Materials and Design 30 (2009) 13371340

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Technical Report

Behaviours of glass bre/unsaturated polyester composites under

seawater environment
Huang Gu *
School of Textiles, Tianjin Polytechnic University, 63 Chenglin Road, Hedong District, Tianjin 300160, PR China

a r t i c l e

i n f o

Article history:
Received 12 March 2008
Accepted 10 June 2008
Available online 18 June 2008

a b s t r a c t
Glass bre reinforced unsaturated polyester laminates were fabricated by using the VARI (vacuum
assisted resin infusion) technique. Laminates were immersed in the articial seawater for various periods. Moisture absorption would increase the weight of the specimen, soluble elements extraction may
decrease the weight of the material. The tensile and bending strength of the seawater treated samples
showed a decreased trend with prolonged treating time implying the degradation of the composites.
The SEM photograph of the broken section after the treatment illustrated serious corrosion of the
interface.
2008 Elsevier Ltd. All rights reserved.

1. Introduction

2. Experimental

Fibre reinforced composites have been the alternatives of steel,

metal and wood in many applications. This may be due to their
high specic tensile and compressive strength, good fatigue and
corrosion resistance and their suitability for the production of
complex-shape components with reduced manufacture times
compared to conventional metallic materials. The application of bre reinforced composites has been driven by various attractive aspects like ease of handling, high adaptability, economy of
fabrication, and damage tolerance.
Among the bre reinforced materials glass bre reinforced
products (GRP) are the cheapest and consequently have the highest
potential of being cost effective [13]. Glass bre reinforced composites are commonly used as light-weight materials in a wide
variety of marine applications such as boats, ships, shing trawlers
and under sea pipes. Wide-scale usage of GRP is seriously hindered
by the lack of experimental data and understanding of durability
aspect in the seawater environment [48]. To assume long-term
durability, a fundamental understanding is essential in terms of
strength and material degradation. The objective of this study is
to investigate the corrosion behaviours of the GRP under seawater
conditions.
Glass bre reinforced unsaturated polyester laminates were
fabricated by using the VARI technique. After treatment by the articial seawater, the weight change, the tensile strength, the bending behaviour of the specimens were measured and analysed.
The SEM image of the broken section of the seawater treated specimen was shown.

The specications of the E-glass fabric (Tianjin Synthetic Fibre

Company, PR China) used in the investigation are listed in Table 1.
Laminates were fabricated by using the vacuum assisted resin
infusion technique. The unsaturated polyester was employed as
the matrix and corresponding accelerator and initiator were used.
Laminates with two and four layers were produced separately.
Specimens prepared for the tensile strength test were cut and
the measurement was carried out according to the Chinese Standard GB1447-1983, the standard was worked out based on ASTM
D3039. The specications of the specimen are presented in Fig. 1.
Dimensions of the specimen are shown in Table 2.
Samples for the bending strength test were prepared with rectangle specimen and the testing was made according to the Chinese
Standard GB3356-1999, the standard was worked out based on
the ASTM D5023. The sample length was 180 mm and width
20 mm. Before exposure to the seawater, all specimens were dried
until constant weight was reached. The articial seawater was
prepared by mixing the sea salt with tap water. The salinity of
the articial seawater was controlled within 3.43.5%. The temperature during the treatment was kept 30 C, which is about
the maximum temperature off the east coast of PR China in the
summer season.
The treating periods employed were 10, 30, 60, 90 and 120 days
separately. Specimens were removed from the bath at different
times and carefully dried with an absorbent paper. Measurement
of the weight gain was done on a microbalance accurate to 10 mg.
The tensile strength was tested by using the Model INSTRON
3369 Universal Tensile Tester (United States). The distance between the two clampers before the test was kept 115 mm, the testing speed was 2 mm/min.

* Tel.: +86 22 24528528; fax: +86 22 24528287.

E-mail address: Huanglll@public.tpt.tj.cn
0261-3069/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2008.06.020

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H. Gu / Materials and Design 30 (2009) 13371340

Table 1
Specications of the glass fabric
Plain weave
119.2
60
57
136.56
0.19
49.43

Weight gain rate (%)

0.6

Fabric structure
Yarn neness (warp and weft, tex)
Warp density (ends/10 cm)
Weft density (picks/10 cm)
Fabric weight (g/m2)
Fabric thickness (mm)
Single yarn (tow) strength (N)

0.5
0.4
0.3
0.2
0.1
0.0
0

20
40
60
80
100
120
Seawater immersion time (days)

Fig. 3. Weight gain rate for the 2-layer specimen.

Fig. 1. Specications of the specimen for the tensile measurement.

Table 2
Dimensions of the specimen for the tensile strength test (mm)
F

180

20 0.5

55 0.5

115 0.5

50 0.5

0.30.7

10 0.2

Three-point-bending test was carried out by using the instrument developed by Tianjin Polytechnic University (PR China). The
conguration of the test is schematically shown in Fig. 2.
The distance between the two pivots was 120 mm, a xed load
(0.05 N for the 2-layer specimens and 0.5 N for the 4-layer specimens) was pressed at the middle of the sample during the test,
1 min later the maximum deection of the specimen was recorded
to represent the bending strength of the samples.
3. Results and discussions
3.1. Weight increase
Fig. 3 illustrates the weight gain rate of the 2-layer composites
at different seawater soaking time.
Percent weight change (weight gain rate) was calculated by

M1 M0
 100;
M0

where M0 was the initial weight, M1 the weight of the specimen at

each immersion time.
When specimens were immersed in the seawater, the water
molecules would penetrate into the material, inducing the weight
gain. On the other hand, the extraction of soluble materials would
cause the weight loss. Thus the weight change would be the joint

load

Weight increase rate (%)

M%

action of the two. The weight gain rate curve for the 4-layer specimen was relatively the same with that of the 2-layer specimen, for
the sake of simplicity the gure was not included.
Origin, a universal graph processing software, was employed to
realize the simulated function of the weight gain rate. Fig. 4 presents the polynomial t curve for the 2-layer specimens.
One might notice that the unit of the abscissa had been designated square root of hours. This was done to expect a relatively
neat and regular curve. In this case 10 days of immersion would
be transferred to 15.5 in the abscissa. From the curve one might
imagine that at the beginning of the seawater saturation, the
weight increased sharply, demonstrating the rapid moisture penetration into the materials. It is believed that higher void content
in the brematrix interface would facilitate the entrance of
humidity. After 30 days seawater treatment, white particles oozed from the specimens, this might be attributed to the extraction
of soluble materials [9,10], which would cause the weight loss of
the specimen. On the other hand, one might see in the later part
of Fig. 4 that the weight of the specimens was still increasing
with the lowered weight increase rate showing that water
absorption was in progress. Thus one might anticipate that the
weight gain rate in the later part of Fig. 4 would be the joint action of the absorption of moisture and the extraction of soluble
compounds.

Initial data
Polynomial fit of initial data

0.6
0.5
0.4
0.3
0.2
0.1

sample

0.0
0

pivot 2

pivot 2
Fig. 2. Conguration of the bending test.

10

20

30

40

50

60

Square root of hours

Fig. 4. Simulated curve of the weight gain rate of the 2-layer specimens.

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H. Gu / Materials and Design 30 (2009) 13371340

The simulated equation is presented as

4

Y 0:0474 0:03031  X  4:1947  10

3.3. Bending behaviour

2

X :

Standard derivation: 0.0433.

The simulated curve for the 4-layer specimen was relatively the
same with that of the 2-layer specimen, for the sake of simplicity
the gure was not shown.
3.2. Tensile strength
The tensile strength variation of the seawater treated specimens
is shown in Fig. 5.
Each datum in the gure was based on ve determinations. The
deceased trend of the tensile strength with increased treating time
might be seen. Statistic calculations were carried out for each case
to see if the tensile strength change was signicant. For the 2-layer
specimens, after 10 days treatment, the tensile strength reduction
began to show signicance. As for the 4-layer specimens, 30 days
saturation was needed to see signicant tensile strength decrease.
Table 3 demonstrates the calculation results for the 4-layer samples (30 days treatment).
Table 3 shows that the tensile strength decrease of the 4-layer
sample after 30 days treatment is highly signicant. Voids and
cracks of the resin would allow moisture to penetrate the composites, which amplied and accelerated the breakdown of the structure. It is known that ester groups of the polyester resin would
undergo hydrolysis when immersed in water. The hydrolysis reaction promoted the extraction of low molecular weight polyester
species, styrene and glycol from the composite into the seawater.
When in the dissolved state, the NaCl in the water would break
apart into their cations and anions. Ions would penetrate along
with the water molecules into the composite, causing damage to
the matrix, bre and interface. These would deteriorate the material, resulting in a decreased tensile strength.

3.4. SEM image of the broken section of the samples

The SEM photographs were conducted by using the Model
KYKY2800 scanning electron microscope (Beijing, PR China). Fig. 7
illustrates the broken sections of the 4-layer specimens.
In Fig. 7a the broken section of the untreated sample shows that
bres were broken neatly. This was the result of the effective bonding of the matrix on the bres. After 120 days seawater immersion
(Fig. 7b), the bre/matrix interface had been seriously damaged.
One might see the cracking of the polyester and the debonding
of the bre/matrix interface, the cracks may be caused by the tensile strains induced by the swelling and/or chemical decomposition
of the matrix. During the tensile strength test, the bres were no
longer broken simultaneously, this implied that the bonding action
of the matrix on the bres had been greatly reduced.

4- Layer

2- Layer
1600
1400

2- Layer (load

1200

0. 05N)

1000
800
600
400
200
0

10

30

60

90

120

Bending distance (mm)

Maximum tensile strength (N)

Fig. 6 illustrates the bending behaviours of the treated

specimens.
It should be noticed that loads used to bend the specimens were
different for samples with different layers, 0.05 N for the 2-layer
sample and 0.5 N for the 4-layer sample. It is important to understand that the greater the value in the gure, the less the bending
resistance of the samples.
A decreasing trend of the bending resistance with prolonged
immersion time could be noticed in the gure. Statistic calculations
were made for each case to see if the bending strength decrease was
signicant. After 10 and 30 days seawater immersion, the bending
strength started to show signicance for the 2-layer and 4-layer
specimens, respectively. Table 4 presents the results of the 4-layer
specimens after 30 days treatment.
From the table one might see that the reduction of the bending
strength was signicant.
It is believed that the oxide of the alkaline metal in the glass bre would reduce its chemical stability, thus the bre may be easier to react with other ions. This would cause the glass bre and
matrix to deteriorate, resulting in a reduced bending resistance.

15

10

Seawater saturation time (days)

4- Layer (load
0 5N)

10

30

60

90

120

Seawater immersion time (days)

Fig. 5. Tensile strength of the seawater treated samples.
Fig. 6. The bending behaviours of the seawater treated samples.

Table 3
Analysis of variance of the tensile strength of 4-layer specimens after 30-day seawater
treatment
Source of
variation

Sum of
squares

d.f.

Mean
squares

F(0.05)

F(0.01)

Treatment
Testing
Total

24,006
137,358
161,364

1
8
9

24,006
17,170

45.77

5.32

11.265

Table 4
Analysis of variance of the bending strength of 4-layer specimens after 30-day
seawater treatment
Source of variation

Sum of squares

d.f.

Mean squares

F(0.05)

F(0.01)

Treatment
Testing
Total

0.033
0.044
0.007

1
8
9

0.033
0.055

6.00

5.32

11.26

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H. Gu / Materials and Design 30 (2009) 13371340

Fig. 7. SEM photographs of the broken section of the 4-layer specimens: (a) Before the treatment (500) and (b) after 120 days treatment (500).

4. Summary

References

The weight gain change of the glass bre reinforced unsaturated

polyester composites after immersing in the seawater was the consequence of two effects: water absorption and soluble material
extraction. In the rst period of the seawater immersion, water
absorption was predominant; in the later part the soluble material
extraction would play a major role.
The gradually reduced bending and tensile strength with prolonged seawater immersion time indicated that the material had
experienced some forms of physical damage and/or irreversible
chemical degradation. The soaked moisture would cause the matrix to swell and break, react with the function groups in the matrix
and lament. All these would cause the material to deteriorate. The
SEM image of the broken section of the specimen after seawater
immersion showed that the bre/matrix interface had been seriously damaged.

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Acknowledgements
Financed by the Key Laboratory of China Education Ministry,
Zhejiang University of Sciences. Project Research on ageing behaviours of composites in moisture environments, No. 2005003.