites had many outstanding and desirable features.
For example, by adding 4.75% MMT to the HDPE produced quality pipes and ttings with the
highest design stress basis of any polyethylene. A signicant increase in the modulus of elasticity
observed, together with an unusual increase in the design stress, approved the HDPE/MMT composite for high pressure piping and membrane vessels used in reverse osmosis desalination plants.
2010 King Saud University. All rights reserved.

1. Introduction
* Corresponding author.
E-mail address: aahajjaj@yahoo.com (A. Al-Hajjaj).
1319-6103 2010 King Saud University. All rights reserved. Peerreview under responsibility of King Saud University.
doi:10.1016/j.jscs.2010.02.018

Production and hosting by Elsevier

Polymeric materials are being increasingly used as construction materials in different industrial plants. The biggest use
of plastics is for piping; sheets are also used for lining vessels
and for fabricated ducting and fan casings. Mouldings are used
for small items; such as, pump impellers, valve parts and pipe
ttings. Many factors have to be considered when selecting
engineering materials, but for Reverse Osmosis plants (RO)
the overriding consideration is usually the ability to resist the
high operating pressure.

252

A. Al-Hajjaj, T.A. Saki

Nomenclature
E
Vf
t
e
r
f
P

Young modulus
volume fraction
Poissons ratio
elongation at break point
stress
nominal design strength
pressure

One of the disadvantages in the application of polymers in

the engineering eld is their low stiffness and strength compared with metals, where their moduli of elasticity and their
strength are about (100) times less metals (Al-Hil et al.,
2007). The mechanical strength and other properties of polymers are modied by melt mixing with particulate and bers
as well as by blending with other polymers. In the last few
years, nano structure polymer composites have generated a
considerable interest in the materials research community because of their potential for remarkable improvement of
mechanical, thermal and physicochemical properties when
compared with conventional polymer composites even at very
low ller concentration (Strawhecker and Manias, 2000; Manias et al., 2001; Zeng et al., 2002; Pandey and Singh, 2004; Jain
et al., 2005; Gurmendi et al., 2006; Crosby and Lee, 2007; Pettarin et al., 2008; Ren et al., 2009). Even though it has been
shown that these materials have the potential to have excellent
mechanical properties, the relatively high costs of development
and manufacturing of nanoscale/polymer composites have
been prohibitive (Odegard et al., 2005; Malicka and Domka,
2008). When reinforced with nano-llers thermoplastic polymers can have a strength equivalent to mild steel, and can be
used for pressure vessels and pressure piping (Sinnott, 2003).
Among the vast nano-reinforcements available for fabricating
polymer nanocomposites, clays have been focused and studied
the most because they are naturally occurring minerals that are
commercially available, exhibit a layered morphology with
high aspect ratios, large specic surface areas, and have substantial cation exchange capacities (Dasari, 2007; Gu et al.,
2009). Many clays are aluminosilicates, which have a sheet-like
(layered) structure, and consist of silica tetrahedra bonded to
alumina octahedra in a variety of ways. A three-layer minerals
(combination of one octahedron with two tetrahedral layers)
results in smectite clays, the most common of which is montmorillonite (Vogt and Vogt, 2004). Montmorillonite (MMT)
is the most common type of clay used for nanocomposite formation; however, other types of clay can also be used depending on the precise properties required from the product
(Strawhecker and Manias, 2000; Reichert et al., 2000; Jain
et al., 2005; Gurmendi et al., 2006).
Polyethylene (PE), a class of high performance engineering
thermoplastics nds important utilization in a wide range of
extrusion, blown objects and injection molding applications.
Probably one of the most important properties of polyethylene
is its mechanical properties. Generally the mechanical performance of a thermoplastic depends upon the molecular structure, the spatial arrangement of molecules, and the type and

Subscript
c
composite
m
polymer matrix
f
ller
p
particles
t
test
d
design
a
at test temperature
n
at design temperature

amount of reinforcing materials. In the recent decade, comprehensive investigations have been conducted to improve the
mechanical properties of polyethylene using organic and inorganic llers (Zeng et al., 2002; Frankland et al., 2003; Lei et al.,
2006; Al-Hajjaj et al., 2007; Ananeva et al., 2008). Although it
has been long known that polymers can be mixed with appropriately modied clay minerals and synthetic clays, the eld of
polymer nanocomposites has gained strong momentum recently (Manias et al., 2001). There are three methods to prepare PE/clay hybrids: in situ polymerization, solution
intercalation, and melt intercalation. Melt intercalation is the
most convenient and appropriate technique for the industrial
preparation of polymer/clay nanocomposites (Lei et al.,
2006; Guo et al., 2009).
The present work aims at studying the mechanical properties of HDPE grade TR-401 hexene copolymer reinforced by
MMT nanoparticles, used to fabricate pipes and membranes
vessels for reverse osmosis desalination plants.
1.1. Theoretical aspects
The overall mechanical response of composite materials when
subjected to mechanical loading is provided by the stress-strain
relationship. An accurate prediction of mechanical properties
is difcult due to the complex interactions of the materials,
as well as the size, orientation and the distribution of the ller
particles. A general theory, such as the rule of mixtures, can
predict the general trends of the properties which requires
the development and application of mechanical properties of
polymer composites, have been discussed in many papers
and reviews (Qian et al., 2000; Liu and Chen, 2003; Van Workum and de Pablo, 2003; Chen and Liu, 2004).The theory of
Nicolais and Narkis (1971) predicts the following relation to
determine the yield stress of the composite:




ryc rym 1  vf =vm 2=3
1
Marrett et al. (2003) reported that Einsteins theory can be
used to predict the increase in Youngs modulus due to the
addition of rigid, spherical llers as shown in Eq. (2) given
by Tavman (1997) from the original work by Nielsen (1967):
Ec Em 1 2:5vf

For polymers containing nearly spherical particles of any

modulus, the Kerner equation (Kerner, 1956) can be used to
calculate the modulus of a composite if there is some adhesion
between the phases. Lewis and Nielsen (1970) showed that the
Kerner equation could be generalized to predict any modulus:

Improving the design stresses of high density polyethylene pipes and vessels used in reverseosmosis desalination plants

253

Mc Mm


Mf =7  5tm Mm 8  10tm Mf fVm =151  tm g


Mm Vf =7  5tm Mm 8  10tm Mf g fVm =151  tm

5
6

3
where M is shear, Youngs, or bulk modulus.
Assuming a perfect adhesion between ller and matrix, the
reduced elongation to break in a system lled with spherical
particles can be estimated using the following equation
(Nicolais and Narkis, 1971):


4
c m 1  v0:33
f
The above theories indicate that the elastic modulus of a
composite material would be independent of the size of the ller particles. However, experiments generally show an increase
in modulus (or viscosity of suspensions) as the particle size decreases (Nielsen, 1991).
The operational pressure of Reverse Osmosis (RO) system
is a function of the salinity of the feed water. The salinity results in a colligative property known as osmotic pressure.
The osmotic pressure of the fresh waters is very much lower
than that of seawater or brine (i.e. the osmotic pressure for
normal seawater is closer to 25 bar). By applying pressure (in
excess of the osmotic pressure) to the brine water, the process
can be reversed and fresh water can be forced through to the
other side of a semi-permeable membrane. Generally RO process is characterized by its high operating pressure, especially
through the membrane vessels and water discharge pipes.
For the purposes of design and analysis, pressure vessels
and pipes are sub-divided into two classes depending on the ratio of the wall thickness to vessel diameter: thin-walled vessels,
with a thickness ratio of less than 1:10; and thick-walled above
this ratio. The majority of the vessels and pipes used in RO
desalination systems are classied as thin-walled vessels.
Beer and Johnston (1992) proposed to determine the stresses exerted on small element of wall of a cylindrical vessel containing a uid under pressure with sides, respectively, parallel
and perpendicular to the axis of the cylinder. Because of the
axisymmetry of the vessel and its continents, it is clear that
no shearing stress is exerted on the element. The principal
stresses acting at a point in the wall of a vessel, due to a pressure load, are shown in Fig. 1. If the wall is thin, the radial
stress r3 will be small and can be neglected in comparison with
the other stresses, and the longitudinal and circumferential
stresses r1 and r2 can be taken as constant over the wall
thickness.
For a cylindrical vessel of inside diameter D and wall thickness t, the longitudinal and circumferential stresses due to pressure (internal or external), given by:

r1 PD=4t
r2 PD=2t

For design purposes it is necessary to decide a value for the

maximum allowable stress (nominal design strength) that can
be accepted in the material of construction. The design stress
for a material, and the value used in any design calculations,
is based on the tensile strength, or on the yield or proof stress.
Proof stress is the stress to cause a specied permanent extension, usually 0.1% of this extension. The national pressure vessel codes and standards require that all pressure vessels be
subjected to a pressure test to prove the integrity of the nished
vessel. The vessel is tested at a pressure above the design pressure, typically 2530% higher. The test pressure is adjusted to
allow for the difference in strength of the vessel material at the
test temperature compared with the design temperature.
Pt 1:25Pd fa =fn

For design purposes it is necessary to decide a value for the

maximum allowable stress (nominal design strength) that can
be accepted in the material of construction. For materials
not subject to high temperatures the design stress is based on
the yield stress, or the tensile strength (ultimate tensile stress)
of the material at the design temperature.
A hydraulic test is normally carried out, but a pneumatic
test can be substituted under circumstances where the use of
a liquid for testing is not practical. Hydraulic tests are safer because only a small amount of energy is stored in the compressed liquid (Sinnott, 2003).
2. Materials and methods
A commercially available grade of HDPE TR-401 hexene
copolymer with a melt ow index (MFI) of 0.12 g/10 min.
and 0.945 g/cm3 density were used in this study. MMT nanoparticles with an average size less than 50 nm, has been used
as reinforcing material.
Seven hybrid HDPE/MMT nanocomposites with MMT
loadings of 1.5, 3, 4.5, 4.75, 5, 6 and 8 wt% were prepared.
Dispersing clay particles in a polymer matrix is very difcult
and the particle surfaces must be modied to enhance the compatibility of the ller with the matrix; therefore alkyl ammonium is used to achieve the desired ller-matrix compatibility.
All the composite samples were prepared by melt compounding. Polyethylene with different weight percentages of
the clay powder was mixed in a Haake rheomix 600 mixer at
165 C and 30 rpm for 15 min. As a reference, unlled polyethylene sample was also processed in the Haake mixer under the
same conditions. A tensile specimen of dumbbell shape with
standard dimensions was obtained by compression molding.
Tensile testing was carried out using an Instron testing machine
1193 with a cross-head speed of 50 mm/min; the tests were carried out at room temperature according to ASTM D638.
In the hydraulic proof test the stresses induced in pipes and
vessels during the test were monitored using strain gauges. The
requirements for the proof testing of pipes and vessels are set
out in the codes and standards (Sinnott, 2003).
3. Results and discussions

Figure 1

Principal stresses in pressure- vessel wall.

The tensile strength is a measure of the basic strength of a

material. It is the maximum stress that the material will with-

254
stand, measured by a standard tensile test. From this test, a
number of important parameters can be calculated, such as
the apparent modulus, the tensile strength at yield, the tensile
strength at break point, and the ultimate elongation to
rupture.
Semi-crystalline polymers such as polyethylene typically
display necking behavior and a yield point in tensile stress/
strain curves. Yield points are always associated with a deformation mechanism which absorbs energy. For semi-crystalline
polymers this mechanism involves orientation and destruction
of micron to colloidal scale semi-crystalline morphologies. The
yielding phenomenon is really due to a dewetting effect in
which the adhesion between the ller and matrix phases is
destroyed.
Fig. 2 shows the tensile properties as a function of MMT
loading. For all compositions, the tensile strengths of nanocomposites were higher than those of pure HDPE. The maximum tensile strength has been observed at 4.75 MMT wt%
with a value of 40% higher than that of the parent polymer.

Figure 2 Tensile properties of the HDPE/MMT nanocomposite

(m). For comparison, macro composite (dp = 20 lm) also shown
(d).

A. Al-Hajjaj, T.A. Saki

Manias et al. (2001) reported that the tensile strength is not affected by the nanocomposite processing since the nanocomposite structure does not change markedly with the
processing conditions (i.e. whether the hybrid is formed by
melt-intercalation or by extrusion), while Reichert et al.
(2000) revealed that considerable tensile enhancements can
be achieved only where appropriate compatibilizers are used
to pretreat the clay mineral in conjunction with specic organic
modication of the MMT.
The adhesion between the ller and matrix play the main
role of the elongation behavior of polymer composites. Significant decreases in elongation percentage are illustrated in the
same gure. This gure shows that a dramatic decrease can
be brought about only by a small amount of ller. The addition of llers decreased the elongation at the break point,
which is a direct contrast to the adhesion force between the ller and the polymer matrix, accordingly to the polymer chain
mobility and elongation (Ward, 1983). In general, the above
results show that adding a small amount of the nanoparticles
drastically enhances the decreasing of the elongation percentage of the polymer composite, since the particle size decreases
tend to decrease with corresponding decreases in maximum
packing volume, Eq. (4).
As can be observed from the gure, the values of Youngs
modulus increased continuously when the clay content was increased. In general, the above results show that adding a small
amount of the nanoller drastically enhances the increasing of
the modulus of the polymer composite. Strawhecker and Manias (2000) and Manias et al. (2001) have revealed that dramatic
increases in Youngs modulus can not be assigned to the use of
higher modulus inorganic ller layers when incorporated with
very low proportions of MMT ller. A layer of affected polymer on the ller surface is one of the recent theoretical approaches which assumed a much higher Youngs modulus
than the bulk equivalent polymer. This was due to the region
of the polymer matrix physisorbing on the silicate surfaces,
that reinforcing the material by the strong bonding and adhesion with the ller surfaces (Shia et al., 1998). In such a case,
where ller aspect ratios are high, then the surface area in contact with the polymer will be very large giving rise to huge increases in the modulus with very low MMT. Generally, the
modulus of a composite depends upon the ratio of moduli of
the two phases, M1/M2, as dened by Eq. (2). The greater
the modulus ratio, the greater is the modulus of the composite.
For comparison, conventionally lled HDPE/MMT macro
composites are also shown on the same gure.
Vessels and pipes materials must be selected to withstand
the maximum pressure to which it is likely to be subjected in
operation. For vessels and pipes under RO process operating
conditions, the design pressure is normally taken as the pressure at which the relief device is set. This is normally being
510% above the normal working pressure, to avoid spurious
operation during minor process upsets. The national pressure
vessel codes and standards require that all pressure vessels be
subjected to a pressure test to prove the integrity of the nished
vessel.
The typical RO membrane vessels are of 8 in diameter
tubes, therefore tube samples with the same diameter have
been made from the prepared HDPE/MMT nanocomposites
to carry out the hydraulic test.
The hydraulic test results for different wall thicknesses were
shown in Fig. 3. As shown from the gure, the 4.75 wt%

Improving the design stresses of high density polyethylene pipes and vessels used in reverseosmosis desalination plants
50

Test pressure (bar)

4.75 wt% MMT/HDPE nanocomposite

40

Pure HDPE

30
20
10
0

Tube wall thickness (mm)

Figure 3

The hydraulic test of the HDPE/MMT nanocomposite.

MMT/HDPE nanocomposite produced quality pipes and ttings with the highest design stress basis of any polyethylene.
The material properties of a polymer composite are strongly
dependent on the degree of intimate contact between the
phases, as for example when nano-scale reinforcing material
is incorporated in the polymer, thus the stresses are much more
effectively transferred from the polymer matrix to the ller and
a remarkable improvement takes place in the design stress
when compared with pure polymer. However, the signicant
increase in the design stress approved the present HDPE/
MMT composite for high pressure piping and membrane vessels used in reverse osmosis desalination plants.
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