European Polymer Journal 137 (2020) 109924

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European Polymer Journal

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Review

Mechanical deformation and fracture mechanisms of polymeric fibres from T

the perspective of fractography – A review
Chin Joo Tana,b,c, Andri Andriyanaa,b, , Bee Chin Anga,d, , Dannee Wonge
⁎ ⁎⁎

a
Centre of Advanced Materials, Faculty of Engineering, University of Malaya, Kuala Lumpur, Malaysia
b
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur, Malaysia
c
IOP Specialists Sdn. Bhd., Klang Central Industrial Park, Selangor, Malaysia
d
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, Kuala Lumpur, Malaysia
e
Department of Mechanical Engineering, Faculty of Engineering, Science & Technology, Nilai University, Negeri Sembilan, Malaysia

ARTICLE INFO ABSTRACT

Keywords: Polymeric fibres, regardless of natural or synthetic, are always found in our surroundings due to their diverse
Deformation real life applications. Aside from their functionalities, the mechanical durability of the fibres is also an important
Fracture element to be considered during their operating service time. The failure of these fibrous samples can be said to
Polymer be originated from the fracture or rupture of the fibres. Therefore, it is crucial to study the fractography of the
Fibres
fibres in order to understand their mechanical deformation and fracture mechanisms. In this study, the fracto-
Fractography
graphy of some common polymeric fibres with the addition of microstructural information are reviewed in order
to support the correlations of the fractography to their deformation and fracture mechanisms. The studies of
polymeric nanofibres fractography which have not been reviewed in the literature are also included in this study.
Peculiar deformation and fracture mechanisms of these nanofibres such as the multiple necking and transition
from brittle to ductile due to the addition of fillers and nanopores are reviewed and discussed in this study.

1. Introduction certain applications. In the textile industry, the assembly of fibres can
be categorized into basic and advanced fibre assemblies [58]. Basic
Polymeric fibres, despite of not being fully aware, are constantly fibre assemblies can be achieved through simple overlapping of ran-
existing in our surroundings and indispensable in our life. In a broad domly oriented fibres to produce nonwovens, as well as through folding
sense, these fibres can be categorized into two groups, which are the and torsion of fibres to construct threads and yarns. Meanwhile, ad-
natural fibres and the synthetic fibres. To a narrower definition, natural vanced fibre assemblies are often achieved through much complicated
fibres can be further categorized into cellulose based fibres and protein techniques, such as weaving, knitting, braiding and looping to produce
based fibres. Cellulose fibres such as cottons [1–4] and flaxes [5–12] are suitable assemblies for different applications.
extracted from plants, whereas protein based fibres such as silks Owing to the diverse possibilities of assemblies, polymeric fibres
[13–23] and wools [24–26] are extracted from animals. As for the possess a great number of applications that can be categorized into
synthetic fibres such as poly(p-phenylene terephthalamide) [27–36], textiles, utensils and industry applications. Among these, the use of
poly(methyl methacrylate) [1,2,37], polyamide and polyester polymeric fibres in textiles and utensils have been well-established,
[1,2,37–54], are chemically fabricated through the spinning of the while the rising potential applications that are still being widely in-
petroleum – based liquids. With the emergence of the electrospinning vestigated include tissue engineering, drugs delivery, filtration and
technique, the synthetic fibres in the submicron to nano scale of dia- electronic applications [55,56]. These constitute the ongoing trend of
meters can be fabricated [55–57]. researches where nanomaterials and nanotechnology play a key role in
Generally, fibres with diameters in the range of micro to nanometres fabricating nanofibres. The reduction in fibre diameters increases the
rarely exist as individual entities for practical applications. An assembly potential of polymeric fibres, due to several improved properties such
of fibres is often utilized to strengthen the structure as well as to pro- as the increased surface area-to-volume ratio and the high porosity with
vide a larger surface area to provide significant functionalities on small pore size distribution.

⁎
Corresponding author at: Centre of Advanced Materials, Faculty of Engineering, University of Malaya, Kuala Lumpur, Malaysia.
⁎⁎
Corresponding author at: Centre of Advanced Materials, Faculty of Engineering, University of Malaya, Kuala Lumpur, Malaysia.
E-mail addresses: [email protected] (A. Andriyana), [email protected] (B.C. Ang).

https://doi.org/10.1016/j.eurpolymj.2020.109924
Received 21 April 2020; Received in revised form 21 July 2020; Accepted 29 July 2020
Available online 06 August 2020
0014-3057/ © 2020 Elsevier Ltd. All rights reserved.
C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

However, it is unavoidable for these fibrous structures to be sub- these fractography studies as mentioned by Hearle et al. [1] are as
jected to mechanical loadings under operating environments. Problems follows.
arise when structures fail unexpectedly, leading to undesirable cir-
cumstances that might be severe and catastrophic in some cases. Hence, 1. To understand the mechanisms and causes of failure in materials.
it is always crucial to develop a proper understanding on the mechan- 2. To improve the processing methods for fabrication.
ical properties of the polymeric fibrous structures to facilitate the de- 3. As a means of diagnosis on the causes of failure.
sign and evaluation of the products. 4. For general scientific interest as to collect the fractographies of
In the past decades, scientists or researchers have conducted nu- various materials as well as for the development and evaluation of
merous mechanical tests in order to determine the mechanical prop- theoretical model for the prediction of crack growth behaviour in
erties of the polymeric fibrous structures. These fibrous structures are materials.
often mechanically characterized to determine their load bearing ca-
pacity, stress–strain behaviours, yield strengths, tensile strengths, The initial fractographic examination was conducted using optical
moduli of elasticity and so on [59–61]. It is found that the structures of microscope. This examination method is feasible for materials of larger
the fibres assemblies can have significant effect on the mechanical scale that do not require detailed investigation into the micro or much
properties of the fibrous samples. For instance, the adhesion between smaller scale. However, the limitations on the depth of focus of optical
the fibres in the assembly can improve the mechanical strength of the microscope obstruct the detailed examination of the microstructures of
assembly [62] and different weaving types can have different load materials [1]. The study of fractography has been greatly improved by
bearing capacities for the fibres assembly [63]. the introduction of scanning electron microscope (SEM), which enables
While it is doubtless that the fibrous structures can have notable the whole fracture surface to be viewed in focus [54]. SEM devices
effects on the mechanical properties or behaviours of the structures, it is allow the detailed observations of the fracture cross-section, which is
the collective ruptures or fractures of the individual fibres that are difficult to be achieved using ordinary optical microscope.
contributing to the final failure of the structures. In the literature, it is In the literature, there are many reviews on the fractography of
found that the mechanical properties and behaviours of the fibres can polymeric fibres. These reviews can be found in the book with the title
be different based on the types of fibres and loading conditions. For “Fiber Fracture” edited by M. Elices and J. Llorca. Several authors in
instance, the stress strain behaviours of the single Kevlar fibres are that book have conducted reviews on different types of polymeric fibres
strain rates independent [31] whereas the stress strain behaviours of such as by highly oriented, chain – extended polymer fibres [71],
the single polyacrylonitrile fibres are significantly affected by the strain synthetic fibres [72], natural fibres [73] and common textile fibres
rates [64] as shown in Fig. 1. It is also observed that the Kevlar fibres [74]. In addition, Morton et al. [75] have also reviewed the fracto-
have brittle fractures where the stresses of the fibres have sharp drops graphy of various common polymeric fibres in the book with the title
to 0 MPa upon failure as shown in Fig. 1(a). Contrarily to the Kevlar “Physical Properties of Textile Fibres” edited by W.E. Morton and
fibres, the polyacrylonitrile fibres experience plastic deformations as J.W.S. Hearle. Other reviews include studies conducted by Hearle et al.
shown in Fig. 1(b) where the fibres are able to sustain loads for longer [1,44], Bunsell et al. [2,37] and Kerr et al. [32]. In these mentioned
strains before total failure. The fractographies associated to these stress studies, the fracture morphology of the fibres under various mechanical
strain behaviours will be further discussed in the following sections. loadings such as monotonic tensile loads, fatigue loads, abrasion and so
However, the mechanical testing on these soft delicate single in- on are described and discussed in detail. The deformation and failure
dividual fibres with diameters in micro to nanometer range can be mechanisms of the fibres are also proposed based on their fracture
difficult by using conventional universal tensile machines. morphologies and mechanical loadings. However, these studies lack of
Consequently, machines dedicated to probe the mechanical properties detail investigations on the effects of microstructures on the fracto-
of the individual fibres such as the universal fibres testers [40,65], graphy of the fibres, which in turn affecting the deformation and
microelectromechanical system test platforms [66] or other atomic fracture mechanisms of the fibres. Nonetheless, the studies reviewed
force microscope based mechanical testing equipment [67,68] are used undeniably lay a strong foundation to the subsequent studies on the
by the researches. As a matter of fact, comprehensive reviews on the fractography of polymeric fibres later on.
mechanical testing techniques on these fibres can be found in the stu- Hence, the authors intend to revisit the fractography of the polymer
dies of Li et al. [69] and Tan et al. [70]. fibres in the reviews mentioned above and refurbish the fractography
In addition to the mechanical properties, the fracture morphologies with more microstructural investigations from the literature in this
of the fibres are also widely studied in the literature. The objectives of study. The focus is to relate the fractography of the polymeric fibres to

Fig. 1. Stress–strain behaviours of the (a) Kevlar [31] and (b) polyacrylonitrile [64] fibres under mechanical tensile loadings of different strain rates.

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

their deformation and failure mechanisms. These microstructural in- this reason, shear stresses are induced and assumed to be maximum
vestigations can be probed using IR/Raman microspectroscopy adjacent to the reversal zones. Finally, surface cracks developed and
[40,50,53,76], polarized light microscopy [51], energy dispersive propagated towards the reversal zone following the spiral angle. The
spectroscopy [43,51] and many more that are not covered in this re- failure of cotton fibre occurs when cracks grew and joined at their ends,
view. In addition, new fractography studies with clearer resolutions leading to tearing of fibre with fibrillar morphology.
using equipment such as atomic force microscopy [30], transmission
electron microscopy [77] and environmental scanning electron micro- 2.1.2. Flax
scopy [12] are also included. Flax fibres, another common type of plant fibres are widely used as
Yet, the scope of polymeric fibres is too wide that it is difficult for reinforcements in composite materials [5]. As illustrated in Fig. 3, these
the authors to discuss on every single polymeric fibre that exists. fibres have layered microstructures with cellulose microfibrils em-
Therefore, the present work focuses on the as spun, extracted and re- bedded inside amorphous polymers. However, the microfibrils are not
ceived polymeric fibres without further processing in the literature with oriented in the direction of the fibre axis.
the size of fibre diameter below 50 μm to narrow down the scope of During tensile mechanical loading in the direction of the fibre axis,
studies. To further narrow down the scope, only the fractured fibres due the cellulose microfibrils would align parallel to the fibre axis [6–9],
to uniaxial tensile mechanical tests under ambient condition are in- evidenced by the fibrillar fracture morphology of the fibre under tensile
cluded in this study. As examples, the fibres fractured under flex fatigue loadings as shown in Fig. 4. This alignment can contribute to the pro-
loading [78] or loaded under the designated environments [41,52,79] gressive stress strain behaviours of the flax fibre.
are not considered in this review. These cellulose microfibrils plays an important role in the de-
Above all, the fractographies of the polymeric nanofibres which formation of flax fibres. As described by Baley [8], the deformation of
have diameters less than 1 μm are the most important highlight in this the fibre is associated with the realignment and deformation of the
study. To the best of the authors knowledge, no review on the fracto- microfibrils within the fibre. It is proposed that the deformation or
graphy of various nanofibres have been conducted in the literature yet. extension mechanism of the fibre due to tensile load can be explained in
It is of utmost important for a review study on the fractography of 3 routes [11] as listed below.
nanofibres as the fractography is found to be distinctive from their bulk
counterparts [64,66,67,77,80–84]. The multiple necking phenomena 1. The length of the fibrils with the amorphous region in between in-
observed during the deformation processes of nanofibres is different creases with the extension of the fibre.
from the single necking in ductile polymeric bulk materials. In addition, 2. Bending and twisting of the fibrils takes place with the extension of
inclusions of fillers, such as carbon nanotubes [67,77,85] and in- the fibre. Simultaneously, the volumes of fibrils, interfibrillar matrix
troduction of nanopores [84] to the nanofibres can alter their fracto- of amorphous material and any voids present diminished.
graphy from brittle to ductile. This transition from brittle to ductile of 3. The shearing of the amorphous region enables it to be conformed
nanofibres is interesting as most bulk polymeric materials have decre- with the new configuration of the fibrillar structure during the ex-
ments in ductility with the addition of ceramic fillers and pores. tension of the fibre.
In order to ease the comprehension of the readers, the structure of
this article is briefly described here. This article is divided into two Undoubtedly, the deformation of the fibres will eventually lead to
major sections, Section 2 and 3 according to the types of fibres. Section fracture in the end. These fracture phenomena will most probably occur
2 consists of the reviews on the fractographies of natural fibres whereas at where the defects located since defects are the weakest regions sus-
Section 3 consists of reviews on the fractographies of synthetic fibres. In ceptible to fracture which is commonly acknowledged in materials
Section 2, natural fibres are further categorized into Section 2.1, cel- science.
lulose based fibres and Section 2.2, protein based fibres. As for the While defects may also present within the flax fibres, studies show
synthetic fibres in Section 3, the fibres are categorized according to that the fracture occurs at the defects on the surface of the fibres
their diameters, in which the fractographies of the microfibres are re- [7–9,12]. It is believed that crack initiation and propagation process
viewed in Section 3.1 while the fractographies of the nanofibres are occur during the fracturing of the flax fibres [7,9]. According to the
reviewed in Section 3.2. Lastly, the reviews on the fractographies of all study conducted by Aslan et al. [7], the crack firstly initiates at the
the fibres mentioned in Section 2 and 3 are concluded in Section 4. largest defect, then it propagates into the fibre and along the fibre axis
until it reaches a smaller defect where the final rupture occurs as illu-
2. Natural fibres strated in Fig. 5(a).
The defects on the surface of the fibre are in the form of kink band
2.1. Cellulose based fibres and can be observed on the longitudinal or transversal direction of the
fibres as shown in Fig. 5(b). These defects may be introduced during
2.1.1. Cotton processing or occur naturally due to the growth of the fibres. It is also
Cotton is a soft, fluffy boll found on cotton plants that is extensively possible that the defects are induced under mechanical loading. Bos
used in textile applications. Cotton fibre possesses fibrillar, layered et al. [12] found that kink bands are formed on the surface of flax fibres
structure with primary and secondary walls that are different in their during mechanical loading.
chemical compositions [2].
The fractures of the cotton fibres due to monotonic and fatigue 2.2. Protein based fibres
tensile mechanical tests often occur adjacent to the reversal zones,
following the spiral angle of the fibrils as suggested in the literature 2.2.1. Spider silk fibres
[1–4]. These reversal zones are the zones over which the helix angle of Spider silk fibres have ensured the survival of spider species by
fibrils is changing. providing protection to the offspring and also food through trapping the
The micrographs captured by Harzellah et al. [3] as shown in Fig. 2 preys due to their outstanding mechanical properties [13]. These out-
are used to illustrate the general fracture mechanism and features of a standing mechanical properties are said to be highly related to the
single cotton fibre. Upon the initial load application, deconvolution microstructure of the fibres. Plaza et al. [14] studied the relationship
takes place and lead to the splitting in secondary wall. Further elon- between the microstructure and mechanical properties of super-
gation of cotton fibres caused the helical arrangement of the fibrils to be contracted spider silk fibres. A two-regime model is proposed to de-
straighten out parallel to the fibres axis, resulting in an untwisting scribe the microstructural deformation of the spider silk fibre under
phenomenon in opposite direction on both sides of the reversal. Due to tensile loading as illustrated in Fig. 6. At the first regime, nanocrystals

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

Fig. 2. (a) Helical fibrils before fatigue tensile mechanical test, (b) straightened fibrils after fatigue tensile mechanical test, (c) propagated surface crack and (d)
fibrillar failure morphology of a cotton fibre [3].

Fig. 3. Schematic representation of a flax fibre with a primary and secondary wall [6,11].

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

process is more probable to be the case.

The flat fracture surface shown in Fig. 7(a) gives the idea that the
fibre fractured uniformly across the cross – sectional area. This idea is
further strengthened when the diameter of the fractured region is found
to be similar along the axis of the fibre, indicating the absence of
necking phenomenon [16]. It is supposed that brittle fracture had taken
place without a clear energy dissipation mechanism [13].
Another apparent feature on the fracture surface can be observed on
the core region of the silk fibre which is the globular morphology as
shown in Fig. 7(b). In the study conducted by Pérez-Rigueiro et al. [13],
it is suggested that this globular morphology is due to the elongation of
voids within the fibre during the mechanical stretching. Indeed, typical
synthetic spun fibres have occluded solvent within the fibre and voids
are formed upon drying [17]. However, the silk fibres are extracted or
spun from spiders. It is doubtful that the spinning process in the spider
is similar to the spinning process of synthetic fibres. In another study
conducted by Pérez-Rigueiro et al. [16], mechanical tensile tests were
Fig. 4. Fractured region of a flax fibre after tensile test [8]. conducted at a very slow strain rate to allow greater extent of viscous
flow within the fibres. It is expected that the viscous flow of the con-
stituents within the fibre will fill the voids and result in a smooth
fracture surface. Nevertheless, the globular morphology of the core
region is still observed. Hence, a more probable scenario is proposed.
The globular morphology is due to the nanofibrils that exist naturally in
the silk fibres [18].
The brittle skin – core fracture surface previously discussed is nor-
mally observed in the spider silk fibres undergoing mechanical test at
low strain rates. Cunniff et al. [19] conducted a tensile mechanical test
with a ballistic fracture rate on spider silk fibres. Aside from the brittle
fracture similar to Fig. 7, the fibres are also found to fracture in a dif-
ferent manner, showing an axial splitting as presented in Fig. 8. Frac-
tures occur along the axis of the fibre causing the fibre to split into
smaller diameter fibrils. The origin of this axial splitting is suspected to
be associated to the lobes found on the surface of the fibre.

2.2.2. Silkworm silk fibres

Silk fabrics are commonly known as the most luxurious textile and it
was first developed in the ancient China [86]. Due to the lustrous and
smooth textures of silk fabrics, the demand for silks is always high in
the textile industry. These silks are normally extracted from the cocoon
of silkworms such as Attacus atlas [15], Bombyx mori [15,20–22], An-
theraea assamensis [23] and Samia cynthia ricini [21,23].
The fractography analyses on the silkworm silk fibres reveal that the
fibres generally fracture in two manners, flat fracture and axial splitting
[15] as shown in Fig. 9.
With reference to Fig. 9(c), the Bombyx mori fibre has a structure
consisting of two irregular shape brins connected together coated with
a layer of sericin protein [15,20–22]. The flat fracture surface indicates
a catastrophic failure. This alignment can contribute to the progressive
Fig. 5. (a) Illustration of crack initiation at large defect denoted by 1 and stress strain behaviours of the flax fibre. A rough or globular mor-
propagation to small defect denoted by 2; (b) Micrograph of a flax fibre with phology is also observed on the fracture surface, likes the spider silk
defects [7]. fibre. This morphology could be also attributed to the fibrils embedded
inside the fibre as fibrils are found to be projecting from the fracture
surface of the fibre in the study of Jiang et al. [20]. Occasionally, the
within the fibre reorient as the stretching increases until the nano-
brin maybe pull out from the coating, leaving a void on the fibre as
crystals are highly oriented. Further stretching will result in the growth
shown in Fig. 9(a,b). The mechanism of this fracture is suggested to
of crystalline fraction which is the second regime, making the fibre
initiate when one of the brins is pulled out, leaving the another brin to
stiffer.
bear the load until the final rupture occurs [15].
From the fractography analyses of the spider silk fibres, the fibres
Another type of fracture, the axial splitting of Attacus atlas fibre [15]
are found to have skin – core morphologies [15,16] as shown in
similar to the spider silk fibre under ballistic fracture rate as discussed
Fig. 7(a). While it is unknown that the skin – core morphology is due to
previously is presented in Fig. 9(d). This axial splitting is said to be a
the chemical segregation caused by different chemical composition or
process of defibrillation, where the fibrils within the fibres are sepa-
physical segregation caused by molecular alignment, Pérez-Rigueiro
rated from each other due to the flaws. These flaws are said to be as-
et al. [16] believe that it is originated from the fibre forming process.
sociated with the packing, distribution and orientation of the fibrils. If
According to their study, the nucleation of the fracture does not occur
the fibre has no flaws at all, the fibrils will fracture or fail at the same
at the interface of the skin – core, suggesting no distinct discontinuities
time, resulting in a flat fracture surface [23] like the Bombyx mori fibre.
at the interface. Instead, a morphology gradient due to the fibre forming
Further zoom into the split fibril, pulled out microfibrils from the fibril

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

Fig. 6. Illustration of two-regime model for the microstructural deformation of a supercontracted spider silk fibre [14].

Fig. 8. Axial splitting of a Nephila clavipe fibre [19].

can be observed as presented in Fig. 9(e). The tip of the microfibril

shows a smaller diameter as compared to the rest of the microfibril as
shown in Fig. 9(f). This necking phenomenon may indicate that ductile
fracture occurs at very small local scales.

3. Synthetic fibres

3.1. Microfibres

3.1.1. Axial splitting

Kevlar or poly(p-phenylene terephthalamide) fibre is a high-per-
formance para-aramid fibre with excellence mechanical properties even
under very high strain rates, making it particularly suitable for the
application of ballistic clothing. Roenbeck et al. [27] highlighted the
Fig. 7. (a) Argiope trifasciata fibre with skin – core morphology; (b) Globular key structural features of this fibre found in the literature
morphology of the core [15]. [29,36,87–90] and are illustrated in Fig. 10. In this fibre model, the
smallest entities are the poly(p-phenylene terephthalamide) or PPTA
crystallites. These crystallites form the microfibrils which in turn or-
ganise into pleated sheets. The core of the PPTA fibres are comprised of
these sheets and are surrounded by a layer of skin.

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

Fig. 9. (a, b, c) Micrographs of a fractured Bombyx mori fibre and (d, e, f) Attacus atlas fibre [15].

Axial splitting is frequently observed in Kevlar under tensile loading pure tensile loading, giving rise to defibrillation, where the decohesion
regardless of strain rate [28–36]. This type of fracturing process is re- between microfibrils within the fibres occurs [33]. As a result, fractures
ferring to the rupture of the fibre due to the crack propagations along its due to axial splitting will take place.
axis. An example of the axial splitting in a poly(p-phenylene ter- However, it is unclear on how the cracks in Kevlar initiate. The
ephthalamide) fibre is as shown in Fig. 11. crack initiation maybe within the fibre or on the surface of the fibre.
According to Cheng et al. [31], a perfectly uniform fibre subjected Kim et al. [35] suggested the crack initiation occurs at the core of the
to pure tension is impossible to fracture by axial splitting due to the fibre due to two factors. First, the core of the fibre has higher degree of
absence of shear stress. However, nothing is perfect without flaws, in- order and crystallinity than the skin. Hence, the core bears most of the
cluding Kevlar. Discontinuities or defects tend to exist within or on the loading applied to the fibre. Second, chain ends are concentrated in the
surface of the fibres. Thus, shear stresses will develop despite under core of the fibre. From the perspectives of materials science, chain ends

Fig. 10. Key structural features of a poly(p-phenylene terephthalamide) fibre in the literature [29,36,87–90] highlighted by Roenbeck et al. [27].

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

of the fibre in the study conducted by Morgan et al. [29]. Since the
undulation morphology is also observed on the surface of Kevlar under
the fatigue tensile loading in vacuum, it is plausible that the molecular
rearrangement has homogenized the core and skin of the fibre in which
the skin properties or morphology are similar to the core of the fibre.

3.1.2. Radial fracture

3.1.2.1. Acrylic fibres. Unlike the axial splitting where the cracks
propagate along the axes of fibres, radial fracture is a type of failure
where the crack propagations are perpendicular to the axes of fibres.
Acrylic fibres fracture in this manner with flat and rough surfaces under
monotonic tensile tests [1,2,37] as shown in Fig. 14(a). The obvious
striations observed on the circumferential surface of the fibre and some
fibrous structures projecting out from the fracture surface suggesting
that the constituents of the fibre consist of fibrils aligning in the
direction of fibre axis. These fibrils are said to have weak cohesion with
each other. During monotonic tensile loadings, the weakest fibril with
Fig. 11. Axial splitting of a poly(p-phenylene terephthalamide) fibre [33]. the most defects will fracture first. After that, the load will be borne by
the neighbouring fibrils. Consequently, the fracturing of the fibrils will
spread in the radial direction of the fibre, resulting in a flat fracture
are the discontinuities or defects that will act as crack initiation sites. In
surface morphology [2,37]. The effect of the low cohesive forces
addition, it is also found that the sheets within the core of the fibres are
between the fibrils on the fracturing of the acrylic fibres is more
only bonded with weak van der Waals forces [91] which are also weak
apparent under the cyclic loadings. Due to these low cohesive forces,
points vulnerable to crack initiation. Despite that it is reasonable that
the fibrils are separated from each other under cyclic loadings. As a
crack initiate within the fibre due to the explanations given, it is dif-
result, the fibres fail by axial splitting [37] just like Kevlar as shown in
ficult to verify through experimental studies or characterisation tech-
Fig. 14(b).
niques.
On the contrary, the crack propagation proposed by Konopasek
3.1.2.2. Polyamide and polyester
et al. [28] starts from the skin toward the core of the fibre as illustrated
3.1.2.2.1. Monotonic and creep tensile failure. Apart from acrylic
in Fig. 12. Indeed, the nanoscopic surface morphology is found to be
fibres, this radial fracture is also commonly observed in polyamide and
damaged during tensile fatigue loading from the observation under
polyester fibres despite not having flat fracture morphologies. These
atomic force microscope conducted by Minoshima et al. [30]. The mi-
fibres are extensively produced for textiles and other industrial
crographs are as shown in Fig. 13. A fibrillar morphology is found on
applications due to the strong demands. As such, the examination of
the surface of the Kevlar before fatigue tensile loading, further verifying
the fracture morphology of these polymeric fibres to understand their
the existence of the microfibrils within the fibre. In the event of fatigue
failure mechanisms are particularly essential in ensuring the
tensile loadings, this fibrillar morphology would change into a nodular
consistency and improving the durability of the textile products.
morphology where nodules are found on the surface. These nodules
From the literatures reported, polyamide and polyester fibres shared
increase in size along with the increment of the loading cycles in air and
similar fracture morphologies when subjected to similar mechanical
maybe considered as the nuclei for crack initiation. Fatigue tensile
tests. In the cases of monotonic and creep tensile mechanical tests, v-
loading on the Kevlar in vacuum, however does not induce the nodular
notch fracture morphologies are observed [1,2,37–54] as illustrated in
morphology as in the fatigue tensile loadings upon the increment in
Fig. 15.
loading cycles. Instead, an undulation morphology is observed. Min-
According to Hearle et al. [44] and Ogata et al. [54], the fracture
oshima et al. [30] inferred that the fatigue loading in vacuum may
surface in Fig. 15 can be divided into five main regions denoted in
promote the molecular rearrangement in the fibre and thus, trans-
sequence by A, B, C, D and E as illustrated in Fig. 16. Region A was
forming the nodular morphology to undulation morphology. This un-
defined as the crack initiation region, Region B as a smooth surface
dulation morphology is observed within the core but not on the surface
rising from the crack initiation point the fibre interior, Region C as a
series of sharp steps, Region D as a less smooth region perpendicular to
the fibre axis and lastly Region E a very rough area at the fibre edge.
On the other hand, Lamb [45] divided the fracture surface in Fig. 15
into two segments, a slow segment and a fast segment. The slow seg-
ment is described as the region where the crack is growing in a finite
speed with smooth ductile cleavage propagation, while the fast segment
is the load bearing region with rough surface before the catastrophic
failure occurs. These two segmented fracture surfaces proposed are si-
milar to the proposal by Averett et al. [39] although the terms fast and
slow segments are not used in that study. A clear and distinct boundary
can be observed between the two segments as shown in Fig. 17, where
fast segments are denoted by F and slow segments are denoted by S. The
slow segment seems to decrease with the increment in the fast segment
area as the strain rate of the tensile test imposed on the fibre increases.
Hence, it is reasonable to infer that the load bearing area is larger under
higher strain rate since the fast segment is the load bearing area before
the total failure of the fibre.
In this study as well, Lamb [45] stated that the crack growth in the
Fig. 12. Illustration of crack propagation in Kevlar proposed by Konopasek fast segments increases the strength of the fast segments despite de-
et al. [28]. creasing the load bearing areas. To put it simply, the breaking stress

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

Fig. 13. Micrographs of Kevlar after fatigue tensile loadings [30].

Fig. 14. (a) Flat fracture surface of an acrylic fibre under a monotonic tensile loading; (b) Axial splitting of an acrylic fibre under a cyclic loading [37].

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

Fig. 15. Illustration of two fractured ends of a fibre due to monotonic tensile
mechanical test [42].

Fig. 17. Micrographs and schematics of the fracture surfaces with two segments
on nylon fibres due to monotonic tensile mechanical tests under the strain rate
of (a) 10-3, (b) 10-2, (c) 10-1, (d) 2, and (e) 20/min [45].
Fig. 16. Five regions of the fracture surface [44].
PEN fibres [42]. During tensile fatigue loading, a crack is initiated at
increases as the fast segment decreases in area. Nevertheless, failure or near the surface and propagates perpendicularly toward the axis of
does not occur rapidly, opposing the Griffith microcrack growth failure the fibre to a distance of 1 µm or less [46,49]. Then, the crack
criterion where failure will occur rapidly due to the higher stress con- propagation deviate at a small angle with respect to the fibre axis.
centration on the fast segment. Judging from this peculiar phenom- This is followed by a gradual penetration of crack perpendicular to the
enon, Lamb [45] proposed that a fibre consists of an assembly of mi- fibre axis which further reduces the load bearing cross-section similar to
crofibrils. Consequently, the strengthening mechanisms in a fibre the monotonic and creep tensile failure as discussed earlier until the
depend on two factors, the average tensile strength and the distribution catastrophic failure of the fibre with a long tongue at one end of the
or density of the tensile strengths of the microfibrils within the fibre. It fractured fibre. The long tongues are always curved inward toward the
is possible that the rearrangement of the microfibrils takes place at a axes of the fibres due to the compressive residual stress in the skin of
large strain close to failure and narrow down the distribution of tensile the fibres [43,49] as shown in the fractography of a PA 66 fibre in
strengths, making the fibre stronger despite having smaller load bearing Fig. 18(b).
area. Nevertheless, Ramirez et al. [43] observed that the fracture
3.1.2.2.2. Fatigue tensile failure. Aside from the monotonic tensile morphologies of nylon 66 and PET fibres can be different from the ty-
mechanical tests, polyamide and polyester fibres also share the similar pical morphology as illustrated in Fig. 18. In some cases, a large cavity
fracture morphology under the tensile fatigue mechanical loadings. was seen on one end of the fracture surface while the complementary
This typical fatigue failure with long tongue at one fractured end as end showed the shape of a crater. This observation indicates that the
illustrated in Fig. 18(a) is observed in nylon fibres fatigue crack is initiated inside the fibre near the surface, which sub-
[2,32,37,40,43,46,49–51,53,76], PET fibres [38,41–43,47,51] and sequently leads to slow crack growth at a small angle with respect to

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

Fig. 18. (a) Illustration of a typical fracture morphology due to tensile fatigue failure [42]; (b) Micrograph of a PA 66 fibre undergone tensile fatigue failure with a
long tongue morphology [40,50].

2. The cracks may exist throughout the fibres during the fatigue
loadings. However, as mentioned earlier, only the cracks near the
skin will contribute to the fracture of the fibres.
3. The first longitudinal crack, which emerges on the surface of the
fibre will propagate in the fastest manner due to the broken trans-
lational symmetry. Other cracks may not able to contribute to the
total failure of the fibres as the propagation speed will be very slow
as compared to the first longitudinal crack on the surface of the
fibre.

In short, the arguments mentioned in the previous paragraph are

built on the basic that the fatal crack initiation sites must be located
within the fibres but near the surfaces. This is because the fibres have
skin/core structures. The boundaries of the skin/core structures are
inhomogeneities and thus highly prone to cracking failure. Clerc et al.
[51] observed PET and nylon fibres under the polarized light. The
micrographs are as shown in Fig. 20. Apart from the inclusions, the
birefringence of the fibres is found to be high with high number of
colour bands, indicating the existence of skin and core structure with
Fig. 19. Schematic illustration of the crack propagation processes which pro- different properties respectively. In addition, the skin/core structure is
duced the conical fracture morphology [43]. also proven through the characterisations of Raman/IR micro-
spectrometry along the diameters of the fibres [40,50,53,76]. This skin/
fibre axis, producing the observed conical morphology as demonstrated core structure is believed to be the result of the cooling gradients during
in Fig. 19. Some fracture surfaces were observed with a foreign particle the spinning process of the fibres [40,51]. The skin will solidify and
at the point of crack initiation, which can act as an inhomogeneity that crystallise faster than the core. Consequently, the skin will experience
is believed to be the origin of the initial failure. plastic deformation due to the slower crystallization of the core. This
The study conducted by Clerc et al. [51] is in agreement with Ra- plastic deformation induces higher orientation and residual compres-
mirez et al. [43]. Both of their Energy Dispersive Spectrometry (EDS) sive stress in the skin.
analyses show the existence of foreign elements such as antimony and In addition to fatigue fracture, monotonic fracture with prior fatigue
silicon within the fibres. These elements are in the form of particles or loading with prescribed number of cycles was conducted to investigate
solid inclusions which maybe the residues of catalysts, active chemical the effect of fatigue on the failure mechanism of nylon 66 and PET
or mechanical additives added into fibres during the fabrication pro- fibres [38,39]. Both studies showed typical fracture morphology of
cess. It is generally acceptable that these foreign inclusions are the seeds tensile or creep, where crack initiation was followed by the formation
of crack initiations since it can facilitate the generation of shear stresses of v-notch, and finally the rapid fracture of fibre. Yet, a slight difference
in the polymer matrix and weaken the local structure within the fibre. was observed for fatigued PET fibres where there were several micro-
However, Clerc et al. [51] further elaborated that not all the par- failure splits formed along fibre axis, indicating a slight damage accu-
ticles will involve in the crack initiation and propagation processes until mulation during fatigue.
the failure of the fibres based on three arguments. By now, it can be concluded that the fracture of polyamide and
polyester fibres involve a skin/core decohesion and crack propagation
1. The particles need to be located at 1 µm or less from the skin to mechanism. The factors affecting these mechanical behaviours or me-
initiate the crack. Otherwise, the particles need to be in the crack chanisms can be summarized as follows [53].
propagation path to assist in the crack propagation.

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

Fig. 20. Optical images of PET and nylon fibres under polarized light [51].

1. The strength and density of chemical bonds per unit volume. Although the crystallites are embedded within the amorphous domains,
2. The size and distribution of the fatal defects, imperfections, or these domains are different within the fibrils and between the fibrils.
heterogeneity. The intrafibrillar regions are the typical amorphous domains, where the
3. The fabrication and loading histories. chains are randomly oriented. On the contrary, the polymeric chains in
3.1.2.2.3. Microstructural models. In the literature, there are two the interfibrillar amorphous domains are aligned. This type of
models commonly used to describe the microstructures of semi amorphous domains with aligned polymeric chains are named as the
crystalline polyamide and polyester fibres, which are the Pervosek mesomorphous domains. As for the Oudet Model, the microfibrils
Model [40,50,53,76,79] and Oudet Model [40,41,48,53,76] as described in the Pervorsek Model are constituents of a bigger entity,
illustrated in Fig. 21. These two models are similar as both models macrofibril. Similar to Pervorsek Model, this Oudet Model has the
are consisting of crystallites embedded inside the amorphous domains. mesomorphous domains between the microfibrils and also the
The crystallites are connected or linked together in series by the macrofibrils.
polymeric chains in the amorphous domains to form microfibrils. In According to Oudet et al.[48], the existence of the microfibrils and
the Pervorsek Model, a fibre is consisting of an assembly of microfibrils. macrofibrils in the Oudet Model can be proven through the striations on

Fig. 21. (a) Pervorsek Model [79] and (b) Oudet Model [48].

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

failure. This minimum load criterion for fatigue failure is in line with
many studies [40,41,46,47,49,50] in the literature.
A structural modifications during cyclic loading of polyamide 66
fibres is proposed by Ramirez et al. [50] and illustrated in Fig. 23. In
Pervorsek Model, the reorganization of the molecular structure in the
fibres below the minimum load criterion for fatigue failure can induce
friction due to interaction between the polymeric chains in amorphous
domains and mesomorphous domains. The chains in the intrafibrillar
amorphous domains will buckle and shear with the polymeric chains in
the interfibrillar mesomorphous domains. At the end, melting occurs
accompanied by the fatigue failure of the fibres due to the heat gen-
eration by the friction between the polymeric chains [40,49]. Nasri
et al. [49] recorded an approximately increase of 6 °C in the tempera-
ture of polyamide 66 fibre as the fibre is undergoing fatigue tensile
loading. This increment in temperature is maybe due to the heat gen-
eration by the friction between polymeric chains. Based on this pro-
posal, the fatigue failure can occur anywhere in the fibres. However,
this is not true. Fatigue failures always initiate on the skin or near the
Fig. 22. Fatigue fractured surface along the fibre axis. The lines represent 1 µm
skin as shown in Fig. 15 and Fig. 18 due to the residual compressive
[48].
stress on the skin [40,51] as discussed in the previous session. Hence,
Ramirez et al. [40] suggested that the fatigue failure of a fibre is caused
the fatigue fractured surface along the axis of a polyester fibre as shown by the loss of compliance of the amorphous domains in the fibre ex-
in Fig. 22. The macrofibrils with diameters ranged from 200 nm to acerbated by the residual compressive stress on the fibre skin.
500 nm are superimposed on the microfibrils with diameters ranged
from 15 nm to 20 nm. Fatigue cracks propagate through the faults or
endings of the macrofibrils in the fibres. 3.2. Nanofibres
Oudet et al. [48] further explain that the mesomorphous domains in
the fibres are responsible for the mechanical behaviors of the fibres. Nanofibres are intriguing nanomaterials with interesting properties
Since the crystallites are already well compacted, only the polymeric such as high surface area to volume ratio and porosity. Hence, they are
chains in the mesomorphous domains can undergo deformations during found to be versatile and useful in healthcare, energy, water and en-
mechanical loadings. The strain hardening occurs when the polymeric vironment applications [55,56]. As mentioned earlier, it is known that
chains in the mesomorphous domains are stretched and failure occurs nanofibres behave differently than their bulk counterparts in many
when these polymeric chains connecting the crystallites ruptures during aspects, including mechanical properties [83,92]. Thus, the study of the
uniaxial mechanical tensile loadings. Thus, the anchorages between the deformation mechanisms and fractography of these nanofibres are of
crystallites and the polymeric chains in the mesomorphous domains interests in this context.
play important roles in determining the mechanical strength and da- An illustration of the deformation mechanism in nanofibres
mage to the fibres. [64,66,67,77,80–82] is presented in Fig. 24. The most distinct feature
The fatigue behaviours of the fibres can be relatable to the mole- in the fractography of nanofibres is the formation of multiple necking or
cular movements in the fibres according to Oudet et al. [48]. In order to surface ripples along the axis of the fibre, indicating local deformation
initiate the fatigue failure, reorganization of the molecular structures in instabilities. Distances between the necking are varied, ranging from
the fibres is needed. This reorganization can be achieved through ap- 1 µm to 7 µm as found in the study of Zussman et al. [80] on poly-
plying a minimum cyclic load threshold level to the fibres. If the cyclic ethylene oxide nanofibres. Neck propagations do not exist in the case of
load is higher than the threshold level, the fibres will have a longer nanofibres since the adjacent necks impede the propagation mutually
lifetime and creep failure is most probably to occur instead of fatigue [64]. Nevertheless, one of the necking will craze, a common phenom-
enon found in the cracking of polymers. In the end, the fibre will

Fig. 23. Proposed structural modifications during cyclic loading of polyamide 66 fibres by Herrera Ramirez et al. [50].

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

Fig. 24. Illustration of the deformation mechanism in nanofibres

[64,66,67,77,80–82].

fracture into two kinds of fracture surface, a flat fractured surface with
core shell structure [67,80] and a pointed fractured surface
[64,66,77,81–83].
Naraghi et al. [66] suggested that the occurrence of the multiple
necking is due to the high surface area to volume ratio of the nano-
fibres. High surface area to volume ratio increases the mobility of the
molecules on the surface of the fibres and thus contributing more to the Fig. 25. (a) Undeformed polyacrylonitrile nanofibre and deformed poly-
mechanical load bearing of the fibres. As a result, the load transfer acrylonitrile nanofibre stretched under the strain rate of (b) 0.00025 s−1, (c)
occurs through the entanglements of the molecular chains network on 0.0025 s−1 and 0.025 s−1 [64].
the surface without much lateral entanglement contributed by the in-
terior or core of the fibres. Thus, cracks or necks are more likely to
occur on the surface. However, unlike nanofibres, macroscopic poly-
meric materials are only able to accommodate one single necking be-
fore failure. This unique multiple necking of nanofibres is attributed to
their much higher length to diameter ratio as compare to the macro-
scopic polymeric materials, allowing them to accommodate many
perturbation wavelengths before failure [80]. Naraghi et al. [64] fur-
ther described nanofibre with a ductile core covered by a brittle shell
structure. The multiple necking deformation mechanism of the fibres is
similar to the fragmentation of a brittle film deposited on a ductile
substrate.
In another study conducted by Liu et al. [67], the multiple necking
of the nanofibres is proposed to be originated from the uneven mole-
cular entanglement density distribution in the fibres. Regions with the
lower molecular entanglement density will be stretched and deformed
easily followed by the formation of multiple necking. This proposal is in
line with a study conducted by Naraghi et al. [64]. In that study,
polyacrylonitrile nanofibres were stretched at different strain rates. As a
result, the fibres stretched under significantly low strain rate shows
lower degree of multiple necking as shown in Fig. 25. This is because
stretching at lower strain rate enables the rearrangement of the mac-
romolecules due to creep and thus, the molecular entanglement density
can be more evenly distributed during the process.
After the formation of multiple necking, crazing occurs subse-
quently as shown in Fig. 24. Intrinsic fibrils are formed, and final Fig. 26. Strengthening mechanism of carbon nanotubes on nanofibres [77].
rupture occurs when the fibrils are unable to sustain the load upon
stretching. This crazing mechanism is said to contribute to the energy
absorbing and toughen the fibres similar to the rubber – modified high

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C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

Fig. 27. (a) Micrographs showing in situ deformation process of a poly (methyl methacrylate)/sodium montmorillonite composite nanofibre; (b) The stress field
under a uniaxial tensile load at crack tips where the load direction is parallel to the fibre axis [84].

impact polymer. However, the fibrils can also act as stress concentra- fibres. The spiral arrangement of the fibrils inside the cotton fibres
tion sites, weakening the fibres [77]. In order to further strengthen the causes an untwisting mechanism to occur during the tensile deforma-
nanofibres, carbon nanotubes can be incorporated into the fibres tion along the axis of the fibres. Failures or fractures happen when
[67,77,85]. The strengthening mechanism of the carbon nanotubes on surface cracks start to form. As for flax fibres, they have different layers
the nanofibres is illustrated in Fig. 26. Initially, a neck or notch forms of fibrils oriented at different direction. However, these fibrils will re-
on the fibre upon stretching. Further stretching would induce the orient to the direction of the loading axes during mechanical tensile
crazing mechanism. At the same time, the carbon nanotubes would also tests, evidenced by the fracture morphology of the fibre showing
align according to the axis of the fibre. During the rupture event, the aligned fibrils in the direction of loading axis.
carbon nanotubes would be pulled out. Some of these nanotubes would The fractography of two types of natural protein based fibres,
connect the two parts of the ruptured fibre avoiding total failure to a namely spider and silkworm silk fibres are reviewed in this study. It is
certain extent. found that the spider silk fibres have a flat fracture morphology, in-
In another study conducted by Kim et al. [84], brittle nanofibres can dicating a brittle fracture. However, the surface is rough, most probably
be altered to become ductile by introducing nanopores into the fibres. due to the fibrils existing inside the fibres. On the other hand, the
According to Kim et al. [84], these nanopores can change the de- silkworm silk fibres are having different fracture morphology de-
formation mechanism of the nanofibres from crazing to shear yielding. pending on the species of the silkworms. Some fibres have flat fracture
Consequently, a brittle fracture is supressed, and a ductile necking is morphology with brins pulled out from a sericin protein coating inside
observed in the fibres during mechanical tensile loading as shown in the fibres. Other fibres have axial splitting failures due to defibrillation
Fig. 27(a). This ductile necking mechanism can be explained based on or decohesion of the fibrils inside the fibres.
fracture mechanics [84] as illustrated in Fig. 27(b). When a nominal For the synthetic microfibres, two types of fractography can be
stress, σo is applied to the fibre, the pores on the surface of the fibre will observed, which are the axial splitting and radial fracture. Axial split-
act as stress concentrators. A maximum stress, σm will be induced at the ting is normally found in Kevlar, fibres used in the ballistic clothing to
tip of a pore with a radius of curvature, ρt. Assuming the pore is resist fracture at very high strain rate. Radial fracture is more com-
hemisphere in shape, the crack length, a is the same as the ρt. The monly found in synthetic microfibres, such as acrylic, polyester and
maximum stress concentrator, K will be at the equator region of the polyamide fibres. However, polyester and polyamide fibres have a skin
pore and since there are a number of pores on the surface of the fibre, – core microstructure. The crack is found to initiate at the region at or
there will be a strong stress overlapping zone at the centre of the fibre. near the skin of the fibres and propagate radially across the diameters of
As a result, a shear yielding or ductile necking is observed during the the fibres. A unique skin peeling morphology can be observed in the
mechanical loading. tensile fatigue fracture of polyester and polyamide fibres. This maybe
attributed to the cooling gradient across the diameter of the fibres
during the spinning process of the fibres.
4. Conclusion Synthetic nanofibres have the most unique fractography. The frac-
tography of microfibres and nanofibres are different despite being the
The fractography of the polymeric fibres with diameter less than same polymeric fibres. These nanofibres seem to have multiple necking
50 µm under uniaxial tensile mechanical loadings are reviewed in this before total fracture, which is different from typical ductile polymeric
study. The deformation and failure mechanisms of the fibres can be bulk materials as only single necking can be observed at the stress
different depending on the nature and microstructure of the fibres. concentration site of the materials during mechanical loading. Another
In the case of natural cellulose fibres, the deformation mechanisms peculiar phenomenon can be observed when carbon nanotubes fillers or
are highly depending on the arrangement of the fibrils embedded in the

15
C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

nanopores are introduced to the nanofibres. Addition of ceramic fillers Major Ampulate Gland Silk Fibers Extracted from Nephila clavipes Spiders, American
and pores into typical polymeric materials will normally become more Chemical Society, Silk Polymers, 1993, pp. 234–251.
[20] P. Jiang, H. Liu, C. Wang, L. Wu, J. Huang, C. Guo, Tensile behavior and mor-
brittle. However, these composite or porous nanofibres are observed to phology of differently degummed silkworm (Bombyx mori) cocoon silk fibres,
have increment in the ductility. Mater. Lett. 60 (7) (2006) 919–925.
In conclusion, the fractography of the polymeric fibres can be un- [21] K. Yamauchi, S. Yamasaki, R. Takahashi, T. Asakura, Microscopic structural ana-
lysis of fractured silk fibers from Bombyx mori and Samia cynthia ricini using 13C
ique and interesting. By studying the fractography of these fibres, a lot CP/MAS NMR with a 1mm microcoil MAS NMR probehead, Solid State Nucl. Magn.
of information on the microstructure and fracture mechanisms of these Reson. 38 (1) (2010) 27–30.
fibres which is useful in the materials design against mechanical failure [22] B. Mortimer, D.R. Drodge, K.I. Dragnevski, C.R. Siviour, C. Holland, In situ tensile
tests of single silk fibres in an environmental scanning electron microscope (ESEM),
can be revealed. Although the fractography studies in this review only J. Mater. Sci. 48 (14) (2013) 5055–5062.
include fracture under the uniaxial mechanical tensile loadings in am- [23] R. Rajkhowa, J. Kaur, X. Wang, W. Batchelor, Intrinsic tensile properties of cocoon
bient condition to limit the scope of the study, it is undeniable that silk fibres can be estimated by removing flaws through repeated tensile tests, J. R.
Soc. Interface 12 (107) (2015).
these fibres can also be subjected to other various loadings under ex-
[24] E. Koh, K.H. Hong, Preparation and properties of wool fabrics dyed with spent
treme operating environments. The fractography of the fibres can be coffee ground extract, Text. Res. J. 89 (1) (2019) 13–19.
different in these operating conditions. Nevertheless, this study can be a [25] C. Bakker, A. Ghosh, S. Tandon, S. Ranford, Surface modification of wool fabric
strong and solid base for subsequent studies on more diverse fracto- with POSS® nanomaterial, Fiber. Polym. 19 (10) (2018) 2127–2133.
[26] S. Mowafi, H. Kafafy, A. Arafa, K. Haggag, M. Rehan, Facile and environmental
graphy studies on the fibres. benign in situ synthesis of silver nanoparticles for multifunctionalization of wool
fibers, Environ. Sci. Pollut. Res. 25 (29) (2018) 29054–29069.
Declaration of Competing Interest [27] M.R. Roenbeck, E.J. Sandoz-Rosado, J. Cline, V. Wu, P. Moy, M. Afshari,
D. Reichert, S.R. Lustig, K.E. Strawhecker, Probing the internal structures of Kevlar®
fibers and their impacts on mechanical performance, Polym. 128 (2017) 200–210.
The authors declare that they have no known competing financial [28] K. L., H.J.W. S., The tensile fatigue behavior of para-oriented aramid fibers and
their fracture morphology, J. Appl. Polym. Sci. 21(10) (1977) 2791–2815.
interests or personal relationships that could have appeared to influ- [29] M.R. J., P.C. O., S.W. J., The relationship between the physical structure and the
ence the work reported in this paper. microscopic deformation and failure processes of poly(p-phenylene ter-
ephthalamide) fibers, J. Polym. Sci.: Polym. Phys. Ed. 21(9) (1983) 1757–1783.
[30] K. Minoshima, Y. Maekawa, K. Komai, The influence of vacuum on fracture and
Acknowledgements
fatigue behavior in a single aramid fiber, Int. J. Fatigue 22 (9) (2000) 757–765.
[31] M. Cheng, W. Chen, T. Weerasooriya, Mechanical properties of Kevlar® KM2 single
This work was supported by the University of Malaya Frontier fiber, J. Eng. Mater. Technol. 127 (2) (2005) 197–203.
[32] M. Kerr, N. Chawla, K.K. Chawla, The cyclic fatigue of high-performance fibers,
Research Grant (FG010-17AFR), Fundamental Research Grant Scheme
JOM 57 (2) (2005) 67–71.
(FP047-2019A, FP048-2019A), University of Malaya Research Grant [33] D.L. Languerand, H. Zhang, N.S. Murthy, K.T. Ramesh, F. Sansoz, Inelastic behavior
(RP041A-17AET) and the Embassy of France in Malaysia. and fracture of high modulus polymeric fiber bundles at high strain-rates, Mater.
Sci. Eng.: A 500 (1) (2009) 216–224.
[34] N. Kimiyoshi, Tensile properties and weibull modulus of some high-performance
References polymeric fibers, J. Appl. Polym. Sci. 128 (2) (2013) 1185–1192.
[35] J.H. Kim, N.A. Heckert, S.P. Mates, J.E. Seppala, W.G. McDonough, C.S. Davis,
[1] J.W.S. Hearle, S.C. Simmens, Electron microscope studies of textile fibres and K.D. Rice, G.A. Holmes, Effect of fiber gripping method on the single fiber tensile
materials, Polym. 14 (6) (1973) 273–285. test: II. Comparison of fiber gripping materials and loading rates, J. Mater. Sci. 50
[2] A.R. Bunsell, J.W.S. Hearle, Fracture and fatigue of fibres, Rheol. Acta 13 (4) (1974) (5) (2015) 2049–2060.
711–716. [36] S. Sockalingam, S.C. Chowdhury, J.W. Gillespie, M. Keefe, Recent advances in
[3] O. Harzallah, H. Benzina, J.-Y. Drean, Physical and mechanical properties of cotton modeling and experiments of Kevlar ballistic fibrils, fibers, yarns and flexible woven
fibers: Single-fiber failure, Text. Res. J. 80 (11) (2010) 1093–1102. textile fabrics – A review, Text. Res. J. 87 (8) (2017) 984–1010.
[4] J.W.S. Hearle, J.T. Sparrow, The fractography of cotton fibers, Text. Res. J. 41 (9) [37] A.R. Bunsell, J.W.S. Hearle, The fatigue of synthetic polymeric fibers, J. Appl.
(1971) 736–749. Polym. Sci. 18 (1) (1974) 267–291.
[5] L. Yan, N. Chouw, K. Jayaraman, Flax fibre and its composites – A review, Compos. [38] R.D. Averett, M.L. Realff, K.I. Jacob, The effects of fatigue and residual strain on the
Part B: Eng. 56 (2014) 296–317. mechanical behavior of poly(ethylene terephthalate) unreinforced and nano-
[6] C. Baley, A. Le Duigou, A. Bourmaud, P. Davies, Influence of drying on the me- composite fibers, Compos. Pt. A-Appl. Sci. Manuf. 40 (6) (2009) 709–723.
chanical behaviour of flax fibres and their unidirectional composites, Compos. Part [39] R.D. Averett, M.L. Realff, S. Michielsen, R.W. Neu, Mechanical behavior of nylon 66
A: Appl. Sci. Manuf. 43 (8) (2012) 1226–1233. fibers under monotonic and cyclic loading, Compos. Sci. Technol. 66 (11) (2006)
[7] M. Aslan, G. Chinga-Carrasco, B.F. Sørensen, B. Madsen, Strength variability of 1671–1681.
single flax fibres, J. Mater. Sci. 46 (19) (2011) 6344–6354. [40] J.M. Herrera Ramirez, P. Colomban, A. Bunsell, Micro-Raman study of the fatigue
[8] C. Baley, Analysis of the flax fibres tensile behaviour and analysis of the tensile fracture and tensile behaviour of polyamide (PA 66) fibres, J. Raman Spectrosc. 35
stiffness increase, Compos. Part A: Appl. Sci. Manufac. 33 (7) (2002) 939–948. (12) (2004) 1063–1072.
[9] S. Ahmed, C. Ulven, Dynamic in-situ observation on the failure mechanism of flax [41] C. Le Clerc, A.R. Bunsell, A. Piant, Influence of temperature on the mechanical
fiber through scanning electron microscopy, Fibers 6 (1) (2018) 17. behaviour of polyester fibres, J. Mater. Sci. 41 (22) (2006) 7509–7523.
[10] P.R. Hornsby, E. Hinrichsen, K. Tarverdi, Preparation and properties of poly- [42] C. Lechat, A.R. Bunsell, P. Davies, A. Piant, Mechanical behaviour of polyethylene
propylene composites reinforced with wheat and flax straw fibres: Part I Fibre terephthalate & polyethylene naphthalate fibres under cyclic loading, J. Mater. Sci.
characterization, J. Mater. Sci. 32 (2) (1997) 443–449. 41 (6) (2006) 1745–1756.
[11] J.W.S. Hearle, The fine structure of fibers and crystalline polymers. III. [43] J.M. Herrera Ramirez, A.R. Bunsell, Fracture initiation revealed by variations in the
Interpretation of the mechanical properties of fibers, J. Appl. Polym. Sci. 7 (4) fatigue fracture morphologies of PA 66 and PET fibers, J. Mater. Sci. 40 (5) (2005)
(1963) 1207–1223. 1269–1272.
[12] H.L. Bos, A.M. Donald, In situ ESEM study of the deformation of elementary flax [44] J.W.S. Hearle, P.M. Cross, The fractography of thermoplastic textile fibres, J. Mater.
fibres, J. Mater. Sci. 34 (13) (1999) 3029–3034. Sci. 5 (6) (1970) 507–516.
[13] P.-R. J., E. M., P.G. R., R. J., G.G. V., Fracture surfaces and tensile properties of UV- [45] G.E.R. Lamb, Studies of tensile failure in oriented polymeric fibers by quantitative
irradiated spider silk fibers, J. Polym. Sci. Part B: Polym. Phys. 45(7) (2007) fractography, J. Polym. Sci. Pt. B-Polym. Phys. 20 (2) (1982) 297–305.
786–793. [46] C. Oudet, A.R. Bunsell, Loading criteria for the fatigue failure of polyamide 66 fi-
[14] G.R. Plaza, J. Pérez-Rigueiro, C. Riekel, G.B. Perea, F. Agulló-Rueda, bres, J. Mater. Sci. Lett. 3 (4) (1984) 295–298.
M. Burghammer, G.V. Guinea, M. Elices, Relationship between microstructure and [47] C. Oudet, A.R. Bunsell, R. Hagege, M. Sotton, Structural changes in polyester fibers
mechanical properties in spider silk fibers: identification of two regimes in the during fatigue, J. Appl. Polym. Sci. 29 (12) (1984) 4363–4376.
microstructural changes, Soft Matter 8 (22) (2012) 6015–6026. [48] C. Oudet, A.R. Bunsell, Effects of structure on the tensile, creep and fatigue prop-
[15] P. Poza, J. Pérez-Rigueiro, M. Elices, J. Llorca, Fractographic analysis of silkworm erties of polyester fibres, J. Mater. Sci. 22 (12) (1987) 4292–4298.
and spider silk, Eng. Fract. Mech. 69 (9) (2002) 1035–1048. [49] L. Nasri, A. Lallam, A.R. Bunsell, Fatigue failure in technical Polyamide 66 fibers,
[16] P.-R. J., E. M., L. J., V. C., Tensile properties of Argiope trifasciata drag line silk Text. Res. J. 71 (5) (2001) 459–466.
obtained from the spider's web, J. Appl. Polym. Sci. 82(9) (2001) 2245–2251. [50] J.M.H. Ramirez, A.R. Bunsell, P. Colomban, Microstructural mechanisms governing
[17] J.W.S. Hearle, Forms of fibre fracture, in: M. Elices, J. Llorca (Eds.), Fiber Fracture, the fatigue failure of polyamide 66 fibres, J. Mater. Sci. 41 (22) (2006) 7261–7271.
Elsevier Science Ltd, Oxford, 2002, pp. 57–71. [51] C. Le Clerc, A.R. Bunsell, A. Piant, B. Monasse, Role of skin/core structure and
[18] S. Putthanarat, N. Stribeck, S.A. Fossey, R.K. Eby, W.W. Adams, Investigation of the inclusions in the fatigue crack initiation and propagation in organic fibres, J. Mater.
nanofibrils of silk fibers, Polym. 41 (21) (2000) 7735–7747. Sci. 41 (20) (2006) 6830–6842.
[19] P.M. Cunniff, S.A. Fossey, M.A. Auerbach, J.W. Song, Mechanical Properties of [52] C. Le Clerc, B. Monasse, A.R. Bunsell, Influence of temperature on fracture initiation
in PET and PA66 fibres under cyclic loading, J. Mater. Sci. 42 (22) (2007)

16
C.J. Tan, et al. European Polymer Journal 137 (2020) 109924

9276–9283. Fracture, Elsevier Science Ltd, Oxford, 2002, pp. 303–328.

[53] C. Philippe, Understanding the nano- and macromechanical behaviour, the failure [74] J.W.S. Hearle, Fracture of common textile fibres, in: M. Elices, J. Llorca (Eds.), Fiber
and fatigue mechanisms of advanced and natural polymer fibres by Raman/IR Fracture, Elsevier Science Ltd, Oxford, 2002, pp. 329–353.
microspectrometry, Adv. Nat. Sci.-Nanosci Nanotechnol 4 (1) (2013) 013001. [75] W.E. Morton, J.W.S. Hearle, 19 - Fibre breakage and fatigue, in: W.E. Morton, J.W.
[54] N. Ogata, S. Dougasaki, K. Yoshida, Fractography of nylon-6 yarn, J. Appl. Polym. S. Hearle (Eds.), Physical Properties of Textile Fibres, fourth ed., Woodhead
Sci. 24 (3) (1979) 837–852. Publishing, 2008, pp. 509–558.
[55] C.T. Kenry, Lim, Nanofiber technology: Current status and emerging developments, [76] P. Colomban, J.M. Herrera Ramirez, R. Paquin, A. Marcellan, A. Bunsell, Micro-
Prog. Polym. Sci. 70 (2017) 1–17. Raman study of the fatigue and fracture behaviour of single PA66 fibres:
[56] S. Ramakrishna, K. Fujihara, W.-E. Teo, T. Yong, Z. Ma, R. Ramaseshan, Electrospun Comparison with single PET and PP fibres, Eng. Fract. Mech. 73 (16) (2006)
nanofibers: Solving global issues, Mater. Today 9 (3) (2006) 40–50. 2463–2475.
[57] C.J. Tan, J.J.L. Lee, B.C. Ang, A. Andriyana, G. Chagnon, M.S. Sukiman, Design of [77] H. Ye, H. Lam, N. Titchenal, Y. Gogotsi, F. Ko, Reinforcement and rupture behavior
polyurethane fibers: Relation between the spinning technique and the resulting of carbon nanotubes–polymer nanofibers, Appl. Phys. Lett. 85 (10) (2004)
fiber topology, J. Appl. Polym. Sci. 136 (26) (2019) 47706. 1775–1777.
[58] M. Cerović, Textile architecture: Exploring the potential of fiber assemblies and [78] J.W.S. Hearle, M. Miraftab, The flex fatigue of polyamide and polyester fibres, J.
their application in architecture, Serb Archit. J. (2012) 280–297. Mater. Sci. 26 (11) (1991) 2861–2867.
[59] L. Jacky Jia Li, A. Andri, A. Bee Chin, H. Bertrand, V. Erwan, Electrospun PMMA [79] D.C. Prevorsek, G.A. Tirpak, P.J. Harget, A.C. Reimschuessel, Effects of thermal
polymer blend nanofibrous membrane: electrospinability, surface morphology and contraction on structure and properties of PET fibers, J. Macromol. Sci. Part B-Phys.
mechanical response, Mater. Res. Express 5 (6) (2018) 065311. 9 (4) (1974) 733–759.
[60] T. Chin Joo, A. Andri, A. Bee Chin, C. Grégory, Inelastic deformation of highly [80] E. Zussman, D. Rittel, A.L. Yarin, Failure modes of electrospun nanofibers, Appl.
aligned dry-spun thermoplastic polyurethane elastomer microfibres, Mater. Res. Phys. Lett. 82 (22) (2003) 3958–3960.
Express 5 (12) (2018) 125301. [81] X.-F. Wu, Y. Kostogorova-Beller, A. Goponenko, H. Hou, Y.A. Dzenis, Rippling of
[61] D. Wong, A. Andriyana, B.C. Ang, E. Verron, Surface morphology and mechanical polymer nanofibers, Phys. Rev. E 78 (2009) 061804.
response of randomly oriented electrospun nanofibrous membrane, Polym. Test 53 [82] M. Naraghi, I. Chasiotis, Mechanics of PAN nanofibers, in: I.M. Daniel,
(2016) 108–115. E.E. Gdoutos, Y.D.S. Rajapakse (Eds.), Major Accomplishments in Composite
[62] V. Negi, R.C. Picu, Mechanical behavior of cross-linked random fiber networks with Materials and Sandwich Structures, Springer, Netherlands, Dordrecht, 2010, pp.
inter-fiber adhesion, J. Mech. Phys. Solids 122 (2019) 418–434. 757–778.
[63] M. Safarabadi, H. Feiz Mohammadi, An investigation into the effects of fiber ar- [83] Z. E., B. M., Y.A. L., K. R., C. Y., Tensile deformation of electrospun nylon-6,6 na-
chitecture on the mechanical behavior of woven preforms, J. Text. Inst. 109 (11) nofibers, J. Polym. Sci. Part B: Polym. Phys. 44(10) (2006) 1482–1489.
(2018) 1501–1509. [84] G.-M. Kim, R. Lach, G.H. Michler, Y.-W. Chang, The mechanical deformation pro-
[64] M. Naraghi, I. Chasiotis, H. Kahn, Y. Wen, Y. Dzenis, Mechanical deformation and cess of electrospun polymer nanocomposite fibers, Macromol. Rapid Commun. 26
failure of electrospun polyacrylonitrile nanofibers as a function of strain rate, Appl. (9) (2005) 728–733.
Phys. Lett. 91 (15) (2007) 151901. [85] X. Liu, Q.-S. Yang, X.-Q. He, K.-M. Liew, Self-densified microstructure and enhanced
[65] A.R. Bunsell, J.W.S. Hearle, R.D. Hunter, An apparatus for fatigue-testing of fibres, properties of carbon nanotube fiber by infiltrating polymer, Carbon 106 (2016)
J. Phys. E-Sci. Instrum. 4 (11) (1971) 868. 188–194.
[66] M. Naraghi, I. Chasiotis, H. Kahn, Y. Wen, Y. Dzenis, Novel method for mechanical [86] L. Talbot, Studies in the Decorative Arts 12(2) (2005) 143–147.
characterization of polymeric nanofibers, Rev. Sci. Instrum. 78 (8) (2007) 085108. [87] M. Panar, P. Avakian, R.C. Blume, K.H. Gardner, T.D. Gierke, H.H. Yang,
[67] L. L.-Q., T. D., P. M., W.H. D., Tensile mechanics of electrospun multiwalled na- Morphology of poly(p-phenylene terephthalamide) fibers, J. Polym. Sci: Polym.
notube/poly(methyl methacrylate) nanofibers, Adv. Mater. 19(9) (2007) Phys. Ed. 21 (10) (1983) 1955–1969.
1228–1233. [88] M.G. Dobb, R.M. Robson, Structural characteristics of aramid fibre variants, J.
[68] E.P.S. Tan, C.N. Goh, C.H. Sow, C.T. Lim, Tensile test of a single nanofiber using an Mater. Sci. 25 (1) (1990) 459–464.
atomic force microscope tip, Appl. Phys. Lett. 86 (7) (2005) 073115. [89] L.C. Sawyer, R.T. Chen, M.G. Jamieson, I.H. Musselman, P.E. Russell, The fibrillar
[69] Y. Li, W. Wan, Exploring polymer nanofiber mechanics: A review of the methods for hierarchy in liquid crystalline polymers, J. Mater. Sci. 28 (1) (1993) 225–238.
determining their properties, IEEE Nanotechnol. Mag. 11 (3) (2017) 16–28. [90] M.G. Dobb, D.J. Johnson, B.P. Saville, Supramolecular structure of a high-modulus
[70] E.P.S. Tan, C.T. Lim, Mechanical characterization of nanofibers – A review, Compos. polyaromatic fiber (Kevlar 49), J. Polym. Sci. Part B: Polym. Phys. 15 (12) (1977)
Sci. Technol. 66 (9) (2006) 1102–1111. 2201–2211.
[71] J.W.S. Hearle, Fracture of highly oriented, chain-extended polymer fibers, in: [91] A.P. Smith, H. Ade, Quantitative orientational analysis of a polymeric material
M. Elices, J. Llorca (Eds.), Fiber Fracture, Elsevier Science Ltd, Oxford, 2002, pp. (Kevlar® fibers) with x-ray microspectroscopy, Appl. Phys. Lett. 69 (25) (1996)
265–286. 3833–3835.
[72] Y. Termonia, Fracture of synthetic polymer fibers, in: M. Elices, J. Llorca (Eds.), [92] A. Pedicini, R.J. Farris, Mechanical behavior of electrospun polyurethane, Polym.
Fiber Fracture, Elsevier Science Ltd, Oxford, 2002, pp. 287–302. 44 (22) (2003) 6857–6862.
[73] C. Viney, Fracture of natural polymer fibres, in: M. Elices, J. Llorca (Eds.), Fiber

17