Mechanical Characterization of Polyurethane Elastomers: For

Retrofitting Application against Blast Effects

H. M. C. C. Somarathna1, S. N. Raman2,*, K. H. Badri3, A. A. Mutalib1

1
Department of Civil and Structural Engineering, Universiti Kebangsaan Malaysia, 43600 UKM Bangi,
Selangor, Malaysia.
2
Department of Architecture, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia.
3
Polymer Research Centre (PORCE), Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor,
Malaysia.
*Email: [email protected]; [email protected]

ABSTRACT: In recent years, structural and materials engineers have focused their attention to
develop feasible, constructible and cost effective retrofitting techniques to enhance the structural
capacity and to minimize the damage due to impulsive loadings such as blast and impact. In this
aspect, elastomeric polymers offer a unique proposition as retrofitting material for civil
infrastructures, due to their attractive characteristics and morphology such as high elongation
and energy absorption capacity. However, comprehensive understanding and proper evaluation
of their characteristics and behavior are vital prior to developing a feasible retrofitting technique
based on these materials. This paper discusses on the findings of experimental investigations
undertaken to evaluate the mechanical properties under uniaxial tensile loading of selected types
of palm-oil based polyurethane which were prepared by varying the chain extender
(Polyethylene glycol, PEG), for it to be utilized as a retrofitting coating material on reinforced
concrete structures, to enhance their resistance to blast effects. It was found that the properties
of polyurethane elastomer are within the desired range and there is a higher possibility to apply
the material as a sustainable and feasible retrofitting application for reinforced concrete
structures under impulsive loadings.

1 INTRODUCTION
Presently, consideration of utilizing polyurethane (PU) polymers for structural and
infrastructural applications becomes a competitive area due to its captivating morphology and
characteristics as a material: highly elastic, flexible and resistant to impact, abrasion and
aggressive weather condition (Chattopadhyay & Raju, 2007). PU covers an extremely wide
range of applications, such as in bedding materials, adhesives, thermal insulation, the
manufacture of tires, as well as in structural elements. PU capitalizes on its wide range of
mechanical properties due to the ability to alter its microstructure. PU is formed by the rapid
chemical reaction of diisocayante [a monomer with at least two isocyanate (–NCO) functional
groups] with diol [another monomer containing at least two alcohol (hydroxyl, or –OH) groups],
in the presence of a catalyst (Chattopadhyay & Raju, 2007; Badri, 2012). Generally, PU is a
linear segmented blocked copolymer comprising of “soft” and “hard” segments, and an increase
in content of hard segment results in increased ultimate strength, and tensile flexural modulus
while decreasing the strain capacity (Russo & Thomas, 1983). Micro separation of those
domains due to the dissimilarity of properties is responsible for the wide range of properties of
the PU and broad class of polymer (O’Sickey et al., 2002).
Most elastomers exhibit a high degree of strain rate dependency, stress–strain non-linearity, and
a high level of pressure dependency when compared with other construction materials mainly
due to the complexity of their microstructures (Bahei-El-Din & Dvorak., 2007; Raman et al.,
2012). In addition, PU demonstrates a higher energy absorption density compared to other
elastomeric materials. In past few decades, polymer spray-in-place application technique has
been introduced, and were used in numerous industrial application as strengthening surface
coating to improve the durability and as secondary coating on several types of structural
elements, including in roofs, bridges, and parking decks, coating for insulation, and protective
coating for tank liners, tunnel and manhole. These polymers have also indicated the capacity as
a strengthening coating application to resist extreme loadings of blast and ballistic in concrete
structures. The findings of previous studies have indicated that in addition to enhancing the
structural capacity against blast effects, the application of elastomeric polymer coatings
(including PU) was also effective in minimizing the fragmentation, controlling the deformation
and displacement, and collapse potential of the several types of structural elements such as
unreinforced masonry walls, metallic structures, composite structural systems, and concrete
structures (Davidson et al., 2004; Bahei-El-Din & Dvorak., 2007; Tekalur et al., 2008; Amini et
al., 2010; Grujicic et al., 2012; Raman et al., 2012; Ackland et al., 2013).
The comprehensive understanding on the behavior of these polymeric materials is necessary
prior to recommending them as an effective and feasible alternative to existing structural
retrofitting materials. The mechanical behavior of elastomeric polymers such as PU and
polyurea has been studied by several researchers in recent times. Generally, impulsive loadings
are associated with high loading rates, therefore synthesis of the characteristics and behavior of
the material under a wide range of strain rates (quasi-static and high strain rates) is essential for
such applications. One of the earlier studies on the high strain rate characteristics of elastomeric
polymers was by Yi et al. (2006), where they investigated the compressive stress–strain
behavior of three types of PU and one polyurea samples using the split Hopkinson pressure bar
system. Their findings highlighted that the polymeric materials show a highly non-linear
behavior in stress–strain relationships, and indicated strong hysteresis and rate dependency.
Sarva et al. (2007) reported on the uniaxial compression stress-strain behavior of one of the PU
sample and the polyurea sample studied by Yi et al. (2006), over a wide range in strain rates
(from 0.001 s-1 to 10,000 s-1). Shim and Mohr (2009) performed relaxation experiments,
continuous and multi-step compression experiments within strain rate ranges of 10-3 to 101 s-1,
and compressive strains up to 1. Roland et al. (2007) reported on the behavior of polyurea in
tension over the strain rate region of 0.06 to 573 s-1, while Raman et al. (2013) reported the
findings of a series of uniaxial tensile test that were conducted on polyurea for strain rates
ranging from 0.006 to 388 s-1. This paper presents the findings of an experimental investigation
program undertaken to analyze the tensile stress-strain behavior of three types of palm-based
PU samples produced by varying the plasticizer (chain extender) content in the quasi-static
regime.
2 EXPERIMENTAL PROCEDURE

2.1 Materials
Palm-based polyol (PKO-p), 2,4-diphenylmethane diisocyanate (MDI), Acetone and
polyethylene glycol (PEG) were synthesized at the Polymer Research Centre (PORCE), of
Universiti Kebangsaan Malaysia (The National University of Malaysia), Bangi, Malaysia.

2.2 Preparations of the Palm oil-based polyurethane elastomer

The palm-based PU elastomer was synthesized from the rapid reaction between PKO-p and
MDI with PEG as the plasticizer via pre-polymerization. Three types of PU were casted with
three different PEG contents (0, 6, and 12 (wt. %)) with respect to the weight of the PKO-p,
while keeping the mix percentage of PKO-p, MDI and Acetone ratio constant at 1: 0.8: 0.35
throughout the experiment. The three types of PU were synthesized by solution casting process
and were referred to as PU0, PU6 and PU12, (PU6 indicate that the PU contained 6% PEG).
Clear yellowish and bubbleless PU samples were prepared, and cured at ambient temperature.

2.3 Tensile test

The tensile specimens were tested uniaxially on a Instron Universal Testing Machine in
accordance to the ASTM D 412: Method A specification. Dumbbell shaped test specimens with
average thickness of 3 mm were cut from the pre-casted PU sheets [Figure 1(a)], in the same
direction of the sheets, in order to minimize the effect of anisotropy or grain directionality due
to the direction of the flow during the preparation and the processing of the PU sheets. All
dumbbell shaped test specimens were cut using a die C in accordance with the dimension
selection procedure described in the specification. The median of three measurements were used
for the dimensions (width and thickness) of each samples. During the testing, all test specimens
were clamped in to the grip automatically with a clamping distance of 65 mm, were tested with
a uniform rate of 50 mm/min [Figure 1(b)], at ambient temperature.

(a) (b)

Figure 3. The: (a) Dimensions of specimens (in mm) prepared for the uniaxial tensile test; and (b)
Performance of the uniaxial tensile test.
3 RESULTS AND DISCUSSION

3.1 Tensile Characteristics

In this study, the tensile test at quasi-static loading condition was performed at a rate of 0.033
s-1. This rate of straining was within the quasi-static strain rates adopted by Roland et al. (2007)
and Raman et al. (2013) in their studies. Figure 2(a-c) show the quasi-static engineering stress-
strain curves for the three types of PU composition that were analyzed in this study. All tensile
characteristics reported in this paper were computed based on the engineering stress-strain
parameters of the samples.

3.1.1 PU0
Sample PU0 (which contained 0 % PEG) exhibited an initial linear region in the engineering
stress-strain curves with an average Young’s modulus of 146 MPa [Figure 2(a)]. Subsequently
after the linear region, the material started yielding after reaching an elongation of 8.5 % with a
yielding stress of 12 MPa, and which resulted in permanent or inelastic deformation. The
material underwent a brief period of yielding until achieving an elongation of 18 % while the
stress increased until it reached a value of 15.5 MPa, and subsequently continued until it
achieved 35 % elongation while reducing the stress to 14.8 MPa. At this stage, the PU samples
would have gone through a structural breakdown in its molecules, and following in permanent
deformations (yielding) and undergoing large elongations while having marginal decrement in
the applied stress. After this stage, the PU exhibited an almost linear curve, before the
subsequent failure after an (average) elongation of 68%, while having an average stress of 14.2
MPa at rupture.

3.1.2 PU6
PU6 samples recorded a Young’s modulus (average) of 61 MPa, where it reached an elongation
of 10% with a yielding stress of 5.2 MPa, and started yielding after that respective point [Figure
2(b)]. The PUs underwent a period of yielding until achieving an elongation of 28% at a stress
of 7.0 MPa. Further application of load after this point resulted in a marginal increase in the
stress, showing a strain hardening mechanism. Subsequently the PUs exhibited a linear
relationship of stress and strain over significant range of strain (28 to 177%), prior to failing
after an (average) elongation of 177%, with a (average) fracture stress of 9.3 MPa.

3.1.3 PU12
The average Young’s modulus of PU12 samples was 12 MPa, with an average yield stress of 2
MPa after reaching an elongation of 12%. Subsequently PU samples underwent a brief period of
yielding until reaching an elongation of 34% at a stress of 2.8 MPa [Figure 2(c)]. Since the
samples will have gone through a breakdown in its molecular structure after this point, it
resulted in permanent deformations with large elongations while showing only a minor
increment in the resulting stress. Further application of load resulted in PU12 samples
undergoing strain hardening mechanism as PU6. Failure occurred at an average elongation of
close to 200%, with an average fracture stress of 4.5 MPa.
 (a) (b)

(c)

Figure 2. The engineering stress-strain curves of: (a) PU0 samples; (b) PU6 samples; and (c) PU12
samples.

3.2 Comparison of tensile properties

The obtained results were analyzed and the variation of the properties are illustrated in Figure 3.
Stress-strain relationship of selected specimens of the three types of PU is shown in Figure 3(a),
and it generally followed the shape of typical elastic-plastic material behavior for PU6 and
PU12. Both PU6 and PU12 also exhibited strain hardening mechanism. Meanwhile, PU0
exhibited the highest Young’s modulus (146 MPa), while the lowest value (12.0 MPa) was
recorded by PU12. From PU0 to PU12 (i.e. when the plasticizer content was increased), the
Young’s modulus decreased significantly. Even though the same amount of plasticizer was
increased in each stage (from PU0 to PU6 and from PU6 to PU12), the reduction of Young’s
modulus from PU0 to PU6 was nearly 1.8 times compared with the decrement from PU6 to
PU12. The addition of plasticizer (i.e. the chain extender) increases the length of pre-polymer
chain, and leads to the polyurethane sample to posses a higher mobility in their molecular
structure, thus resulting in reduced stiffness in the material.
In addition, the failure stress gradually decreased from PU0 to PU12, and the decrement shows
approximately similar value. The failure strain increased during this period and the strain
increment from PU0 to PU6 is significant compared to the increment from PU6 to PU12.
Therefore it can be concluded that, the content of plasticizer has significantly affected to the
tensile properties of PUs.

(a) (b)

(a) (d)

Figure 4. The tensile mechanical characteristics of the three PU samples: (a) Stress-strain curve; (b)
Young’s modulus; (c) Tensile stress at rupture; and (d) Strain at rupture.

3.3 Strain energy

In the initial elastic region of the stress-strain curve, the deformation resulting from the applied
axial load was not accompanied by dissipation of energy. The applied load was stored as strain
energy in the material throughout its volume which resulted in elastic deformation, due to the
“work” (product of applied load and deformation) done by the material (Hibbeler, 2011). The
energy absorption capacity of the material is another key property which should be considered
for a retrofitting material. The resilience modulus and the toughness modulus characterize the
density of embedded strain energy for a given volume of the material. The resilience modulus of
the material depicts the ability of the material to absorb the energy imparted without
experiencing permanent deformation or damage. The resilience modulus for PU0, PU6 and
PU12 were 0.56, 0.30 and 0.14 x 106 J/m3, respectively, and the toughness modulus were 9.44,
13.28 and 6.97 x 106 J/m3, respectively. Even though the resilience modulus showed a
decreasing trend from PU0 to PU12, PU6 recorded the highest toughness modulus, since strain
capacity was increasing from PU0 to PU12. The toughness modulus represents the strain energy
density in the material just before undergoing failure (Hibbeler, 2011). The PUs evaluated in
this study have exhibited toughness modulus that were almost 17, 44 and 50 times higher their
resilience modulus. These findings have provided a good agreement to the main objective of the
current study to investigate the PU as a retrofitting material for structures subjected to high
impulsive loadings. It indicates that PU would be able to absorb considerable amounts of energy
even after yielding of the material. This characteristic is preferred in a retrofitting material,
distinct to most brittle materials that are used in construction such as concrete and ceramics,
which would fail suddenly after their yielding.

(a) (b)

Figure 4. The tensile mechanical characteristics of the three PU samples: (a) Strain energy density vs.
strain; (b) Strain energy at failure.

4 CONCLUSIONS
This paper presented the findings from the experimental investigation undertaken to analyze the
behavior of three types of palm-based PU samples with varying plasticizer content, under
uniaxial tension. The following conclusions have been drawn based on the findings this study.

1. Stress-strain relationship indicated that all types of PU samples deform significantly

after reaching its yield point and it will not fracture suddenly without a warning prior to
failure, and PU12 exhibits the higher performance while PU0 showing the lower
performance under this behavior.

2. Addition of plasticizer significantly influenced the tensile characteristics of the PU

samples, i.e. by decreasing the Young’s modulus and fracture stress, while enhancing
the elongation capacity from PU0 to PU12.

3. Even though the resilience modulus was decreased from PU0 to PU12, PU6 shows best
energy absorption capacity among all, since it exhibited the highest toughness modulus.

4. PU0 shows a behavior of a material which is high in stiffness but lower in terms of
toughness, while the behavior of PU12 was like a material which is high in toughness
but lower in stiffness. PU6 exhibited a behavior of a material which has desirable
stiffness and toughness qualities.
ACKNOWLEDGEMENT
The authors would like to extend their gratitude to the Ministry of Education of Malaysia in
providing the necessary funding for this research through the ERGS Grant Scheme
(ERGS/1/2013/TK03/UKM/02/6).

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