Journal of Materials Processing Technology 124 (2002) 238–243

The influence of humidity on the deformation and

fracture behaviour of PMMA
A.M.S. Hamouda*
Faculty of Engineering, Department of Mechanical and Manufacturing Engineering,
Universiti Putra Malaysia, Serdang, 43440 Selangor, Malaysia

Abstract

The effect of relative humidity on the tensile deformation and fracture of poly(methylmethacrylate) (PMMA) has been studied. Seven sets
of samples were conditioned under different environment: as-received specimens; dry specimens (zero moisture content); outdoor exposed
specimens; water saturated specimens; specimens conditioned at three different relative humidities (75.5, 85.1, and 94.6%) using saturated
salt solutions (NaCl, KCl, and KNO3, respectively). The main objective of this study is to investigate the effects of sorbed water on tensile
mechanical properties of PMMA. Properties investigated include development of crazing, tensile fracture stress, strain to fracture and fracture
surface morphology. # 2002 Published by Elsevier Science B.V.

Keywords: Poly(methylmethacrylate); Tensile deformation; Relative humidity

1. Introduction about by polymers. No less dramatic and certainly more

Most materials are subject to weathering. The earth’s crust
is degraded by chemical and physical processes as a result of
exposure to the surrounding environment. The rate of dete-
rioration depends on the nature of the material; for the
hardest rocks the time scale stretches to millions of years
whereas for some organic polymers major changes can be
induced by exposure of a few days.
Synthetic polymers offer an impressive range of attractive
properties and in many of their applications they are exposed
to the outdoor environment (e.g. sunlight, temperature,
moisture). This could lead to the changes of physical and
mechanical properties of polymers. For example, polymers
and composites are widely used externally as well as intern-
ally in aircraft because of the substantial weight saving they
provide. Likewise in boat construction, plastics, composites
and synthetic fibres are displacing more conventional
materials. A similar development has occurred in the build-
ing industry where plastics are competing successfully with
wood, glass, metal and stone as construction materials. The
modern sports stadium with its transparent canopy, row of
injection-moulded ABS seats and polypropylene ‘grass’ in
many ways highlights the revolution in materials brought
*
Tel.: þ603-948-6101-2083; fax: þ603-894-8839.
E-mail address: hamouda@eng.upm.edu.my (A.M.S. Hamouda).
important has been the impact of plastics in agriculture.
Whatever the application, there is often a natural concern
regarding the durability of polymeric materials partly
because of their relative newness but also because of the
useful lifetime of these materials can be predicted where
their maintenance and replacement can be planned.
The deterioration of a material depends on how and to
what extent it interacts with its surroundings. The outdoor
environment if considered in terms of sunshine, temperature,
rainfall and wind, varies widely in duration, intensity and
sequence. As regards the durability of materials the weight-
ing, which should be given to severe climatic conditions,
depends on the confidence level required in the performance
of the material but in general it is the time-averaged climatic
factors, which should be considered. It is through the pre-
valence of certain elemental features for prolonged periods
that the concept of climate has evolved.
In this study, poly(methylmethacrylate) (PMMA) was
selected to investigate the effects of moisture content on
its properties. PMMA is an amorphous glass below 110 8C
and exhibits brittle fracture under normal conditions below
80 8C [1]. PMMA have wide range of applications, which
are principally concerned with transparency and light trans-
fer, with good weathering resistance, and with high surface
hardness and durability. They include glazing in aircraft and
other transport, transparent guards and covers, lenses, baths,
washbasins and sanitary ware, and rear-light assemblies for
road transport. Since most of the PMMA applications are

0924-0136/02/$ – see front matter # 2002 Published by Elsevier Science B.V.

PII: S 0 9 2 4 - 0 1 3 6 ( 0 2 ) 0 0 0 9 6 - 1
 A.M.S. Hamouda / Journal of Materials Processing Technology 124 (2002) 238–243
subjected to wet environment, residual stress in the shaping,
which can add to the moisture absorption and lead to
crazing. Further development of crazing will result crack
and rupture.
The tensile deformation behaviour of PMMA has been
examined by various investigators over a wide range of
temperature and strain rate [2–4]. However, the influence of
humidity on mechanical properties of PMMA has received
much less attention compared to nylon [5,6].
In this paper, experiments were carried out to identify the
values of tensile stress and strain to fracture for PMMAs
specimens with different percentage of water concentra-
tions. Scanning electron microscope (SEM) analysis was
focused on the effects of the moisture on the deformation
behaviour and fracture mechanics of PMMA at the fracture
point.
2. Material and methodology
2.1. Material and conditioning
The material used was commercially available PMMA
rod, 16 mm in diameter. Solid cylindrical samples were
machined using CNC turning machine from the rods into
tensile specimens with dimension f 16 mm  210 mm with
gauge diameter 9.70 mm. Two sets of tensile test were
performed, the first set was carried out on dry specimens
(zero moisture), and the second set was carried out on
specimens with different level of moisture contents. The
second sets of the specimens were conditioned at three
different relative humidities (75.5, 85.1 and 94.6%) using
saturated salt solutions (NaCl, KCl and KNO3, respectively)
at ambient temperature. All the specimens were conditioned
until the water content reach equilibrium. Samples of high
water content were observed to be somewhat hazy and less
transparent than normal PMMA.
To obtain dry samples, the test specimens were heated in a
vacuum oven at 50 8C for a period of 70 h [7]. Water
saturated samples were obtained by storing test specimens
in liquid water for 45 days at room temperature.
2.2. Moisture absorption isothermal
The moisture sorption isotherm was constructed using
gravimetric method (continuous registration of weight
changes). Sellable glasses made containers were used to
contain the saturated salt solution and the specimens, which
were placed about 3 cm above the water level and separated
by a filter paper [8].
2.3. Tensile test
Methods of tensile test are based on British Code of
Practice (BS.2782) [9] and ASTM Standard (D638-91)
[10], wherever applicable. All the specimens with different
239
level of moisture content were tested using Instron 8020
Universal Testing Machine with capacity of 250 kN with
ram velocity of 1.00 mm/min. Tensile stress–strain curves
are obtained. The main objectives of the tests are to obtain
the values of tensile strength and strain to fracture, and the
relation of tensile strength and tensile stress–strain to frac-
ture versus water contents for PMMA.
2.4. Surface morphology
Fracture surfaces are examined using JEOL JSM 6400
SEM. Prior to SEM examination, the fracture surfaces were
coated with a thin layer of gold–palladium using Polaron
E5100 SEM Coating Unit to prevent surface charging.
3. Result and discussion
3.1. Water absorption in PMMA
In order to obtain variety of relative humidities (75.5,
85.1, and 94.6%), three types of saturation salt solutions
(NaCl, KCl, and KNO3, respectively) were prepared. Inten-
sities of these saturated salt solutions were calculated as
shown in Table 1. Relative humidities were not monitored as
this was previously done by Greenspan [11].
The changing in the weights of PMMA samples during the
conditioning process to different relative humidities and
liquid water environment were monitored from time to time
to get the water content in the samples as a function of time.
It has been found that all the samples exhibited the same
behaviour as time increases water content increases. How-
ever, the rate of water absorption decreases with respect to
time. It was found that samples in liquid water environment
leads to the rate of water absorption; followed by 94.6, 85.1,
and 75.5% relative humidity.
It was also found that increasing relative humidities from
75.5 to 94.6% had lead to the increasing of water content in
PMMA from 0.30 to 0.54% after being conditioned for 45
days in room temperature. This indicates that the increase of
water content in PMMA is due to the increases of relative
humidity at surrounding. For water saturated PMMA, it was
found that the water content has the highest value, 0.80%. It
is clear that PMMA will absorb more water in liquid water
environment rather than in water vapour surrounding. How-
ever these values are relatively low compared to other
Table 1
Intensities of saturated salt solutions
Salt Volume of still Intensity of saturated
water used (ml) salt solution (g/ml)
Type Weight (g)
NaCl 119.0070 450 0.2646
KCl 122.1578 450 0.2715
KNO3 126.0266 450 0.2801
240 A.M.S. Hamouda / Journal of Materials Processing Technology 124 (2002) 238–243

Fig. 1. The tensile strength response at different humidity levels.

Fig. 2. Average stress versus water content.

polymers such as Nylon 6 that can absorb both liquid water
and water vapour from surrounding in a proportion app-
roaching 9% by weight [12].
3.2. Calculation of mechanical properties
Overall, the values of mechanical properties were
obtained directly from the Instron machine during the tensile
testing. The tensile stress–strain response for different water
contents is shown in Fig. 1. Input parameters just before the
testing were carried out were gauge length and gauge
diameter. All the calculations for desired output parameters
had been carried out by the computer attached to the
machine. The average and standard deviation values were
also calculated.
but reduction in hardness and stiffness as described by
Hertzberg [13].
At water contents to 0.80%, the strain to fracture increases
and there is a significant reduction in the modulus. This
behaviour is indicative of water acting as a mild plasticizer
for PMMA, a conclusion similar to that drawn from rheo-
optical studies [14]. However, the behaviour of stress to
fracture and strain to fracture above 0.80% water concentra-
tion cannot be obtained since the highest water concentration
in samples is 0.80%. However, as water concentrations reach
1% or so, it is suggested [15] that some water molecules

3.3. Influence of water on mechanical behaviour of PMMA

The tensile stress–strain response is shown in Fig. 1 for

individual test samples having 0, 0.40, and 0.80% of sorbed
water. The average stress at fracture sf as a function of water
concentration is shown in Fig. 2 while the strain to fracture ef
is shown as a function of water concentration in Fig. 3.
With increase of water content to 0.40%, the average
stress to fracture falls gradually from 75.519 to 62.566 MPa
and then increase to 67.080 MPa at 0.44% water content
before falls more rapidly to 43.250 MPa at 0.80% water
content. The mechanism by which water is accommodated
in the PMMA microstructure appears to be changing with
increase in water concentration. The sorbed water, probably
by hydrogen bonding to the carbonyl groups in the PMMA
side chain, lowers inter-chain interaction and thereby
reduces glass transition temperature. This leads to the imp-
rovement of flexibility, ductility and toughness of polymers Fig. 3. Average strain at fracture versus water content.
 A.M.S. Hamouda / Journal of Materials Processing Technology 124 (2002) 238–243 241

Fig. 5. Fracture of dry.

in Fig. 6(a). Figs. 7–10 show similar scan for sample with
water content 0.30, 0.40, 0.44, and 0.46%, respectively.
Several broad, ribbed bands surround the smooth, slow-
growth portion of the fracture surface and the fast growth
region beyond the banded area is rough. The smooth pre-
crack source area, the ribbed bands and the remaining rough
fracture surface are characteristic features of tensile fracture
Fig. 4. Average tensile strength versus water content. in the PMMA. The ribbed bands are indicative of instability
in the crack propagation process. Their presence has been
discussed by Doyle [16] and attributed by him to a periodic
begin to cluster and act more as filler particles than as a slowing of the crack front movement due to energy expen-
plasticizer which leads to stress concentration effects, accent- diture in the development of craze bundles ahead of the fast
uates craze development and causes early fracture. moving crack front.
The influence of sorbed water on tensile strength for the The fracture surface for samples with 0.54% water con-
PMMA is shown in Fig. 4. All values cited are average tent is different from samples with lower water content.
values obtained from tests on three specimens. Dry samples Necking appeared prior to fracture as shown in Fig. 6(b)
have the highest average tensile strength, 73.397 MPa. With indicates that new deformation modes have developed and
the increase of water content, the tensile strength falls
gradually to 63.194 MPa at 0.40% water content and then
increases to 74.414 MPa at 0.54% water content before
reduces to 59.843 MPa at 0.80% water content. The drop
in tensile strength at 0.80% (water saturated) is about 18.5%
compared to the dry specimens.
As water content increases from 0 to 0.80%, there was a
significant change in deformation behaviour for PMMA
from brittle mode to ductile mode as shown in Fig. 1.
The area under the stress–strain curve up to fracture for
PMMA, which indicates the toughness, increases with
increasing of water content in PMMA from 0 to 0.80%.
This means that the increase of water in PMMA has led to Fig. 6. Diagrams of necking: (a) dry; (b) wet.
the increment of toughness. With higher water content,
ability of PMMA to absorb energy up to fracture will be
improved.

3.4. Surface morphology

The fracture surface morphology of PMMA did not vary

appreciably with the water content of the samples range
from 0 to 0.46%. The reason for this is that all the samples
fractured without shear yielding by craze breakdown and
subsequent rapid crack propagation. Fig. 5 shows a portion
of the fracture surface near to the fracture origin for a dry
sample. No necking was found for the dry sample as shown Fig. 7. Fracture at 0.30% water content.
242 A.M.S. Hamouda / Journal of Materials Processing Technology 124 (2002) 238–243
Fig. 8. Fracture at 0.40% water content.
Fig. 9. Fracture at 0.44% water content.
the fracture surface morphology changes. Both crazes and
shear bands are present. Instead of continued craze growth,
shear deformation modes develop which lead to necking and
more extensive plastic deformation. The surface crazes are
relatively small, and the growth is impeded by shear bands.
In many of the surface crazes the SEM scan shows that a
central cavity has started to form. With continued deforma-
tion, some of these small cavities open up into relatively
large diamond shaped, or truncated diamond shaped cav-
ities. While many of the small cavities have formed at the
centre of surface crazes, others have apparently formed in
regions where there is no visible evidence of crazes. These
may have initiated from local stress concentration sites
arising from the presence of contaminants. Similar cavities
are reported to occur in cellulose by Cornes et al. [17], which
does not craze.
Fig. 10. Fracture at 0.46% water content.
Fig. 11. Fracture at 0.54% water content.
Fig. 12. Fracture at 0.80% water content.
Fig. 11 shows a high magnification scan of a portion of the
fracture surface of 0.54% water content sample near to the
source of the fracture. Fracture has developed from lateral
extension and tearing of a small surface diamond cavity and
features of equivalent geometry are present on the opposite
fracture surface. The semi-circular, fan-shaped region show-
ing radial tear lines indicates the extent of the relatively slow
crack growth prior to rapid crack extension. Characteristics
such as those discussed above can be explained by; the
presence of small crazes and diamond shaped cavities on the
external surfaces, and a fracture that develops by further
extension and growth of one of the diamond cavities, are also
noted in water saturated samples with 0.80% water content
whose fracture surface is shown in Fig. 12.
4. Conclusions
The following conclusions can be drawn:
1. The strain to fracture for PMMA increases with the
increasing of water content.
2. The tensile strength for PMMA reduces with the
increasing of water content.
3. It is suggested that the water acts as mild plasticizer for
PMMA at water contents to about 0.80%.
4. The fracture toughness of PMMA increase as the water
content increase from 0 to 0.80%, which indicates that
the ability of energy absorbing up to fracture will be
increased.
 A.M.S. Hamouda / Journal of Materials Processing Technology 124 (2002) 238–243
5. PMMA samples with higher water content have
tendency to deform plastically before fracture where
crazes, shear bands, and diamond shaped surface
cavities were observed.
6. Fracture has occurred from growth, and then breakdown,
of a surface craze and the smooth region surrounding the
source is indicative of the extent of craze growth prior
to the length of the bar, which is the direction of the
principal stress.
Acknowledgements
The financial support provided by the Department of
Mechanical and Manufacturing Engineering, UPM, is grate-
fully acknowledged. The author would thank and express his
sincere appreciation to Mr. Te Chuan Keat, for his help with
the experimental work and Dr. Elsadig Mahdi and Ms.
Rohani Yusof, for their help in preparing the manuscript.
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