Journal of

Marine Science
and Engineering

Article
Prediction of the Deterioration of FRP Composite Properties
Induced by Marine Environments
Goran Vizentin * and Goran Vukelic

Marine Engineering Department, Faculty of Maritime Studies, University of Rijeka, Studentska 2,

HR-51000 Rijeka, Croatia; [email protected]
* Correspondence: [email protected]

Abstract: In this paper, a model for the prediction of fatigue life degradation of fiber-reinforced
(FRP) composite materials exposed for prolonged periods to real marine environments is proposed.
The data collected during the previous phases of a more comprehensive research of real marine
environment-induced changes of mechanical properties in FRP composites are used to assess the
influence of these changes on the durability characteristics of composites. Attention is paid to the
classification societies’ design and exploitation rules on this matter. The need for the modification of
the process used for obtaining composite material S–N curves, considering the influence of the marine
environment, is studied. A regression analysis of the experimental data is conducted, resulting in a
mathematical model of strength degradation over time. The regression analysis shows an acceptable
correlation value. The S–N curves for E-glass/polyester composites with three different fiber layout
configurations are evaluated and modified to encompass the findings of this research.

Keywords: composites; marine environment; material degradation; fatigue life






Citation: Vizentin, G.; Vukelic, G. 1. Introduction
Prediction of the Deterioration of FRP
The use of fiber-reinforced polymer (FRP) composites is becoming increasingly ac-
Composite Properties Induced by
cepted in almost every industry sector, either for entire structures [1,2] or in combination
Marine Environments. J. Mar. Sci.
with other, so-called traditional materials [3–5]. The marine industry sector is no exception
Eng. 2022, 10, 510. https://doi.org/
to this trend [6], as FRP composites are finding application in the transportation industry,
10.3390/jmse10040510
especially in the maritime sector, whether it be in the construction of lightweight ship
Academic Editors: Erkan Oterkus structures [7,8] or other marine structures [9,10].
and Cristiano Fragassa A number of studies carried out in this field over the last couple of decades have aimed
Received: 7 March 2022
to consolidate the experimental and scientific knowledge obtained so far with the goal of
Accepted: 4 April 2022
developing prediction models that can be used to achieve the sustainable and safe design of
Published: 6 April 2022
engineering structures [11–14]. It is likely that the most important advantage of composite
materials is their adaptability to specific application demands by defining layup sequences,
Publisher’s Note: MDPI stays neutral
the number of plies, and the fiber orientation in the principal loading directions [15–17].
with regard to jurisdictional claims in
Such flexibility in application makes FRP composites increasingly appealing to engineers
published maps and institutional affil-
when designing marine structures of complex shapes. As the application field for marine
iations.
composites widens, the request for mechanical and environmental resilience rises. Limit
stress states, durability and life span, failure modes, fracture toughness, fire resistance,
and environment influence parameters are crucial for an efficient, sustainable, and secure
Copyright: © 2022 by the authors.
design process for structures in this demanding industry sector [18–21].
Licensee MDPI, Basel, Switzerland. In practice, marine structural designers tend to avoid the micromechanics of com-
This article is an open access article posites as they can be too convoluted and tedious for everyday use, resulting in them
distributed under the terms and ignoring this aspect in the design process and turning to rules and procedures which can
conditions of the Creative Commons be conservative, empirical, and not completely encompass all the specificities of newly
Attribution (CC BY) license (https:// emerging materials such as FRP composites. The design results are consequently often
creativecommons.org/licenses/by/ not optimal for failure modeling. It is up to the scientists in this field of study to define,
4.0/). develop, and produce simple engineering tools to improve the design process.

J. Mar. Sci. Eng. 2022, 10, 510. https://doi.org/10.3390/jmse10040510 https://www.mdpi.com/journal/jmse

J. Mar. Sci. Eng. 2022, 10, 510 2 of 11

The dominating methods used for composite failure data collection are experiment-
based. The main downside of these methods is the cost and time needed for such ex-
periments if all aspects of real marine environments are to be taken into consideration.
The dominant parameters influencing the mechanical properties of composite materials
in marine applications are the absorption of seawater [22,23] and the negative effects of
polluted process waters from ship systems to constructive materials [24].
The prevailing composite chosen as a construction material in the civil sector of the
marine industry for both commercial and small-hull vessels is glass fiber-reinforced plas-
tics [25]. This choice is the result of the favorable material characteristics, yielding a more
cost-effective product. The strict rules, standards, and recommended practices of the classi-
fication societies restrict the choice of matrix and fiber materials used in marine structures to
E-glass or carbon fibers and epoxy, polyester, or vinyl-ester resins [26]. The same standard
dictates that the effect on the “properties under long term static and cyclic and high rate
loads” and the “influence of the environment on properties” must be considered during
the design process of marine structures.
The regulations acknowledge that material properties can “change gradually with
time and long exposure times” and that significant changes can occur after 1 year but
neglect to consider the real marine environment influences. Only the effects of seawater
and freshwater are mentioned, with it being stated that freshwater has more severe effects
on the composite mechanical properties than seawater. Furthermore, any marine structure
is subjected to actions of fouling marine organisms, which is not described in the standards
regarding the design of the structure but is considered separately (protection coatings,
anti-fouling devices, etc.).
The fatigue of composites immersed in water has been investigated in the past [27,28].
Early research assumed that the absorbed moisture has no influence on the material fatigue
strength in sinusoidal tension conditions, with a moisture content no greater than 0.2 per-
cent [29]. However, newer research acknowledges the effects of water absorption on the
fatigue strength of composites [30,31]. A phenomenological base fatigue life model of glass
fiber-reinforced polymer composite materials has also been proposed [32]. Researchers
have also tried to simplify this complex problem to facilitate the engineering application of
fatigue life calculations [33].
Some research has taken into account the influence of a protective gel coat on the
fatigue of glass polyester composites [34], concluding that polyester content is the only
factor determining fatigue strength, while both polyester and gel coat contents have effects
on tensile strength. A comprehensive review of S–N curve models for the characterization
of composite materials [35] indicated which S–N curve models have the highest fitting
capabilities for experimental fatigue data.
Nonetheless, the research presented in this paper aims to encompass the real marine
environment effects, including the effects of moving seawater (waves, tidal changes),
weather influences, and the impact of the marine organisms that live attached to any
typical marine structures. All of these effects are difficult if not impossible to evaluate in
laboratory conditions.

2. Materials and Methods

2.1. Experimental Investigation
The analysis of the data collected during the experimental testing phase of this research
(250 × 25 × 5 mm coupons, 50 ± 5% fiber reinforcement volume) [21,36] showed the
influence of the real sea environment on epoxy/glass and polyester/glass composite
materials (with 3 distinct fiber layout configurations—namely, unidirectional UD0◦ , cross-
ply (0/90) s and (0/45/90) s) in the form of reduced mechanical strength for the material
submerged in the sea. The marine microorganisms embedded in the resin and invertebrates
attached to the surface of the material were identified as a factor that influenced the
composite’s mechanical properties. The mechanism (or mechanisms) of the effects that these
organisms exert on the material structure needs deeper analysis and research. Nonetheless,
J. Mar. Sci. Eng. 2022, 10, 510 3 of 11

the importance of testing in a real marine environment instead of laboratory conditions

has become evident. The various marine organisms and microorganisms attached to the
coupons are shown in Figure 1.

Figure 1. Attached bio-layer: (a) coupons in submerging fixture; (b) coupons after 2 years of
submersion; (c) detail of marine organisms attached; (d) scanning electron image of embedded
organisms after 6 months of exposure.

This research was conducted keeping in mind the inspection and maintenance proce-
dures of marine structures. Eventual damage points that can occur during the exploitation
of the hull or any other point of such structures constructed using composites would
represent an entry point for seawater. Marine vessels and structures are generally protected
by a final gel coat layer or paint that protects them from water penetration. When damage
occurs on this protective layer during application, a more significant seawater intake rate
in the structure material can be expected. Inspection and maintenance procedures should
be planned in a manner that will identify such problematic spots in time to minimize the
negative effects of the environment on the structure itself.
The material used in this research was exposed to a real marine environment in the
form of standardized coupons [37] for a period of two years, with testing and analysis
performed after 6, 12, and 24 months. Most studies concerned with the environmental
degradation of the material properties were based on laboratory experiments and either
simulated real environments [38] or were conducted in an accelerated manner [39]. Since
marine structures need to operate in corrosive environments for long periods, there is a
certain gap in research when it comes to experiments that are conducted in the natural
environment for prolonged periods [40]. Laboratory results can be useful, but a compre-
hensive overview can be gained only by studies performed in a natural environment [41].
The parameters evaluated in this study were mass gain due to seawater absorption, dimen-
sional variations, tensile strength changes, and material morphological variations. Special
attention was given to the influence of marine organisms on the material strength.
J. Mar. Sci. Eng. 2022, 10, 510 4 of 11

2.2. Numerical Analysis

2.2.1. Tensile Test Modelling
The experimental tensile test for dry coupons was modeled in the ANSYS FEA soft-
ware with the intent to verify the correlation between experimental testing and numerical
modeling. The ACP (ANSYS Composite PrepPost) analysis system was used to model
the three fiber layout configurations. The FE model was meshed using 4-node shell el-
ements (ANSYS element designation SHELL181), comprising a total of 1034 nodes and
930 elements. The FEA model is shown in Figure 2.

Figure 2. Tensile test FE model: (a) mesh; (b) boundary conditions; (c) ACP layup plot.

The material characteristics for the polyester resin used were a density of 1200 kg/m3 ,
elasticity modulus of 3240 MPa, effective stress limit of 42 MPa, and Poisson’s ratio of 0.316.
The mechanical characteristics of the E-glass fibers were custom specified according to the
manufacturer’s specifications: a density of 2000 kg/m3 , elasticity modulus of 52.7 GPa in
the fiber direction and 10 GPa in the transverse direction, effective tensile stress limit of
573 MPa along the fiber direction and 35 MPa in the transverse direction, shear stress limit
of 74 MPa, and Poisson’s ratio of 0.3. The ply type was set as woven. Separate stack-up
properties were defined for each fiber layout configuration in the ANSYS ACP tool for the
8-layered coupons and the tabs.
The critical loads were identified ply-wise by the first ply failure (FPF) criteria for each
fiber layout configuration.

2.2.2. Regression Analysis

The data collected during a 2-year period were consequently used for a regression
analysis to obtain a mathematical model for the strength degradation correlated to the
exposure time in the marine environment. The obtained mathematical model was used to
predict the loss of strength over a 10-year period.

2.2.3. Structural Durability Assessment

Every marine structure (and/or component) has to pass a certification process pre-
scribed by the regulations in order to prove its safety and functionality up to the end of its
design life. A typical expected life period for such structures is from 25 to 40 years. The
behavior of the structure in that period is closely related to durability. Much of the research
in this field is ongoing and only a small number of marine composite standards reference
J. Mar. Sci. Eng. 2022, 10, 510 5 of 11

long-term material properties. The long-term properties of composite materials exposed to

the demanding marine environment must be determined in order to integrate the durabil-
ity issues into the design standards. Current regulations tend to make very conservative
assumptions regarding long-term structural behavior, mainly due to a lack of detailed data.
For example, the DNV standards [26,42] prescribes the procedure for the identification of
critical failure mechanisms and the need for a redesign if necessary. The same standards
emphasize the need for a reliable analysis, and, at the same time, the acknowledgement of
several uncertainties in loads, materials, and engineering models, consequently referring
the designer to component and material testing for long-term data. The marine structure or
vessel qualification process requires the identification of static strength, resistance to cyclic
fatigue (full fatigue analysis using SN curves at different R-ratios required), stress rupture,
damage tolerance, and the effects of the environment on the structure. It is important to
mention that if the need for testing arises from the qualification process, static data and
long-term data must be measured for the actual product, which further complicates the
design process.
The classification societies’ rules prescribe the procedure for obtaining S–N curves
for composite materials. Various authors have reported results obtained in modeling
S–N curves for composites [29,34,35] and the prediction of the fatigue life of composite
structures [27,43,44]. A failure model for groups of similar glass/polyester composites,
such as the ones used in this research, can be defined in the form:

log(N) = α(δu /δmax )β , (1)

where N is the number of fatigue life cycles, δu is the ultimate tensile strength (UTS)
value, δmax is the maximal tensile stress occurring in the loaded structure, and α and β
are experimental data fitting coefficients [44]. Using material data for design purposes
obtained previously or by other researchers for similar material types and configurations is
acceptable according to the classification societies’ rules.
The loads on marine structures and vessels depend mainly on environmental condi-
tions [45]. The most influential are wave, wind, and water current loads. Ocean waves are
predominantly irregular and random in shape, height, length, and speed of propagation.
However, for structural design properties, this load can be simplified by deterministic or
stochastic methods. In order to determine the quasi-static response of marine structures
and vessels, design procedures prescribed by classification societies allow the definition
of wave loadings by wavelength and corresponding wave period, wave height, and crest
height [46].

3. Results
The results of the experimental investigation of polyester/glass coupons exposed
to the marine environment are presented in the form of diagrams, images, and tables in
previously published works by the authors of this article. The experimental testing results
shown here pertain to the tensile strength determination and surface morphology change
observations as a continuation of previous work. A regression analysis was performed on
the accumulated data and the results are shown here. A prediction model of fatigue life
behavior of the material is proposed.

3.1. Regression Analysis Results

Regression results are shown in Figure 3.
The dots represent the experimental data obtained during a 2-year period, whilst the
line represents a future forecast of the degradation.
J. Mar. Sci. Eng. 2022, 10, 510 6 of 11

Figure 3. Mathematical strength degradation prediction model: (a) UD0◦ ; (b) (0/90) s; (c) (0/45/90) s
fiber layout configuration.

The model of regression that showed the best correlation to experimental data was an
exponential equation in the form of:

δu = AeBt , (2)

where δ is the tensile strength value, t is the time of exposure to the marine environment,
and A and B are experimental data fitting coefficients. The coefficient A represents the
average ultimate tensile stress of the non-submerged specimens tested.
The regression parameters for the three considered fiber layout configurations are
given in Table 1.

Table 1. Regression model data.

Fiber Layout Configuration Coefficient A Coefficient B R2 Value

UD0◦ 165.50 −0.0349 0.7079
(0/90) s 153.37 −0.0252 0.6557
(0/45/90) s 143.51 −0.0162 0.6540

By combining Equations (1) and (2), a modified S–N curve equation can be obtained
in the form:
log(N) = α[(AeBt )/δmax ]β , (3)
J. Mar. Sci. Eng. 2022, 10, 510 7 of 11

3.2. Prediction of Fatigue Life Behavior

The predicted changes in the S–N curves caused by the change in the ultimate strength
value of the unidirectional samples due to the degradation of properties are shown in
Figures 4–6.

Figure 4. S–N curve change, UD0◦ polyester/glass composite.

Figure 5. S–N curve change, (0/90)s polyester/glass composite.

Figure 6. S–N curve change, (0/45/90)s polyester/glass composite.

The predicted decrease in expected fatigue life caused by the comprehensive effects of
the marine environment is shown in Figure 7.
J. Mar. Sci. Eng. 2022, 10, 510 8 of 11

Figure 7. Normalized (α and β set to a single value) decrease in the expected number of fatigue life
cycles, polyester/glass composite: (a) UD0◦ ; (b) (0/90) s; (c) (0/45/90) s fiber layout configuration.

4. Discussion
The results of the previous research phase conducted by the same authors have shown
that the real marine environment has considerable effects on composite materials in the
form of reduced mechanical strength after prolonged exposure [21]. Fatigue life decrease
intensity has been predicted for all fiber layout configurations with respect to the initial
value calculated for dry coupons. The percentage of the strength reduction varies for
different fiber layout configurations.
According to the model proposed in this work, after 5 years of exposure to the marine
environment, the expected fatigue life decrease (log10 value) for the UD0◦ coupons is
−3.9, −2.6, and −2.0 for 25%, 50%, and 75% UTS, respectively. The other fiber layout
configurations exhibited similar behavior—namely, the (0/90) s coupon values are −3.1,
−2.1, and −1.6, while for the (0/45/90) s coupons these values are −2.3, −1.5, and −1.2.
This loss of ultimate strength implies that corrections in predicting the fatigue life
have to be made considering the period of time for which the material has been submerged
in the sea. The value of δu from Equation (1) practically becomes time-dependent. In order
to incorporate the variation of ultimate strength, a regression analysis of the tensile test
experimental data was performed and a modified S–N curve was obtained.
The actual values of the number of life cycles shown in the Results Section are not to be
considered for design purposes, as the curves shown here are normalized to single values
of coefficients α and β. These coefficients should be determined experimentally for the
actual type of composite material that would be used for a specific structure. The analysis
J. Mar. Sci. Eng. 2022, 10, 510 9 of 11

was performed stepwise, meaning that firstly a fatigue life was estimated for reference (dry)
coupons not exposed to the sea and then re-estimated for the UTS values after each year.
There is no doubt that additional experimental data both for the 2-year long period of
exposure (sea temperature at the location of experiment varies between 10–14 ◦ C annually,
salinity changes between 37.8–38.3 PPT, while the pH value is between 8.22–8.29) and
longer would refine and raise the accuracy of this prediction model. New research has
already been planned to broaden the database for composite material behavior in the
marine environment for strength and fatigue structural design aspects. Exposing coupons
in various marine environments with different parameters (temperature, salinity, wave, and
wind characteristics) would broaden the applicability of this approach as well as increase
the models’ validity and accuracy.
Furthermore, as the UTS value continually changes over time, a numerical method
should be developed to obtain a continuous degradation S–N curve. This is the aim for
further research.
Future work will strive to incorporate the continuous UTS change in the fatigue life
decrease model described here and broaden the experimental database in order to develop
a more comprehensive predictive numerical model that could successfully replace the
time and resource-consuming experiments related to composite material fatigue behavior
characterization. The results of this study could prove helpful to determine the compos-
ite material type and fiber layout configuration during the engineering design phase of
marine vessels and structures. With the acceptance of the importance of the marine envi-
ronment’s influence on the mechanical behavior of composites and the application of the
predictive model for the fatigue life estimation process, the rules and recommendations of
classification societies in this industry sector could be amended to improve the design of
such structures.

5. Conclusions
The influence of real-time exposure to actual marine environments on the fatigue char-
acteristics of glass/polyester composite materials was investigated in this study, showing
the need to incorporate time-decaying ultimate tensile stress in the procedures used for
obtaining S–N curves.
As the previous research phases have shown, the changes in the mechanical character-
istics of composite materials induced by the actions of both water and marine organisms of
the real sea environment were manifested as a reduction in ultimate mechanical strength.
For example, the submerged polyester/E-glass UD0◦ , (0/90) s, and (0/45/90) s coupons
lost 11%, 5%, and 1% of their ultimate mechanical strength after 6 months of submersion;
50%, 37%, and 13% of their ultimate mechanical strength after 12 months in the sea; and
55%, 48%, and 24% of their ultimate mechanical strength after 24 months in the water. The
results also indicate the dependency of the UTS changes on the fiber layout configurations,
with the (0/45/90) s layout showing the greatest resilience to the marine environment. The
research up to this phase has made it evident that further study is needed due to two main
reasons. Firstly, the polyester coupons were made using the hand-layup process, which
can significantly affect the mechanical characteristics of the composite. Secondly, the exact
mechanism of marine organisms’ attachment on the surface and marine microorganisms
embedding in the resin, as well as the consequences of these phenomena on the mechanical
properties of composites exposed to the sea is not known to a satisfactory level. These
issues will surely be topics of future research.
Research findings summary:
1. An initial mathematical model of these phenomena was developed based on the
experimental data gathered.
2. The loss of ultimate strength required corrections of the procedures used for predicting
the fatigue life of composites exposed to the sea.
3. The reduction in ultimate tensile strength for composite materials exposed to the
marine environment has a direct influence on the materials’ fatigue behavior.
J. Mar. Sci. Eng. 2022, 10, 510 10 of 11

4. The research results confirmed once again the importance of biofouling in the envi-
ronmental degradation of the mechanical properties of composite materials in the
marine environment.
5. Future work is needed to develop a numerical method to encompass the continuous
UTS decay and increase the accuracy of the prediction model.

Author Contributions: Conceptualization, G.V. (Goran Vizentin); methodology, G.V. (Goran Vizentin);
formal analysis, G.V. (Goran Vizentin); investigation, G.V. (Goran Vizentin); writing—original draft
preparation, G.V. (Goran Vizentin); writing—review and editing, G.V. (Goran Vukelic); visualization,
G.V. (Goran Vizentin); supervision, G.V. (Goran Vukelic); project administration, G.V. (Goran Vukelic);
funding acquisition, G.V. (Goran Vukelic). All authors have read and agreed to the published version
of the manuscript.
Funding: This research was funded by the University of Rijeka, under the project numbers uniri-technic-
18-200 “Failure analysis of materials in marine environment” and uniri-technic-18–42 “Investigation,
analysis and modeling the behavior of structural elements stressed at room and high temperatures”.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analysis, or interpretation of data; in the writing of the manuscript; or
in the decision to publish the results.

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