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Materials and Design 57 (2014) 298–305

Contents lists available at ScienceDirect

Materials and Design


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

Bombyx mori silk fibre and its composite: A review of contemporary


developments
A.U. Ude ⇑, R.A. Eshkoor, R. Zulkifili, A.K. Ariffin, A.W. Dzuraidah, C.H. Azhari
Department of Mechanical and Materials Engineering, Faculty of Engineering & Built Environment, The National University of Malaysia, 43600 UKM Bangi, Selangor, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: Application of natural fibres in composite plastics is gaining popularity in many industries and particu-
Received 29 July 2013 larly the automotive industry. Using natural fibres in polymers provides many advantages over other
Accepted 20 December 2013 techniques, and the application areas appear limitless. There is currently a shift of paradigm in the auto-
Available online 30 December 2013
motive industry towards a ‘‘green’’ outlook, due to consumers’ demand for more environmentally
friendly vehicles. Natural fibres are biodegradable and are renewable natural source. These two charac-
Keywords: teristics are most important for disposal of components at end-life. They are recyclable and can be easily
Bombyx mori silk fibre
converted into thermal energy through combustion, without leaving residue. Among the natural fibres
Composites
Natural fibres
with proven potential application as reinforcement for polymers, Bombyx mori woven silk fibre is one that
Biomedical material recently received special attention from researchers. B. mori silk fibre is one of the best fibres discovered
in nature, providing high mechanical properties over frequently used natural fibres like sisal, jute, hemp
and coir. This review presents a summary of B. mori woven silk fibre and its composite.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction industries [7–10]. The recent development in the use of B. mori silk
as a reinforcement in composites has raised great interest and
The focus of this review is Bombyx mori natural silk fibres. For expectations amongst materials scientists and engineers [11–17].
over 400 years, B. mori cocoon has been providing silk for the tex- The major studies on B. mori silk, carried out over the years can
tile industry. The cocoon is made of silk fibres consisting of two fi- be mostly divided into the following sub-headings:
broin brins and conglutinated by sericin binder. Silk fibroin is a
natural fibroin protein with a semi crystalline structure, which  Properties of B. mori silk fibres: Mechanical and thermal proper-
provides stiffness and strength. Sericin is an amorphous protein ties of B. mori silk have been studied. Scanning Electron Micro-
polymer, which acts as an adhesive binder to maintain the struc- scope (SEM), Thermogravimetry (TG), Dynamic Mechanical
tural integrity of the fibre and the cocoon. Studies on silk which Analysis (DMA), Differential scanning calorimetry (DSC) etc.,
has been on-going [1–4] for centuries, revealed that among known have been used to determine the structural characteristics of
natural fibres, natural silks fibres spun by silkworms possess excel- B. mori silk fibre and provide theoretical support for processing
lent mechanical properties in terms of high strength, elongation and application of this fibre.
and energy absorption, as a result of millions of years of evolution.  Interface properties between B. mori silk fibres and matrix: the
Silkworm spin silk for the protection of its larvae [5]. Mechanical main purpose here is to modify the fibre surface structure by
properties of silkworm silk, for instance; tensile strength, rival using chemical methods in order to enhance the bond strength
some synthetic fibres such as E-glass [1,2]. In terms of weight ratio between fibre and matrix and improve qualities.
and elongation at break, silkworm silk is better. Being one of the  Properties of woven B. mori silk-reinforced composites: the
strongest known natural fibre, B. mori silk seems to be the perfect matrix used in woven B. mori silk reinforced composites,
alternative to replace synthetic fibres. Studies has shown that it include: thermoplastics (polypropylene, polyethylene, etc.,),
possesses a high tensile strength [6], harvesting B. mori silk is easy thermosets (epoxy, polyester, etc.,) and elastomers (natural
and they are cultivated on a very large scale domestically. rubber etc.,). The effect of processing methods, fibre orienta-
Although B. mori silk fibre is one of the best quality natural fibres, tions, fibre lengths, fibre-surface treatment and fibre volume
a large quantity of this renewable resource is still under-utilised. fraction on the mechanical and physical properties of woven
Currently, B. mori silk fibre is mainly used as textiles for textile B. mori silk fibre-reinforced composites have been investigated.
industries, tissue engineering and suture material in biomedical
In this scientific review article, the overall characteristics of
⇑ Corresponding author. Tel.: +60 162843058. B. mori fibre, chemical composition and mechanical properties;
E-mail addresses: albertuche@yahoo.com, uchenna1@eng.ukm.my (A.U. Ude). properties of B. mori as a reinforced composite, its behaviour under

0261-3069/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.matdes.2013.12.052
A.U. Ude et al. / Materials and Design 57 (2014) 298–305 299

impact loading, as well as crashworthiness and possible applica- Raw silk reeling may be classified as (1) direct reeling method,
tions in automotive industry, will be reviewed. Besides, the manu- this is performed on a standard size reel; this method is commonly
facturing processes will be discussed, and the key technical issues used in traditional reeling process, Fig. 2 describes this process, the
that need to be solved in the future, will also be addressed. Whilst basic set-up in traditional silk reeling process include: a pot for
articles on the properties of B. mori natural fibre have been pub- pre-heating the cocoon with an attached reel, silk brins are pulled
lished, the authors have concluded that a detailed review article out of the cocoons to form a single fibre, the fibre is passed through
on the contemporary developments of B. mori and its composites a hole in the wooden design to the moving reel [18]. (2) Indirect
has not yet been published; it is believed that such an article method, which means reeling on small reels and transfer the reeled
should be of substantial value to the materials and composites re- silk to a standard size reel on a re-reeling machine. This last tech-
search world. nique is primarily applied in modern silk reeling processes. The
modern technique of reeling has advantage over traditional tech-
2. Life cycle of Bombyx mori silkworm nique as good quality of silk yarn is obtained from this technique.
In modern techniques, the size of silk yarn is maintained uniform
The cultivation of silkworm is known as sericulture. Silk fila- by the use of denier indicator, and reduced reeling speed which
ment produced by B. mori, the mulberry silk moth, passes through is vital in producing quality silk yarn is also maintained.
different stages. The first stage of silk production is the laying of
silkworm eggs; this is done in a controlled environment, the fe- 3. Properties of Bombyx mori silk fibres
male deposits 300–400 eggs at a time. The female dies almost
immediately after depositing the eggs and the male lives only a Presently, B. mori silk is the most researched silk in biotechnol-
short period after that. Second stage, the eggs are incubated for ogy, textiles, fibre composite; and biomedical fields [18,20–32].
about ten days until they hatch into larvae (caterpillars). The third Physically, silk fibre is eco-friendly, and very transparent with well
stage is the feeding period; the larvae are fed with mulberry leaves ranged structure.
for about six weeks [18]. As soon as the silkworms stopped eating,
they are ready to spin silk cocoon. Fig. 1 shows pictorial diagram of 3.1. Chemical composition of Bombyx mori silk
the production cycle of B. mori silk by silkworm. Silkworms spin
silk fibres to construct cocoons. A cocoon, with weight of only sev- B. mori silk fibre is naturally created with two different protein-
eral grams, is made of a single continuous silk strand with a length based layers (Fig. 3), fibroin in an inner layer and a sericin coating
in the range of 700–1500 m. The silk spun by the silkworm, B. mori in an outer layer. Every silk thread consists of fibroin filaments of
silk, consists mainly of two self-assembled proteins, sericin and fi- 10–14 lm, each embedded in the sericin coating, which acts like
broin, the former forming a sheath around the latter. an envelope to bind the fibroins together. The composition of fi-
broin and sericin include matters such as, fats, wax, and sand pig-
2.1. Bombyx mori silk reeling process ments plus minerals, have been well investigated [33,34]. Fibroin
comprises of a high content of the amino acids glycine and alanine,
Silk reeling is a process by which a number of cocoon baves are 42.8 g and 32.4 g respectively. The amino acids in sericin are serine
reeled together to produce a single thread. Continuous fibre can only (30.1 g), threonine (8.5 g), aspartic acid (16.8 g) and glutamic acid
be spun when the sericin coating is removed from the cocoon struc- (10.1 g), see Table 1 for a complete data.
ture. The process of removing the sericin is called degumming treat-
ment, which is performed by soaking the B. mori silk in hot water 3.2. Mechanical properties of Bombyx mori
[19]. Silk reeling is then achieved by unwinding filaments collec-
tively from a group of cooked cocoons at one end in a warm water Many investigations have been made on the mechanical proper-
bath and winding the resultant thread onto a fast moving reel. ties of silkworm silks and their dependence relationship with the

Fig. 1. Life cycle of Bombyx mori silkworm.


300 A.U. Ude et al. / Materials and Design 57 (2014) 298–305

Fig. 2. Traditional set-up of Bombyx mori silk reeling process.

Table 1
Amino acid composition of fibroin and sericin in B. mori silk.

Amino acids Fibroin Sericin Amino acids Fibroin Sericin


Glycine 42.8 8.8 Glutamic acid 1.7 10.1
Alanine 32.4 4.0 Serine 14.7 30.1
Leucine 0.7 0.9 Threonine 1.2 8.5
Isoleucine 0.9 0.6 Phenylalanine 1.2 0.6
Valine 3.0 3.1 Tyrosine 11.8 4.9
Arginine 0.9 4.2 Proline 0.6 0.5
Histidine 0.3 1.4 Methionine 0.2 0.1
Lysine 0.5 5.5 Tryptophan 0.5 0.5
Aspartic acid 1.9 16.8 Cystine 0.1 0.3

Tsukada et al. [40] investigated the effect of silk filament size on


the properties of silkworm silk. They found that the tensile
Fig. 3. Schematics diagram showing Bombyx mori silk unique features (source [35]). strength and breaking energy of fine silk fibres are significantly
higher, while the elongation at break does not change with the fi-
bre diameter. Kawahara et al. [41] found that after B. mori silk was
microstructures. Shao [36] examined the effect of the harvesting treated with meth-acrylamide, its Young’s modulus was increased
conditions on the mechanical properties of B. mori silk. They found markedly, its elongation-to-break was decreased significantly, and
that silkworm silk produced by artificial reeling could be stronger, while its breaking strength had no evident change. Rajkhowa et al.
stiffer and more extensible than that spun naturally. Pérez-Rigue- [42] studied the tensile stress–strain behaviour of four kinds of In-
iro et al. [28,29,37,38], systematically studied the mechanical dian silk fibres. They found that in comparison with non-mulberry
properties (e.g., Young’s modulus, shear modulus, yield stress silk, mulberry silk has higher initial modulus, tenacity along with
and tensile breaking strain) of silkworm silk under different condi- lower elongation-to-break and toughness, and superior elastic
tions. Using a combination of mechanical deformation and Raman recovery capability; other mechanical properties comparison of
spectroscopy, Sirichaisit et al. [39], studied the relationship be- some natural and synthetic fibres are shown in (Table 2). Jelinski
tween the tensile deformation behaviour and molecular structures. [43] reported the stress–strain relationship of B. mori silk structure,
A.U. Ude et al. / Materials and Design 57 (2014) 298–305 301

Table 2
Mechanical properties comparison of some natural and synthetic fibres.

Material Density (kg/cm3) Tensile strength (MPa) Young’s modulus (GPa) Elongation at failure (%) Source
B. mori silk 1.3–1.8 650–750 16 18–20 [44]
Spider silk 1.3 1300–2000 30 28–30 [45]
Flax 1.5 345–1035 50 2.7–3.2 [46]
Hemp 1.48 690 70 1.6 [46]
Jute 1.3 393–773 26.5 1.5–1.8 [46]
Coir 1.2 175 4.0–6.0 10.0 [46]
Sisal 1.5 155–635 9.2–22.0 2.0–2.5 [46]
Cotton 1.5–1.6 287–597 5.5–12.5 7.0–8.0 [46]
E-glass 2.7 1200 73 2.5 [46]
Carbon 1.8 4000 131 2.8 [46]
Kevlar49 1.44 3600–4100 131 2.8 [45]

Fig. 4. A representative tensile stress–strain curve of Bombyx mori silk. Fig. 5. Comparison of force–displacement curves of adjacent fibres submerged in
ethanol, acetone and air (gauge length^ 30 mm).

and the curve is shown in Fig. 4. Elastic region, plastic region, elas-
tic modulus (E), yield point and breaking point were well investi- 4. Bombyx mori silk fibre composites
gated. Further investigation reports on B. mori silk fibre
properties show that they have higher tensile strength than glass 4.1. Bombyx mori silk fibre in biomedical applications
fibre or other synthetic organic fibres, good resilience and excellent
elasticity [38]. Considering the thermal properties, B. mori silk fibre B. mori silk fibre has been used as biomedical suture material for
is reported stable at a temperature up to 140 °C and the thermal centuries. The unique mechanical properties of these fibres pro-
decomposition temperature is greater than 150 °C. The density vided important clinical repair options for many applications. Re-
has been reported in the range of 1320–1400 kg/m3 with sericin ports shows that silk proteins have provided an important set of
and 1300–1380 kg/m3 without sericin [19]. polymer materials to be applied in scaffolds for tissues, biocompat-
ible coatings and drug delivery, due to strength, biocompatibility
and low immunogenicity advantages it possess [47–50].
3.3. Mechanical properties of Bombyx mori silk fibres in different
solutions
4.2. Bombyx mori silk fibre in automotive applications
Pérez-Rigueiro et al. [28] reported tensile test involving B. mori
silk in different solutions, silkworm silk fibres were submerged in Recently, B. mori silk has been introduced as reinforcement in
liquid environments (acetone, water, isopropanol and ethanol) and different polymeric matrix for automotive applications. Oshkovr
tested for tensile strength. The report stated that liquid media were et al. [11,14,15], investigated on the crashworthiness characteris-
initially chosen in other to weaken non covalent interaction. How- tics of reinforced B. mori silk composite. Square tubes energy
ever, only immersion in water leads to a decrease in mechanical absorbers of varied lengths were fashioned out of B. mori silk nat-
properties of silk, indicating the weakening of hydrogen bonds. ural silk/epoxy composite and compared for crashworthiness
Immersion in acetone, ethanol and isopropanol leads to an increase Fig. 6. Parameters measured were the crash force efficiency (CFE),
in the stiffness of the fibre. In addition, all three organic solvents and the total absorbed energy (E-total). Under axial compression
produce similar force–displacement curves (Fig. 5), which can be tests, all the samples showed catastrophic failure. Samples failed
explained by the desiccating effect that these solvent exert on silk. with mid length buckling, which was failure originated from the
These results indicate that water disrupts hydrogen bonds initially mid of the tubes which then progress to other areas.
present in the amorphous phase, while the other solvents elimi- Eshkoor et al. [12,13], applied the use of trigger mechanism as
nate water and contribute to the formation of new hydrogen bonds they investigated the effect of trigger configuration on the crash-
in the amorphous phase of silk. This interpretation was developed worthiness characteristics of natural silk/epoxy composite tubes
through the shear lag model of the elastic modulus (E) of silk, and a using two different trigger configurations, as shown in Fig. 7. The
good agreement has been found between the model and the exper- failure modes of the natural silk/epoxy composite tubes were
imental values of E. investigated using representative photographs taken during the
302 A.U. Ude et al. / Materials and Design 57 (2014) 298–305

Fig. 6. Comparisons of varied Bombyx mori composite square tubes (A) 50 mm (B) 80 mm and (C) 120 mm lengths respectively.

quasi-static compression test. Other parameters measured were as was reported in [14] above (Fig. 8). It also retained energy
load–displacement graphs and the crashworthiness characteristics. absorption capability similar to the non-triggered samples. The
The results disclosed that with the four-piece trigger mechanism, plug trigger mechanism caused a significant reduction in load car-
the tubes failed in a progressive manner, instead of catastrophic rying capacity and energy absorption capability of samples.
A.U. Ude et al. / Materials and Design 57 (2014) 298–305 303

Fig. 7. Trigger configurations used.

Fig. 8. Trigger effect on failure mechanism (a) plug (b) four piece.

Fig. 9. Damage fragmentation of sandwich composite panels under 32 J impact load: (a) NS/Epoxy/Honeycomb; (b) NS/Epoxy/Foam; (c) NS/Epoxy/Coremat; (d) NS/Epoxy.

4.3. Bombyx mori silk fibre reinforced composite under impact loading has been investigated by Zulkifli et al. [51], they studied the inter-
laminar fracture toughness, GIC of woven silk reinforced epoxy
One major setback to the use of composite is that they are composite. Silk fibre has been treated with silane coupling agent
known to be susceptible to fail by dynamic load (impact) of foreign and the silk/epoxy composites has been fabricated with different
objects. Ude et al. [16,17] investigated the impact toughness of B. number of silk fibre layers. The test specimens were fabricated
mori silk fibre as a reinforced composite face-sheet for cores sand- using silk fibre of between 8 and 14 layers. The first set of compos-
wich. They investigated the degree of damage inflicted on the con- ites panel consisted of plain silk fibre while the second sets con-
tact surface, through thickness and rear surface of the sandwich sisted of silk fibre which has been treated with 3-aminopropyl
panels (Fig 9). The sandwich specimens were prepared in configu- triethoxysilane. Mode I test based on double cantilever beam spec-
rations of natural silk (NS)/Epoxy/Foam, NS/Epoxy/Coremat, NS/ imens (DCB) method has been used over all the specimens. The re-
Epoxy/Honeycomb and reinforced NS/Epoxy serving as referral. sults of the GIC were plotted and compared. GIC of the composites
For all experiments, drop weight impact test was carried out under in set 2 were found to be higher than the value in set 1. Comparison
low velocity impact energies of 32, 48 and 64 J. Parameters mea- of failure mode/damage fragmentation of B. mori silk composite
sured were load bearing capability, energy absorption capability with some other natural fibre composites such as Sisal and hemp;
and damage fragmentation of the specimen with regards to synthetics fibre composites such as carbon fibre and E-glass show
increasing impact loads. Results show dominant deformation that under axial loading, B. mori silk composite experienced pro-
modes as upper face-sheet compression failure, lower face-sheet gressive failure mode, whilst synthetics and natural fibres experi-
delamination and tensile failure. The results of fracture toughness enced brittle and catastrophic failure mode[11,13,52,53].
304 A.U. Ude et al. / Materials and Design 57 (2014) 298–305

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