materials

Review
Melt-Spun Fibers for Textile Applications
Rudolf Hufenus 1, *, Yurong Yan 2 , Martin Dauner 3 and Takeshi Kikutani 4
1 Laboratory for Advanced Fibers, Empa, Swiss Federal Laboratories for Materials Science and Technology,
Lerchenfeldstrasse 5, CH-9014 St. Gallen, Switzerland
2 Key Lab Guangdong High Property & Functional Polymer Materials, Department of Polymer Materials and
Engineering, South China University of Technology, No. 381 Wushan Road, Tianhe,
Guangzhou 510640, China; [email protected]
3 German Institutes of Textile and Fiber Research, Körschtalstraße 26, D-73770 Denkendorf, Germany;
[email protected]
4 Tokyo Institute of Technology, 4259-J3-142, Nagatsuta-cho, Midori-ku, Yokohama,
Kanagawa 226-8503, Japan; [email protected]
* Correspondence: [email protected]; Tel.: +41-58-765-7341




Received: 19 August 2020; Accepted: 23 September 2020; Published: 26 September 2020


Abstract: Textiles have a very long history, but they are far from becoming outdated. They gain
new importance in technical applications, and man-made fibers are at the center of this ongoing
innovation. The development of high-tech textiles relies on enhancements of fiber raw materials and
processing techniques. Today, melt spinning of polymers is the most commonly used method for
manufacturing commercial fibers, due to the simplicity of the production line, high spinning velocities,
low production cost and environmental friendliness. Topics covered in this review are established and
novel polymers, additives and processes used in melt spinning. In addition, fundamental questions
regarding fiber morphologies, structure-property relationships, as well as flow and draw instabilities
are addressed. Multicomponent melt-spinning, where several functionalities can be combined in
one fiber, is also discussed. Finally, textile applications and melt-spun fiber specialties are presented,
which emphasize how ongoing research efforts keep the high value of fibers and textiles alive.

Keywords: man-made fibers; bicomponent fibers; melt-spinning; fiber formation; spinnability;

orientation; instabilities; technical textiles

1. Introduction
Man-made fibers have a long history. Robert Hooke first brought up the idea to create silk-like
fibers in 1665, followed by René-Antoine Ferchault de Réaumur, who actually produced the first
artificial filaments from different kinds of varnish in 1734 [1]. In 1883 Joseph Swan injected dissolved
nitro-cellulose into a coagulation bath and thus obtained filaments for light bulbs [2]. In 1938 DuPont
de Nemours (Wilmington, DE, USA) launched the production of Nylon® (PA 6.6), the first commercial
melt-spun fiber, invented by Wallace Carothers [3]. In the same year Paul Schlack developed Perlon®
(PA 6), a fiber declared vital to the war by Nazi Germany [4]. The first polyester fiber, Terylene® (PET),
was created in 1941 by Imperial Chemical Industries (ICI) [5]. The commercial production of polyolefin
fibers started in 1957, based on the Ziegler-Natta catalyst recognized by a Nobel Prize in 1963 [6].
Today, chemical fibers are spun by drawing a melt or solution of a polymer or an inorganic material
from a spinneret into a medium (quenching or solvent removal by air/gas, water or coagulation bath)
where it solidifies. Drawing can either be applied by godets (rollers) and winders, by a high-velocity
air stream, or by an electrostatic or centrifugal force. Table 1 lists fiber spinning methods used to
produce filaments, staple fibers and nonwovens.

Materials 2020, 13, 4298; doi:10.3390/ma13194298 www.mdpi.com/journal/materials

Materials 2020, 13, 4298 2 of 32

Table 1. List of fiber spinning methods.

Spinning Method Material Product

melt-spinning polymer or inorganic melt filaments, staple fibers, textured yarns
wet-spinning, dry-spinning polymer solution filaments, staple fibers
gel-spinning polymer gel (polymer and solvent) filaments
preform drawing polymer or inorganic melt filaments
film-split spinning polymer melt slit-tape filaments
spun-bonding, melt-blowing polymer melt nonwovens
electrospinning, centrifuge spinning (force-spinning) melt or solution of polymer or inorganic material nonwovens
flash-spinning polymer solution nonwovens

In the last 80 years melt-spun fibers became by far the most important fibers for apparel, but even
more so for technical textiles, where they spawned a myriad of novel applications. The aim of this
review is to provide information about the current state of research and development regarding
melt-spun fibers. The field has shown steady and continuous progress, and it is high time to summarize
the technology from a contemporary point of view. This review provides insights in thermoplastic
polymers as well as extrusion and bicomponent technology, with a strong focus on the main markets
for melt-spun fibers.

2. Raw Materials for Melt-Spinning

2.1. Polymers and Their Spinnability

Most commonly used materials for melt-spinning are polyamides, polyesters and (linear)
polyolefins [7]. Table 2 lists a selection of polymers used for fiber melt-spinning, together with
some relevant properties. Basic requirement for melt-spinning is that the polymer becomes fusible
below its degradation temperature. Note that the maximum allowed extrusion temperature can fall
well below the decomposition temperature Td quoted in Table 2, while some polymers have their
melt-processing window near Td . In addition, such thermoplastic polymers should ideally have the
following properties to ease processability and to yield sufficient fiber properties [8–10]:

• withstand extrusion temperature and shear strain at minimal degradation and without
crosslinking (thermal stability);
• have sufficiently high molecular weight and thus enough melt-strength to prevent filament
break under draw-down strain (too high molecular weight and thus too high viscosity can
hamper processability);
• exhibit small polydispersity (narrow molecular weight distribution) to ensure consistent melt flow
rheology (constant flow);
• have high enough mobility of the molecular chains to disentangle and unfold under stress and to
orient in fiber direction under strain (linear polymers are most suitable);
• show high uniformity and purity to prevent fluctuations and blockage in processing.

The polydispersity of commercially available polymers ranges from two to 12 or more; as a rule of
thumb, the polydispersity should not exceed three for stable melt-spinning [11]. Temperature, moisture,
air humidity, residence time and shear forces significantly promote molecular weight degradation
during extrusion and spinning. Local shear heating may increase the spinning temperature by as much
as 10–15 ◦ C [12].
Moisture can strongly influence processability and cause degradation of polymers in extrusion,
thus drying of polymers is very important before extrusion [8]. This is especially true for polyesters like
PET, PBT or PLA, which can suffer considerable loss in molecular weight by hydrolytic degradation
(hydrolysis) of the melt in presence of water [13]. For water removal, either a batch procedure in
fluidized bed or vacuum (tumble) dryers can be applied, or continuous drying in the feed hopper
with desiccated air or nitrogen at normal pressure. However, over-drying polyamide by more than
two orders of magnitude below the equilibrium moisture content can negatively influence extrusion
processing, because moisture impacts the chemical equilibrium of the polycondensate and acts as
Materials 2020, 13, 4298 3 of 32

a plasticizer for polyamide [14]. Non-hygroscopic polymers like polyolefins usually need not to be
dried before processing. However, even hydrophobic fluoropolymers like PVDF should be dried to
remove surface moisture, which otherwise could dissolve hydrogen fluoride (HF) monomers to form
the highly corrosive and toxic hydrofluoric acid.
Polymers for man-made fibers can not only contain residual water, but also dissolved and
dispersed gases, as well as volatile liquids and solids (e.g., unreacted monomers, reaction by-products)
that boil at processing temperatures [15]. During extrusion of the polymer, these substances are kept in
the melt by hydrostatic pressure. As their solubility decreases with the pressure drop at the die exit,
gas bubbles and/or a pitted surface can evolve in the melt strand, which impair fiber quality or hinder
spinnability [16]. Volatiles evaporating from the spinneret must be removed by an exhaust, both to
protect operators and to avoid agglomeration at the die exit.
By far most of the man-made fibers are spun from semi-crystalline polymers. The crystalline
structure stabilizes the highly orientated molecular chains, which otherwise tend to recoil above Tg ,
resulting in pronounced fiber shrinkage [17]. In consequence, mainly amorphous polymers with high
Tg , like PEI and PC, are used for fiber melt-spinning (Table 2).

Table 2. Typical properties of selected polymers used for melt-spinning [18–27]. Density, Tg and Tm
are average values (exact data depend on degree of crystallinity and molecular weight). In the case of
PLA, 98:2 L to D lactic acid is assumed [28]. The decomposition temperature Td is defined by 5 wt%
loss in N2 , measured by thermogravimetric analysis (own unpublished data). Properties: TP = tensile
properties, Res = resilience, ChR = chemical resistance, AR = abrasion resistance, UV = UV resistance,
FR = flame retardancy. Performance: ++ = very good, + = acceptable, - = poor.

Polymer Density [g/cm3 ] Tg [◦ C] Tm [◦ C] Td [◦ C] TP Res ChR AR UV FR

PA 6 1.14 50 225 387 ++ ++ + ++ + +
PA 6.6 1.14 50 260 407 ++ ++ + ++ + +
PET 1.39 75 260 402 ++ + + + + +
PBT 1.33 50 220 373 ++ ++ + + + +
PLA 1.25 60 165 321 + + + - + +
PP 0.91 −15 170 399 ++ - ++ + - -
LDPE 0.92 −125 110 440 + - ++ - - -
HDPE 0.95 −125 130 436 ++ - ++ + - -
PVDF 1.78 −40 170 431 - ++ ++ - ++ ++
PEEK 1.32 145 335 569 ++ ++ ++ ++ ++ ++
PPS 1.34 85 285 494 ++ ++ ++ ++ - ++
PEI 1.27 215 - 515 ++ ++ ++ ++ ++ ++
PMMA 1.18 110 - 334 - + - + ++ -
PC 1.20 150 - 471 - + - - ++ +

2.2. Polyamides
Globally, PA 6 and PA 6.6 are by far the most used polyamides that are also significant for
large-scale production of melt-spun fibers [29]. PA 6.6 is produced by the condensation reaction of
hexamethylenediamine and adipic acid, while PA 6 is synthesized by ring-opening polymerization of
ε-caprolactam [30]. Both fiber types exhibit similar properties, i.e., outstanding wear and abrasion
resistance, high tenacity and toughness, excellent fatigue behavior and good resilience (Table 2);
slight dissimilarities mainly stem from differences in molecular weight distribution and draw-induced
molecular orientation [18]. For industrial applications, fibers are drawn with DR 4–5 to achieve high
mechanical performance, while DR 2-2.5 is applied for apparel applications to achieve high uniformity
in dye diffusion [18]. Other well-tried fiber-forming aliphatic polyamides are PA 11 (Tm ~185 ◦ C), PA 12
(Tm ~180 ◦ C), PA 6.12 (Tm ~210 ◦ C), PA 6.10 (Tm ~215 ◦ C), PA 4 (Tm ~260 ◦ C), PA 4.6 (Tm ~295 ◦ C). In the
nomenclature PA x.y, x and y represent the respective number of carbon atoms in the diamine and
diacid monomer, respectively [31].
Materials 2020, 13, 4298 4 of 32

PA 5.6, which can be synthesized by direct polycondensation of 1,5-pentamethylenediamine

obtained from L-lysine and adipic acid, is a biobased alternative to PA 6 and PA 6.6, with a high
potential in fiber applications [32]. With Tm ~250 ◦ C, PA 5.6 shows thermal properties and a heat
resistance comparable to the commercially available PA 6 [33]. The melt-spinning of PA 5.6 in the form
of segmented pie bicomponent fibers has been reported in combination with PET [34].
Some partially aromatic polyamides like polyphthalamides (e.g., PA 6T, Tm ~325 ◦ C, and PA 9T,
Tm ~300 ◦ C) or PA MXD6 (Tm ~237 ◦ C, produced from m-xylenediamine and adipic acid) can also be
melt-spun; respective filaments are commercially available but scarce [35,36]. Aromatic polyamides
(aramids), on the other hand, cannot be melt-processed, since their melting temperature exceeds the
degradation temperature; aramid fibers are produced by solution spinning.

2.3. Polyesters
PET is the predominant polyester used for fiber production, not only because of its good end-use
properties and economy of production but in particular because of the ease of physical and chemical
modification, suppressing negative and enhancing positive properties of PET [37]. Due to its relatively
high glass transition temperature (Tg ~75 ◦ C), as-spun PET forms a stable, supercooled melt with
molecular orientation in fiber direction, which develops oriented crystallites only when fully drawn [19].
Their excellent properties (Table 2) are responsible for polyester fibers and filaments finding use in
all fields of fiber application [19]. To obtain higher molecular weight PET for improved performance,
solid phase polymerization is applied below Tm , where pre-crystallized chips are heated in a stream of
hot inert gas or agitated in a vacuum drier to remove small traces of volatiles [37].
Other commercially viable polyesters suitable for fiber production are PBT and PTT, which exceed
PET in crystallization rate, resilience, elasticity and dyeability (they can be dyed at 100 ◦ C, while PET
requires 130 ◦ C) [22,37]. 1,3-propanediol, the crucial substrate to polymerize PTT (Tm ~230 ◦ C),
can either be derived petrochemically, or by enzymatic fermentation of renewable resources [38].
PEN, the last of this melt-spinnable semi-aromatic polyester family, has higher melt temperature
(Tm ~270 ◦ C), tensile modulus, chemical and UV-resistance than PET and as such is beneficial for
industrial fibers [22,39]. Respective high performance melt-spun fibers are commercially available but
scarce [40].

2.4. Polyolefins
The most prominent polyolefins used for melt-spinning are PP, LDPE and HDPE, consisting essentially
of saturated aliphatic hydrocarbon macromolecules [41]. Technologies to convert polyolefins into fibers
and fabrics include monofilament and multifilament spinning, staple fiber, spunbond, melt blown, and slit
film [20]. Polyolefin-based spunbond and melt blown fabrics are the material of choice for disposable
hygiene and medical applications like diapers, incontinence pants, sanitary napkins, surgical gowns
and masks [42]. Polyolefin filaments, being polymeric hydrocarbons, possess luster and a waxy handle,
which can be reduced by non-circular fiber cross-sections like triangular or cross-shaped [41]. The main
properties and characteristics of polyolefin fibers are summarized in Table 2. Worth mentioning is their
lightness (density below 1 g/cm3 ), poor dyeability and adhesion, as well as low resilience and high
tendency to creep [20]. UHMWPE yields fibers with extraordinary tensile properties, but its very high
molar mass hinders melt-spinning; the polymer needs to be gelled in a solvent before being extruded
through a spinneret (gel-spinning) [43]. Toyobo (Manufacturer, Tokyo, Japan) introduced a melt-spun
high-strength polyethylene fiber under the brand name Tsunooga® [44].

2.5. Chemically Inert Polymers

Filaments from chemically resistant polymers like fluoropolymers, polyetherketones,
polysulfides and polyetherimide find applications in e.g., hot medium filters or protective textiles [45].
The best-known fluoropolymer is PTFE (Tm ~330 ◦ C), but its high molecular weight hinders
flowability to an extent that it cannot be melt-spun [46]. Respective fibers are produced by
Materials 2020, 13, 4298 5 of 32

paste extrusion, where PTFE powder is mixed with a lubricant and transformed into film to
be calendered, slit, sintered and stretched [45]. A melt-processable PTFE material (Tm ~315 ◦ C),
comprising small amounts of perfluoropropylvinylether, was launched in 2006 under the brand name
Moldflon® (ElringKlinger Kunststofftechnik, Bietigheim-Bissingen, Germany) [47]. PVDF (Tm ~170 ◦ C),
PVF (Tm ~200 ◦ C), and co-polymers of tetrafluoroethylene with e.g., hexafluoropropylene, have lower
melting points and can be melt-spun to filaments with good tensile properties and high chemical
resistance [24,27].
The melt-spinnable PEEK (Tm ~335 ◦ C) is the foremost member of the aromatic thermoplastic
polyetherketones [24]. The advantage of PEEK fibers is their ability to operate in extreme conditions
(high temperature, chemical impact and abrasion) over long lifetimes [45]. PPS (Tm ~285 ◦ C) is
inherently flame-resistant, has outstanding high-temperature stability and oil and solvent resistance
(no known solvent below 200 ◦ C) [15,26]. PEI (Tg ~215 ◦ C) is an amorphous polymer and can be
melt-spun into fibers which are resistant against specific chemicals, have a lower strength and melting
point than PEEK or PPS and are more extensible [24].
LCPs, characterized by a highly ordered fluid state, are resistant to virtually all chemicals [48].
The principal monomer in all commercial thermotropic LCPs is hydroxybenzoic acid [49]. By subjecting
a LCP to shear and extension forces via melt-spinning, the molecular chains become highly oriented
without post-drawing [50]. Subsequent heat-treatment (annealing) for solid phase polymerization
under reduced pressure results in filaments with superior tensile properties [51,52]. The first
commercially available, melt-spun LCP fiber was introduced in 1990 under the brand name Vectran® ,
now manufactured by Kuraray (Osaka, Japan) [53].

2.6. Thermoplastic Elastomers

Elastomeric fibers, produced from polymers with thermoreversible physical cross-links,
are characterized by high elastic recovery (up to 99%) and high extensibility (up to 500%) [54,55].
Their elasticity performance mainly stems from the combination of soft and hard segments of the
polymer structure [56]. Most conventional elastomeric fibers are produced by dry spinning of PU,
but melt-spun products are available; although they often lack in yarn uniformity and recovery,
they are of interest due to ecological and economic advantages [57]. In filaments, melt-spun from TPU,
their outstanding elasticity originates from the chemical composition of polyols (soft segments) and
isocyanates (hard segments) [58]. PEE, a multiblock copolymer comprising segments of semicrystalline
polyester (hard, mostly PBT) and noncrystalline polyether (soft), is a low-cost melt-spinnable polymer
with adequate characteristics as thermoplastic elastomer [54,59]. TPOs are melt-spun to produce elastic
filaments that are chemically resistant [56,60]. Elastic recovery, heat-resistance and long-term stability
of thermoplastic elastomers can be achieved by subsequent covalent crosslinking [59,61].

2.7. Amorphous Polymers

The morphology of solid-state polymers typically fluctuates continuously between ideal crystalline
and fully amorphous states, where “amorphous” is widely used in polymer science to mean
non-crystalline [62,63]. Polymers with irregular molecular structures cannot crystallize under any
condition, so the only important morphological feature that can be changed through processing
is molecular orientation [64]. X-ray diffraction studies have confirmed the presence of oriented
non-crystalline domains in filaments, melt-spun from fully amorphous polymers, indicating that the
degree of orientation is directly proportional to the fiber draw ratio [65,66].
Fully amorphous polymers tend to be transparent, in contrast to semicrystalline polymers,
which typically are translucent or opaque due to a usually heterogeneous crystalline structure that
leads to refractive index inhomogeneities and thus light scattering at the interfaces between crystalline
and amorphous regions [67,68]. Most prominent examples of polymers used for melt-spinning
transparent fibers are PMMA (Tg ~110 ◦ C), PC (Tg ~150 ◦ C) and PS (Tg ~95 ◦ C) [26,69]. The application
Materials 2020, 13, 4298 6 of 32

temperature of respective fibers is below Tg , since their oriented macromolecules tend to recoil above
Tg , resulting in strong shrinkage of the fibers.

2.8. Biopolymers
The term “biopolymer” generally refers to biobased (produced from biogenic substances which
are considered renewable resources), but is every so often used for biodegradable (degradable by
biological means), biocompatible (no adverse effect on humans or animals) or bioresorbable polymers
(dissolved or absorbed in the body). The main biopolymers considered for fiber melt-spinning are
PLA, PCL, PGA, PBAT, PEF and PHAs.
PLA is produced from lactic acid, whose raw material is naturally occurring starch, which is usually
extracted from corn [23]. Fiber grade PLA, mostly consisting of L lactic acid (LLA) containing less or
equal to 8% D lactic acid (DLA), is commercially one of the most promising bio-based, biodegradable and
biocompatible polymers (PLA with a D-isomer level exceeding 8% does not crystallize) [21,23,70].
The biodegradability of PLA in the natural environment is lower than that of other biopolymers, since it
is less susceptible to microbial attack [71]. Its main drawback regarding melt-processing is the low
thermal stability in the presence of moisture (hydrolysis) [72]. However, mechanical performance and
thermal resistance can be enhanced by adjusted LLA/DLA mixing and adequate spinning parameters
to obtain stereo-complex crystals with strong interaction between LLA and DLA sequences [28,73–75].
PCL (Tm ~60 ◦ C) is a petroleum-based biodegradable and biocompatible aliphatic polyester
with good mechanical properties, consisting of a sequence of methylene units with in-between ester
groups [76]. Its slow biodegradation rate in the human body make PCL suitable for implantable
long-term drug delivery systems [77]. PCL is highly miscible and combines well with other
polymers, and thus has been investigated as a polymer blend component or copolymer for various
applications [78–81]. PCL in the form of filaments is also of interest for technical textiles, but its low
melting point limits the application and thus only a few studies discuss the conventional melt-spinning
of PCL homo-component fibers [82–85].
PGA (Tm ~225 ◦ C), a highly biocompatible and biodegradable petroleum derived aliphatic polyester
of simple molecular structure, can be melt-spun in fibers with good mechanical properties [77,86].
Since the product placement of the first man-made absorbable suture named Dexon® in 1972,
PGA and its copolymers dominate the biodegradable suture market [87,88]. However, the narrow
processing window makes it difficult to spin high-strength fibers under ordinary industrial conditions,
while laboratory trials with modifications in the spinning line led to fibers of high tensile strength and
toughness [89,90].
PBAT (Tm ~120 ◦ C) is an aliphatic-aromatic copolyester, which degrades within a few weeks
with the aid of naturally occurring enzymes [91]. Considering both tensile and biodegradation
properties, a random copolymer with 44 mol% of polybutylene terephthalate was found to be ideal [92].
PBAT shows good melt-spinnability, and the copolymer’s hard (aromatic) and soft (aliphatic) monomer
segments yield elastic fibers with low modulus and high resilience [93]. The copolyester is also
considered a good candidate for the enhancement of PLA [91].
PEF (Tm ~210 ◦ C) is produced by polycondensation of ethylene glycol and furan dicarboxylic
acid (as such chemically analogous to PET), which can be derived from plant-based resources [94].
Despite its slow crystallization and low Tm , PEF has recently gained attention as a potential bio-based
replacement for PET [95]. In analogy to PET, solid phase polymerization is the key to attain high
molecular weight and thus suitability for engineering applications [95]. Own unpublished data show
that PEF can be melt-spun into fibers with properties similar to PET fibers.
PHAs are produced by bacteria for intracellular carbon and energy storage [96–100]. PHAs,
either in the form of homopolymers or copolymers of various hydroxyalkanoic acids, are thermoplastic,
biodegradable, biocompatible and nontoxic [101–103]. The bacteria-synthesized, perfectly linear and
isotactic polymer chains promise superior properties [104–106]. However, their rapid thermal degradation
at temperatures just above the melting temperature, variations in quality and molecular weight,
Materials 2020, 13, 4298 7 of 32

and lack of purity commonly resulting from the biotechnical production process, hamper melt-spinning
of virgin PHAs [107]. Melt-spinning trials have been reported for P3HB (Tm ~180 ◦ C) [107–112],
PHBV (Tm ~170 ◦ C) [113–115] and PHBH (Tm ~145 ◦ C) [116–119]. In 2007, Tepha (Lexington, KY, USA)
launched P4HB (Tm ~60 ◦ C) mono- and multifilaments for medical applications [120,121].

3. Additives for Melt-Spinning

3.1. Function of Additives

Additives are considered to facilitate processing, to provide additional functions, or to improve
properties and durability of the final fiber (Table 3). The additive should exhibit thermal stability
and good processability. As additives also can lead to blockage and fluctuations in processing, their
quantity and variety should be kept as low as possible. The maximum tolerable amount depends on
miscibility in the case of polymers, and solubility in the case of liquids.

Table 3. Typical additives used in melt-spinning.

Type Function Examples

Processing aids Antioxidant Hindered phenols and amines, phosphites
Hydrolysis stabilizer Carbodiimide
Nucleating agent Talcum powder, boron nitride, organic phosphate salts
Lubricant Stearates, low molecular wax
Polymer processing aid Fluoropolymers
Surfactant Stearates, PEG
Enhancing additives Plasticizer Tributylcitrate, acetyltributylcitrate
Chain extender Difunctional acid derivatives, anhydrides and epoxides
UV-stabilizer HALS, TiO2 , ZnO, carbon black
Flame retardant Phosphorous and halogen derivatives, HALS
Thermal protection Zirconia
Functional additives Colorant Pigments and dyes, carbon black
Delustrant TiO2 , ZnO, mica, optical brightening agents
Antistatic Carbon black, carbon nanotubes, graphene, ZnO
Antimicrobial TiO2 , ZnO, Ag+ , Cu2+ , Zn2+ , plant extracts, phenol
Water/oil repellent Silicone and fluorine compounds

Solid additives (powders) should exhibit uniformity, dispersibility, particle and aggregation size
below 5% of the fiber diameter, good wettability with the matrix polymer, and they should not be
prone to clogging. As a rule of thumb, to maintain processability, the amount of solid additives
should not exceed 5%. Depending on additive and filament type, far less might be acceptable to
avoid impairing spinnability and mechanical properties. Additives can also cause problems like
degradation of the polymer, unwanted chemical reactions and gas liberation during processing. In the
final filament, the presence of foreign matter can cause failure by cavitation, as well as fibrillation at
the polymer-additive interface.
The benefit of additives turns into a challenge when degradability or recyclability of the polymers
are required. Additives in biodegradable polymers must also be degradable and ecologically friendly,
which limits availability. Widely used inorganic fillers like TiO2 can cause problems when released
to the environment in substantial quantity. Upon recycling, residual additives that lost their original
function are incorporated in the recycled mixed materials and impair targeted properties. The success
of PET bottle flakes in fiber production mainly stems from the absence of colorants, which would turn
fibers from recycled PET grey.

3.2. Processing Aids

The drawback of melt-spinning, that the polymer can oxidatively decompose during processing,
can be counteracted by antioxidants that suppress radical chain reactions until consumed;
Antioxidants are for example used to enable melt-blowing of polypropylene spunbond waste [122].
Hydrolytic degradation of polyesters can be mitigated by stabilizers that react preferably with water
Materials 2020, 13, 4298 8 of 32

and/or carboxylic groups and thus affect the reaction kinetics of hydrolysis [123]. Nucleating agents
like talcum powder or boron nitride are used to improve the onset of crystallization with the result
that crystals become smaller and more homogenous, leading to better mechanical properties of
spun filaments [124]. Dispersive additives can act as lubricants for the matrix polymer by reducing
apparent viscosity, and thus temperature or pressure required for extrusion [125]. In consequence,
lubricants can even render polymers melt-spinnable whose melting temperature exceeds their
degradation temperature [126]. Polymer processing aids like fluoropolymers can delay the onset of
flow instabilities by thinly coating the die wall, thus reducing adhesion between polymer and wall and
in consequence promote slippage [127,128].

3.3. Enhancing Additives

Stabilizers improve longevity of polymers by suppressing degradation resulting from UV radiation
and other high-energy sources. Hindered phenols and hindered amine light stabilizers (HALS)
deactivate existing radicals, while UV absorbers dissipate the harmful radiation as less harmful
heat [129]. Flame retardant additives can act either in the gas phase by quenching radicals in the flame
and/or in the condensed phase by catalyzing the formation of a protective char layer [130]. They can
also work synergistically with other polymer additives (light stabilizers, surfactants, fillers etc.) [131].
Plasticizers are blended with polymers to improve their flexibility and elasticity [132]. On the other
hand, fillers can constrain the mobility of polymer chains, resulting in higher stiffness and resistance to
creep [133,134].

3.4. Functional Additives

Dyes and pigments are used to impart color; while dyes are solubilized in the polymer matrix,
pigments are polymer insoluble, non-migrating additives. Dope-dyed filaments are produced by
adding inorganic and organic pigments in the form of colorant masterbatches to the matrix polymer
during extrusion. These masterbatches often contain further additives like UV-stabilizers. To reduce
gloss of man-made fibers, TiO2 or other metal oxides are added as delustrants. In order to melt-spin
intrinsically antistatic fibers, mainly fillers like carbon black, carbon nanotubes, graphene or metal
powders are used as electrically conductive additives [135–137]. Adding metal and metal oxide
nanoparticles directly into the polymer matrix is a common approach to render man-made fibers
antimicrobial [138]. Typically, the mechanical properties of man-made fibers change significantly
when fillers are used; hence, bicomponent fibers with a functional compound as minor element are
an interesting approach [34]. Examples are conductive fibers as described in paragraph 7.5, or the
translucent fiber Bodyshell® (Toray, Tokyo, Japan) with star-shaped pigmented core, which prevents
white swim suits from losing their opaqueness in wet condition [139].

4. Polymer Melt-Spinning

4.1. Melt-Spinning Technique

A typical melt-spinning line comprises a screw extruder, a spin pack and a filament draw-down
unit (Figure 1). Polymer pellets, granulates or chips are fed from the hopper to a single screw extruder to
be melted and pressurized. In addition, a side extruder (not shown in Figure 1) can feed masterbatches,
mainly applied for dope-dyed yarns. A melt pump ensures a defined and accurate throughput rate.
The spin pack comprises polymer filtering and distribution parts, as well as the spinneret that is
responsible for the filament formation. The overall design of the extrusion and spinning line must
avoid melt stagnation by abrupt tapering or dead spots, where the polymer can degrade locally and
discharge intermittently into the melt stream.
Leaving the spinneret, the extruded strands are either spun into a quenching chamber or a water
bath for solidification. After cooling and application of a spin finish, the filaments are drawn (online or
offline) by several godets. To improve drawability, the godets are heated, or the filaments can be
masterbatches, mainly applied for dope-dyed yarns. A melt pump ensures a defined and accurate
throughput rate. The spin pack comprises polymer filtering and distribution parts, as well as the
spinneret that is responsible for the filament formation. The overall design of the extrusion and
spinning line must avoid melt stagnation by abrupt tapering or dead spots, where the polymer can
degrade locally and discharge intermittently into the melt stream.
Materials 2020, 13, 4298 9 of 32
Leaving the spinneret, the extruded strands are either spun into a quenching chamber or a water
bath for solidification. After cooling and application of a spin finish, the filaments are drawn (online
or offline)
guided byhot
over several
platesgodets. To improve
or through drawability,
stretching the godets
ovens. Finally, areisheated,
a winder used toorspool
the filaments can be
the filaments on
guided
a bobbin. over hot plates or through stretching ovens. Finally, a winder is used to spool the filaments
on a bobbin.
Feed Static
hopper mixer Melt
pump
Spin pack

Screw extruder

Quenching Godets
chamber

Spin finish applicator

Winder
Figure
Figure 1.1. Schematic
Schematicassembly
assembly
of aofmelt-spinning
a melt-spinning line.
line. By wayBy way of illustration,
of illustration, theis polymer
the polymer is
represented
represented
in yellow. in yellow.

4.2.
4.2. Extrusion
Extrusion Line
Line

In
In most
most cases,
cases, polymers
polymers in in the
the form
form of of pellets
pellets are
are melted
melted in in aa screw
screw extruder
extruder by by applying
applying heat heat
and shear. Additives for coloring or to impart other properties are usually added with a carrier resin
and shear. Additives for coloring or to impart other properties are usually added with a carrier
(masterbatch).
resin (masterbatch).The use Theofusepowders
of powders andand liquids sometimes
liquids sometimes cannot
cannot bebeprevented,
prevented,but butitit makes
makes
processability very challenging. The role of the extruder is not only to melt, but also to homogenize
processability very challenging. The role of the extruder is not only to melt, but also to homogenize
the
the polymeric
polymericmaterial
materialand andtotobuild-up
build-upthe theprimary
primary pressure
pressure needed
needed forfor
an effective operation
an effective operationof the
of
melt
the meltpump.
pump. In large-scale
In large-scale applications,
applications, thethe melt is is
melt fedfed totothe
thespinning
spinningsystem
systemdirectly
directly from
from the
the
polycondensation line.
polycondensation line.
The
The main function of
main function of the
the melt
meltpump
pumpisisto tobuild
buildup upandandmaintain
maintainthe therequired
required spin
spin pressure,
pressure, andandto
to provide a controlled throughput of the melt [140]. Most common are gear pumps, where the
provide a controlled throughput of the melt [140]. Most common are gear pumps, where the rotating
rotating
gears aregears
filledare
fromfilled
the from the extruder
extruder side and discharge
side and discharge the polymer theonpolymer on the downstream
the downstream side (Figure side
2).
(Figure
As long2).as As
the long as the intermeshing
intermeshing gear teeth are gear teeth are completely
completely filled by thefilled
melt,byandthe melt, fit
tightly andin tightly fit in
the housing
the housing to minimize leakage flow, the discharge pressure stays virtually constant, independent
to minimize leakage flow, the discharge pressure stays virtually constant, independent of inlet pressure
of inlet pressure
fluctuations [64].fluctuations
However, the [64].throughput
However, the throughput
is not is not only
only a function a function
of capacity andofrotation
capacity ofand
the
rotation
pump, but of the
alsopump, but also accuracy,
of mechanical of mechanical
pressure accuracy, pressure
difference over difference
the pump, over the pump,
and melt and melt
compressibility
compressibility (at processing temperature and pressure). In this context, note that the density
(at processing temperature and pressure). In this context, note that the density of a polymer of a
increases
polymer increases
with decreasing with decreasing
temperature temperature
and increasing and increasing pressure.
pressure.
A homogeneous melt is a must to achieve good processability and reproducibility, as well as
decent mechanical properties of spun fibers. As mixing in a single-screw extruder is poor, static mixers
(Figure 3 left) can be utilized to improve the distributive mixing and temperature uniformity of the melt
stream [64,140]. Oerlikon Barmag (Remscheid, Germany) was the first to promote a gear pump with
integrated rotating mixer for melt homogenization [141]. Filters made of steel screens, special sand
or sintered metals remove foreign particles, gel particles and undesirable conglomerate additives,
and thus prevent downstream equipment to be damaged by contaminants in the melt (Figure 3 right).
Filters also build up additional melt pressure to improve melt quality and homogeneity due to their
torturous path and high shear [142].
Materials 2020, 13, 4298 10 of 32
Materials 2020, 13, x FOR PEER REVIEW 10 of 32

Figure 2. Working principle of a melt (gear) pump. By way of illustration, the polymer melt is
represented in yellow.

A homogeneous melt is a must to achieve good processability and reproducibility, as well as

decent mechanical properties of spun fibers. As mixing in a single-screw extruder is poor, static
mixers (Figure 3 left) can be utilized to improve the distributive mixing and temperature uniformity
of the melt stream [64,140]. Oerlikon Barmag (Remscheid, Germany) was the first to promote a gear
pump with integrated rotating mixer for melt homogenization [141]. Filters made of steel screens,
special sand or sintered metals remove foreign particles, gel particles and undesirable conglomerate
additives, and thus prevent downstream equipment to be damaged by contaminants in the melt
(Figure 3 right). Filters also of
build up(gear)
additional melt pressure to improve melt quality isand
Figure 2.
Figure 2. Working
Working principle
principle of aa melt
melt (gear) pump.
pump. By
By way
way of illustration, the
of illustration, polymer melt
the polymer melt is
homogeneity due to their torturous path and high shear [142].
represented in yellow.
represented in yellow.

A homogeneous melt is a must to achieve good processability and reproducibility, as well as

decent mechanical properties of spun fibers. As mixing in a single-screw extruder is poor, static
mixers (Figure 3 left) can be utilized to improve the distributive mixing and temperature uniformity
of the melt stream [64,140]. Oerlikon Barmag (Remscheid, Germany) was the first to promote a gear
pump with integrated rotating mixer for melt homogenization [141]. Filters made of steel screens,
special sand or sintered metals remove foreign particles, gel particles and undesirable conglomerate
additives, and thus prevent downstream equipment to be damaged by contaminants in the melt
(Figure 3 right). Filters also build up additional melt pressure to improve melt quality and
homogeneity due to their torturous path and high shear [142].

Figure 3. Examples of static mixers (a) and stainless steel filters (b).
Figure 3. Examples of static mixers (a) and stainless steel filters (b).
4.3. Spinneret
4.3. Spinneret
At the end of the extrusion line, the pressurized polymer melt is forced through the tiny holes
(dies) ofAt thethe end of the
spinneret to extrusion line, the filaments.
form continuous pressurizedThe polymer
designmelt
of theis forced through
spinneret the precision
and the tiny holes of
(dies) of the spinneret to form continuous filaments. The design of the spinneret and the precision of
the dies are crucial for good spinning results. A spinneret can consist of one up to several hundred
the dies are crucial for good spinning results. A spinneret can consist of one up to several hundred
fine holes which are quite sensitive to abrasion, corrosion and clogging by impurities (thus filtering
fine holes which are quite sensitive to abrasion, corrosion and clogging by impurities (thus filtering
the melt is of utmost importance). Filament uniformity and production yield strongly depend on die
the melt is of utmost importance). Filament uniformity and production yield strongly depend on die
layout and length/diameter ratio (L/D) of the die [142], which has to be chosen taking the rheological
layout and length/diameter ratio (L/D) of the die [142], which has to be chosen taking the rheological
behavior of a specific polymer into account.
behavior of a specific polymer into account.
WhenWhen passing
passing through
throughthe thespinneret,
spinneret, thethe polymer
polymer is is subjected
subjectedto toshear
shearflowflowthat
thatresults
resultsinin
anan
increase
increase of ofmolecular
molecular orientation.
orientation. When
When the the melt
melt emerges
emerges fromfrom the thespinneret,
spinneret,the thebuilt-up
built-upelastic
elastic
energy is released andFigure
the 3. Exampleseffects
combined of static
of mixers
surface (a)tension
and stainless
and steel filtersof(b).
relaxation molecular orientation
energy is released and the combined effects of surface tension and relaxation of molecular orientation
result
result in die
in die swell
swell (Figure
(Figure 4)4)[143].
[143].When
Whenthe thedraw-down
draw-down force force is
is too
toohigh,
high,the
themeltmeltmight
mightbebe drawn
drawn
4.3. Spinneret
outout of the
of the die,die, hindering
hindering thedevelopment
the developmentofofdie dieswell
swell and
and leading to to unsteady
unsteadyspinning
spinningconditions.
conditions.
At the endthe
Although of spinneret
the extrusion line, the
is mainly pressurized
responsible polymerthe
for shaping melt is forced
filament, through
designs the other
of dies tiny holes
than
(dies) ofhave
circular the spinneret
to be handledto form
with continuous filaments.
care. Trilobal The design
cross-sections of the
(Figure spinneret
5) are and the
for example precision
used of
in carpet
the dies
yarns to are crucial
achieve for and
luster goodhigher
spinning results.
stiffness, or A
forspinneret
specialtycan consistpurposes
filtration of one up[144].to several
Givenhundred
enough
fine holes
time, which are quite
the cross-section sensitive
of the polymer to melt
abrasion, corrosion
exiting and adopt
the die will clogging by impurities
a circular shape due(thustofiltering
surface
the meltand
tension is ofelasticity
utmost importance).
of the melt, Filament
independent uniformity and production
of the capillary profile.yield strongly depend
Consequently, on die
the original
layoutof
shape and thelength/diameter
capillary can beratio (L/D)the
retained of the die [142],
better, which
the faster thehas to be chosen
filament solidifiestaking the rheological
during quenching.
behavior
Apart from of surface
a specific polymer
tension, alsointo
dieaccount.
swell can contribute to a distortion of the cross-sectional profile.
When passing through the spinneret, the polymer is subjected to shear flow that results in an
increase of molecular orientation. When the melt emerges from the spinneret, the built-up elastic
energy is released and the combined effects of surface tension and relaxation of molecular orientation
result in die swell (Figure 4) [143]. When the draw-down force is too high, the melt might be drawn
out of the die, hindering the development of die swell and leading to unsteady spinning conditions.
 Die

Die swell

Materials 2020, 13, 4298 11 of 32

Materials 2020, 13, x FOR PEER REVIEW 11 of 32

Melt troughput
Melt
Die
strand

Die swell

Draw-down
force

Melt
strand
Figure 4. Die swell and fiber drawing. By way of illustration, the polymer melt is represented in
yellow.

Although the spinneret is mainly responsible for shaping the filament, designs of dies other than
circular have to be handled with care. Trilobal cross-sections (Figure 5) are for example used in carpet
Draw-down
yarns to achieve luster and higher stiffness, or for specialty filtration purposes [144]. Given enough
force
time, the cross-section of the polymer melt exiting the die will adopt a circular shape due to surface
tension and elasticity of the melt, independent of the capillary profile. Consequently, the original
shape of the capillary can be retained the better, the faster the filament solidifies during quenching.
ApartFigure
from 4. Dieswell
swell and fiber
also drawing.
drawing. By By
die swell canway of illustration, the polymer
Figure 4. Die and fiber way of illustration, the polymer melt ismelt is represented
represented in
in yellow.
surface tension, contribute to a distortion of the cross-sectional profile.
yellow.
a b c d
Although the spinneret is mainly responsible for shaping the filament, designs of dies other than
circular have to be handled with care. Trilobal cross-sections (Figure 5) are for example used in carpet
yarns to achieve luster and higher stiffness, or for specialty filtration purposes [144]. Given enough
time, the cross-section of the polymer melt exiting the die will adopt a circular shape due to surface
Figure
Figure 5. Typical diedie
for for
trilobal cross-sections (a) and(a)resulting trilobal filaments gaining in gaining
roundness
tension and5.elasticity
Typical of the trilobal
melt, cross-sections
independent of the and resulting
capillary trilobal
profile. filaments
Consequently, in
the original
due to
roundnessincreasing solidification
due to increasing time (b–d).
solidification By way
time the of
(b–d). illustration,
By way the polymer
of illustration, melt is
the polymerrepresented
melt is
shape in
of the capillary
yellow. in yellow.
can be retained the better, faster the filament solidifies during quenching.
represented
Apart from surface tension, also die swell can contribute to a distortion of the cross-sectional profile.
4.4. FilamentaDraw-down Unit b c d
4.4. Filament Draw-down Unit
The melt strand is commonly spun into a quenching chamber with adjustable air flow and
The melt strand is commonly spun into a quenching chamber with adjustable air flow and
quenching temperature. Thick filaments with diameters exceeding ~100 µm must be quenched in
aquenching
water bath, temperature. Thick filaments
because convective with diameters
heat transfer by air isexceeding
limited [145].~100 µm As themust be quenched
molten filament inisa
water bath, because convective heat transfer by air is limited [145].
accelerated down to the take-up roll, it is simultaneously cooled down and stretched uniaxial. In the
As the molten filament is
accelerated
case ofFigure down
high-speed
to
5. Typical the take-up
die for(PET:
spinning
roll,
trilobal it is simultaneously
cross-sections
winding speed >(a) 3500and cooled down
resulting
m/min),
and
thetrilobal
imposed
stretched
filaments uniaxial.
stress isgaining
orienting
In
in thethe
case roundness
of high-speed due spinning
to increasing(PET: winding speed
solidification time >3500Bym/min),
(b–d). way of the imposedthe
illustration, stress is orienting
polymer melt is the
polymer chains and crystallizing the polymer (Figure 6) [143]. Depending on the type of polymer,
polymer chains
represented and crystallizing
in yellow. the polymer (Figure 6) [143]. Depending on the type of polymer,
orientation and crystallization might also develop at lower speed. The ratio between die exit velocity
orientation and crystallization might also develop at lower speed. The ratio between die exit velocity
and take-up velocity is called draw-down ratio (DDR).
and take-up velocity
4.4. Filament Draw-down is called
Unit in draw-down ratio (DDR).
The degree of orientation the filament depends on the extent of spin-line stress, which increases
The degree of orientation in the filament depends on the extent of spin-line stress, which
with The melt strand is commonlywith
decreasing melt temperature, spun into a quenching
increasing molecularchamberweight ofwith adjustable
the polymer, asair
wellflow and
as with
increases with decreasing melt temperature, with increasing molecular weight of the polymer, as well
quenching temperature.
progressing quench and Thick stretchfilaments with diameters
rates [7,145]. However, exceeding ~100 µmand
too high viscosity musttoobe quenched
fast cooling in cana
as with progressing quench and stretch rates [7,145]. However, too high viscosity and too fast cooling
water bath, because convective heat transfer by air is limited [145]. As the molten filament is
subdue the drawability of the filament and prevent the necessary degree of deformation before the start
can subdue the drawability of the filament and prevent the necessary degree of deformation before
accelerated
of down
solidification to the
[10]. Thustake-up
materialsroll, with
it is simultaneously
long relaxationcooled times and down low and stretched uniaxial.
spinnability are oftenIn the
spun
case aofpost-heater
into high-speed(hot spinning
shroud)(PET: winding
installed underspeed >3500 m/min),
the spinneret the imposed
to improve stability, stress
lower is orienting the
pre-orientation
polymer
and reduce chains and crystallizing
the solidification the polymer (Figure 6) [143]. Depending on the type of polymer,
rate [7,146].
orientation and crystallization
The melt-strength, which mightdepends alsoondevelop at lowerweight
the molecular speed. of The ratio
the between
polymer, mustdie be
exitsufficient
velocity
and take-up velocity is called draw-down ratio (DDR).
to resist the forces of gravity, inertia and air or water friction [10]. Due to the high forces applied,
The degree
a considerable of orientation
viscous stretching can in the
leadfilament depends
to a failure on the
of filaments, i.e.,extent
surface oftension-induced
spin-line stress,breakup which
increases
into droplets,withasdecreasing melt temperature,
the melt tends to minimize the with increasing
surface molecular weight of
area (Plateau-Rayleigh the polymer,
instability) as well
[10,143].
as with progressing quench and stretch rates [7,145]. However, too high viscosity and too fast cooling
can subdue the drawability of the filament and prevent the necessary degree of deformation before
Materials 2020, 13, x FOR PEER REVIEW 12 of 32

the start of solidification [10]. Thus materials with long relaxation times and low spinnability are
Materials 2020, 13, 4298 12 of 32
often spun into a post-heater (hot shroud) installed under the spinneret to improve stability, lower
pre-orientation and reduce the solidification rate [7,146].

Figure
Figure 6.6. Orientation
Orientation development
development along
along spinline
spinline in the case
in the case of
of high-speed
high-speed spinning.
spinning. By
By way of
way of
illustration, the polymer
illustration, the polymer melt
melt is
is represented
represented in
in yellow.
yellow.

The melt-strength,
The polymer has towhich solidify either through
depends glass transition
on the molecular weightorofcrystallization
the polymer, must before bethe filaments
sufficient to
hit the take-up roll, otherwise they might stick to each other, on godets
resist the forces of gravity, inertia and air or water friction [10]. Due to the high forces applied,or winder. When the filaments a
solidify and travel
considerable viscous downstream
stretching at high
can lead speed, the surface
to a failure friction i.e.,
of filaments, through
surfaceair tension-induced
generates static electricity.
breakup
A well-studied
into droplets, asapproach
the melt tends to improve the structural
to minimize the surfacedevelopment of as-spun fibers
area (Plateau-Rayleigh is to guide
instability) them
[10,143].
through a liquid isothermal bath during spinning [147–150]. By replacing
The polymer has to solidify either through glass transition or crystallization before the filaments the quenching air with
a
hitliquid, heat is
the take-up transferred
roll, otherwisefaster, and stick
they might the increased frictional
to each other, dragorcan
on godets impose
winder. Whenhigher spin-line
the filaments
stress [147].
solidify and travel downstream at high speed, the surface friction through air generates static
To adjust
electricity. frictional properties,
A well-studied approach prevent static charging
to improve and facilitate
the structural downstream
development processes,
of as-spun fibersa is spin
to
finish (neat oil formulation or aqueous emulsion composed of lubricating
guide them through a liquid isothermal bath during spinning [147–150]. By replacing the quenching oils, antistatic agents,
emulsifiers,
air bactericides
with a liquid, heat is and other stabilizers)
transferred faster, and is the
usedincreased
to lubricate the filaments
frictional drag can [142]. The spin
impose higher finish
spin-is
applied just before
line stress [147]. the first godet by metering it onto the running filament with a gear pump.
Orientation
To of the macromolecules
adjust frictional properties, preventis mainly achieved
static charging by and
post-drawing in the solidified
facilitate downstream state by aa
processes,
set of godets operated at different revolving speeds [151]. Prime examples
spin finish (neat oil formulation or aqueous emulsion composed of lubricating oils, antistatic are polymers like PE, PP or
agents,
PET, that canbactericides
emulsifiers, only be partially and otheroriented in the fluid
stabilizers) state
is used to[9]. During
lubricate thethe drawing[142].
filaments process,
Thethespin as-spun
finish
filament
is applied just before the first godet by metering it onto the running filament with a gear pump. roll
is stretched up to several times its original length. The ratio between speeds of take-up
and winder is called
Orientation of the draw ratio (DR). is mainly achieved by post-drawing in the solidified state by
macromolecules
a set As high molecular
of godets operated mobility
at differentconditions
revolving favor homogeneous
speeds [151]. Prime drawing,
examples thearerespective
polymerstemperature
like PE, PP
of slow crystallizing polymers (e.g., PET, PPS, PEEK) should
or PET, that can only be partially oriented in the fluid state [9]. During the drawing be slightly above the glass
process,transition
the as-
temperature
spun filament isgstretched up to several times its original length. The ratio between speeds of[152,153].
(T ), and a low crystallinity of the as-spun filament should be aimed for take-up
If as-spun
roll filaments
and winder startdraw
is called to crystallize
ratio (DR). before drawing, they become brittle and undrawable [154].
Fast crystallizing polymers like
As high molecular mobility conditions PE and PP, on favor
the other hand, usually
homogeneous alreadythe
drawing, crystallize in an
respective unoriented
temperature
state
of slowbefore drawing is
crystallizing applied (e.g.,
polymers [155].PET,
Here,PPS, molecular
PEEK) orientation develops
should be slightly in thethe
above crystallized stage,
glass transition
while slow crystallizing polymers orient in the non-crystalline state and
temperature (Tg), and a low crystallinity of the as-spun filament should be aimed for [152,153]. If as- develop oriented crystals
during annealing
spun filaments start(thetolatter drawnbefore
crystallize from the amorphous
drawing, they state,
become while polyolefins
brittle are drawn
and undrawable fromFast
[154]. the
crystalline state)
crystallizing [55]. like PE and PP, on the other hand, usually already crystallize in an unoriented
polymers
When crystallizable
state before drawing is applied polymers areHere,
[155]. subjected
molecularto high axial tension
orientation at a temperature
develops belowstage,
in the crystallized their
melting point, they typically show necking (ductile failure), provided
while slow crystallizing polymers orient in the non-crystalline state and develop oriented crystals that the melt strength is high
enough to prevent premature breakage [12]. This abrupt and drastic decrease in cross-sectional area
generated in the filament by high local stress is characteristic to extension-thinning polymers [143,156],
Materials 2020, 13, x FOR PEER REVIEW 13 of 32

during annealing (the latter drawn from the amorphous state, while polyolefins are drawn from the
crystalline state) [55].
When crystallizable polymers are subjected to high axial tension at a temperature below their
Materials 2020, 13, 4298 13 of 32
melting point, they typically show necking (ductile failure), provided that the melt strength is high
enough to prevent premature breakage [12]. This abrupt and drastic decrease in cross-sectional area
generated in thewith
and is associated filament by highcrystallization
stress-induced local stress is[37].
characteristic
The reason atoformed
extension-thinning polymers
neck grows is that stress
[143,156],
of force perand unitisarea
associated
and thuswith stress-induced
extension crystallization
rate are highest [37].[157].
in the neck The reason a formed
Operating belowneck grows
the natural
is thatratio
draw stress of force
(Figure 7) per
can unit area filaments
produce and thus with
extension rate arenecked
alternating highest andin undrawn
the neck [157]. Operating
segments [154],
below can
which the natural draw
be utilized to ratio (Figure
produce 7) can“thick
so-called produce filaments
& thin” highlywith alternating
aesthetic fibersnecked and undrawn
[158]. Depending on
segments
the polymer, [154], which can
excessive be utilized
necking can betoprevented
produce so-called
by operating“thickclose
& thin”
to Thighly
g (e.g.,aesthetic
PET), byfibers [158].
increasing
Depending
drawing on the polymer,
temperature, excessive necking
or by distributing can be
the drawing prevented
process by operating
over several stages.close to Tg (e.g.,
To produce PET),
ultra-fine
by increasing
PET fibers, a flowdrawing
drawingtemperature, or by distributing
process is applied before regularthe drawing,
drawing process
since noover several
necking stages.
occurs in flowTo
produce ultra-fine PET fibers, a flow drawing process
drawing, and the development of orientation is minimal [159]. is applied before regular drawing, since no
necking occurs in flow drawing, and the development of orientation is minimal [159].
Stress

Filament
shape

Yield
point

Natural draw ratio

Elongation
Maximum draw ratio
Figure 7. Stress-strain behavior of an as-spun filament.
filament.

The
The morphological
morphologicalchanges
changesininneck-drawing
neck-drawing ofof
anan
already crystallized
already as-spun
crystallized filament
as-spun (e.g.,(e.g.,
filament PE)
can be explained as follows (Figure 7) [9,143]:
PE) can be explained as follows (Figure 7) [9,143]:
•• aa strain
strain imposed
imposed on on aa stack
stack ofof crystal
crystal lamellae
lamellae initially
initially causes
causes stretching
stretching of of the
the interlamellar
interlamellar
amorphous
amorphous phases supporting the applied load (first, elastic part of the stress-straincurve);
phases supporting the applied load (first, elastic part of the stress-strain curve);
•• further stretching leads to slip-tilting and breakup of lamellae at the weakest points through
further stretching leads to slip-tilting and breakup of lamellae at the weakest points through chain
chain pulling and unfolding, leading to the initial abrupt change in filament cross-section (yield
pulling and unfolding, leading to the initial abrupt change in filament cross-section (yield point,
point, indicates
indicates transition
transition from to
from elastic elastic to plastic
plastic deformation);
deformation);
•• afterwards, as merely slippage of the lamellar fragments occurs,
afterwards, as merely slippage of the lamellar fragments occurs, the the filament
filament shows
shows deformation
deformation
without much
without muchresistance
resistanceand andthethe required
required force
force remains
remains practically
practically constantconstant (natural
(natural draw
draw ratio);
• ratio); all the chains are unfolded and the lamellar fragments, still connected by the pulled chains
finally,
• (tie finally, all the chains
molecules), are unfolded
form fibrils and crystal
of alternating the lamellar
blocksfragments,
and stretched stillnon-crystalline
connected by regions.
the pulled
chains (tie molecules), form fibrils of alternating crystal blocks and stretched non-crystalline
Drawing can be followed by annealing (heat setting) of the filaments under strain, to partially
regions.
relax frozen-in stresses, and to perfect and stabilize the microstructure [145]. This reorganization is a
resultDrawing can be
of increased followed
chain mobility by at
annealing
elevated(heat setting) of(i.e.,
temperatures thebetween
filamentsdrawing
under strain, to partially
temperature and
Trelax
m ). Asfrozen-in
a result,stresses,
shrinkage,andbrittleness
to perfect andand tendency
stabilize the microstructure
to fibrillate [145]. This reorganization
can be suppressed, and the filamentsis a
result ofsoft
become increased chain mobility
and flexible. at elevated
The transition temperatures
from brittle to ductile (i.e., between
behavior of drawing
fibers is atemperature
consequenceand of
Tm). As a result,
molecular shrinkage,
reorientation, brittleness
which can evenandbe tendency
inducedtoinfibrillate can be suppressed,
the amorphous and the handling
state. To facilitate filaments
become
of soft and flexible.
a multifilament The transition
in subsequent processes,from brittle to ductile
intermingling behavior of
of individual fibers iscan
filaments a consequence
be applied by of
molecular
passing themreorientation,
through an which can even be induced
air jet intermingler before theyin the
are amorphous
wound up [155]. state.Man-made
To facilitatefilaments
handlingcanof
a multifilament
also be texturizedintosubsequent processes,
improve elasticity, intermingling
tactility, bulkiness of andindividual
insulationfilaments
properties, canto be applied
avert by
a glossy
appearance, or to create special effects (fancy yarns) [160].
The main purpose of the winder is to provide a good package build (winding of filaments
around and along bobbin) that permits high speeds in the downstream process, without impairing the
Materials 2020, 13, 4298 14 of 32

filaments [160]. To achieve this, crossing and taper angles have to be optimized and filament tension
between godets and winder has to be balanced. Post-shrinkage that can break fibers or crush the
bobbin, or filament lengthening that would lead to a loose package, have to be prevented.

5. Physics of Melt-Spinning

5.1. Orientation in Polymer Fibers

In melt-spinning, drawing is the crucial step for extension and parallelization of macromolecules
and crystallites along the filament axis, and thus achieving man-made fibers with a tensile strength about
ten times higher than that of the as-spun filament [161,162]. Proper drawing results in row nucleated
lamellae rather than spherulitic structures which would turn the fiber brittle [143]. In consequence,
the physical properties of melt-spun fibers primarily derive from throughput rate (melt stream
velocity) through the die, quenching rate (rate of cooling to solidify the filament) and take-up velocity
(draw-down ratio) [142]. They are basically an indirect function of the molecular weight, as high
molecular weight favors formation of highly oriented fibers. A main factor driving uniaxial orientation
of the macromolecules is the stress at the solidification point, caused by air friction, mass inertia and
rheological forces during filament formation [10]. With increasing strain rate, the polymer molecules
start to disentangle and to align in the direction of flow [8]. Deformability and alignment of the
polymer chains is mainly limited by their entanglements; less flexible, rigid-chain polymers (e.g., LCPs)
repress chain entanglements and thus facilitate high molecular orientation [154].
As the filament cools in the spin-line, and entropic relaxation times exceed process (residence)
times, imposed molecular orientation starts to persist [154]. Unless spinning speed is very high,
flexible-chain polymers can only partially be oriented in the melt state, and their orientation has
to be completed by post-drawing in the solidified state to build up their tensile properties [9].
To achieve further orientation of crystalline and non-crystalline regions, the as-spun filament is
stretched between godets and winder (draw ratio). In semicrystalline polymers, drawing not only
promotes orientation and morphology, but also rate and degree of crystallinity (crystallization induced
by molecular deformation and orientation effects); this can lead to fibers with outstanding tenacities
and moduli [7,163]. The crystallization rate during drawing is strongly affected by any previously
introduced molecular orientation [142]. High orientation of macromolecules and crystallites results in
a fibrillar structure; this explains why highly oriented fibers can be prone to fibrillation.
High take-up speeds result in high strain rates in the spin-line, giving rise to increased
molecular orientation and strain-induced crystallization, and thus to reduced drawability of the
as-spun filament [164]. In other words, improvements in tensile strength level off when the highest
achievable orientation is reached. Delayed quenching by a post-heater (hot shroud) pushes the
onset of solidification further in direction of the spin-line and thus reduces freeze-point stress [165].
As-spun fibers with a low degree of crystallinity are easier to draw, more extensive draw ratios are
possible and higher tensile strength may be obtained [9]. As-spun filaments of slowly crystallizing
polymers can remain nearly amorphous when a high cooling rate in the spin-line is applied [153].

5.2. Mechanical Properties of Melt-Spun Fibers

Tensile properties of melt-spun fibers, in general, depend on molecular weight, molecular structure
and orientation, glass transition temperature, and degree of crystallinity of the fiber [164]. Tensile properties
of the most common melt-spun fibers, based on the linear flexible-chain polymers HDPE, PP, PET, PA 6
and PA 6.6, are in the range of 0.3–1.2 GPa tensile strength, 0.5–15 GPa Young’s modulus and 8–50%
strain at break [166,167]. Fully drawn fibers, i.e., fibers drawn beyond their natural draw ratio (Figure 7),
typically show load-strain curves as depicted in Figure 8.
Table 4 gives an example of physical properties of PET filaments produced in a one-step process,
where the as-spun filament is directly taken up by a winder. In high-speed spinning (>3500 m/min),
even slowly crystallizing polymers like PET undergo strain-induced crystallization. Excessive spinning
Materials 2020, 13, 4298 15 of 32

speeds, however, can lead to reduced crystallinity (due to less crystallization time) and reduced
Materials 2020,
molecular 13, x FOR PEER
orientation, REVIEW
leading to poor mechanical performance of the resulting fibers [168]. 15 of 32

Figure
Figure 8. Typical
8. Typical stress-strain
stress-strain curves
curves (own (own unpublished
unpublished data) ofdata) of common
common melt-spun
melt-spun monofilaments
monofilaments (PA 6.6,
PP(PA
and 6.6,
PET,PPalland PET, all diameter 80 µm).
diameter 80 µm).

Table 4. Physical properties of PET filaments as a function of spinning speed (one-step process) [169].
Table 4 gives an example of physical properties of PET filaments produced in a one-step process,
where theSpinning
as-spunSpeed
filament is directly taken
[m/min] up by a winder.
2000 4000 In high-speed
6000 spinning (>3500 m/min),
8000
even slowly crystallizing
Ultimate tensile stress polymers
[MPa] like PET undergo
140–220 strain-induced
290–470 440–570crystallization.
430–500 Excessive
spinning speeds,
Ultimate however,
tensile can lead to reduced
stress [cN/tex] 10–16 crystallinity
21–34 (due to less crystallization
32–41 31–36 time) and
reduced molecular orientation,
Ultimate tensile strain [%]leading to poor mechanical
200–250 performance
110–125 45–65of the resulting
25–35 fibers [168].
Young’s modulus [GPa] 2.1–2.8 3.5–6.1 8.2–9.5 11.5–12.8
Boiling water shrinkage [%] 58–62 20–57 3–5 2–3
Table 4. Physical properties of PET filaments as a function of spinning speed (one-step process) [169].
Birefringence ∆n 0.01 0.05 0.11 0.10–0.11
Spinning Speed [m/min]
Degree of crystallinity [%] 2–11 2000 4–27 4000 40–48 6000 41–50 8000
Ultimate tensile stress [MPa] 140–220 290–470 440–570 430–500
Ultimate tensile stress [cN/tex]
5.3. Melt-Spinning Instabilities 10–16 21–34 32–41 31–36
Ultimate tensile strain [%] 200–250 110–125 45–65 25–35
Flow instabilities at best compromise performance and appearance of melt-spun filaments [143,146],
Young’s modulus [GPa] 2.1–2.8 3.5–6.1 8.2–9.5 11.5–12.8
and at worst completely impede melt-spinning. A typical instability affecting the flow of a polymer
Boiling water shrinkage [%] 58–62 20–57 3–5 2–3
melt extruded through a capillary die is melt fracture, where a highly viscous extrudate exhibits
Birefringence Δn 0.01 0.05 0.11 0.10–0.11
a wavy distortion at high shear stress [170–172]. Occurrence of melt fracture depends on polymer
Degree of crystallinity [%] 2–11 4–27 40–48 41–50
type, average molecular weight and polydispersity, interface between polymer melt and die wall,
capillary throughput (shear stress) and spinneret design. Melt fracture can be counteracted by
5.3. Melt-Spinning Instabilities
increasing temperature, thus reducing viscosity, but with the risk of polymer degradation and loss
Flow instabilities at best compromise performance and appearance of melt-spun filaments
in melt-strength.
[143,146],
Spinning and at worst
below completely
a critical impede
shear stress melt-spinning.
usually A typical
results in smooth fiberinstability
surfaces, affecting
but with the flow of a
increasing
diepolymer
throughputmelttheextruded
surface through a capillary
can develop so-calleddiesharkskin
is melt fracture,
(Figure 9a),where a highly
which viscousadhesive
is a periodic extrudate
exhibits
failure a wavy
at the distortion
die exit at high shear
due to dynamic stress [170–172].
crack penetration Occurrence healing
and subsequent of melt [173].
fracture dependsison
Sharkskin
polymer
most type, average
commonly observed molecular
in highlyweight and polydispersity,
entangled linear polymersinterface between polymer
with sufficiently melt and die
narrow molecular
wall,distribution;
weight capillary throughput
amplitude(shear stress) and of
and wavelength spinneret design.
this small periodicMelt fracture
surface can be counteracted
distortion increase withby
increasingrate
throughput temperature, thus reducing
[127]. Increasing viscosity,
the capillary diameterbut with
while themaintaining
risk of polymer degradation
the throughput and loss
reduces
in melt-strength.
shear stress and thereby diminishes sharkskin formation.
Spinning
Polymers below
that a critical
exhibit shear
sharkskin stress usually
typically also show results in smooth known
a discontinuity fiber surfaces, but with
as stick-slip increasing
or oscillating
diefracture
melt throughput the surface Figure
(“bambooing”, can develop so-called
9b) when sharkskin
the shear stress(Figure
exceeds 9a), which is
a second a periodic
critical valueadhesive
[173].
In failure
contrast atto
the die exit due
sharkskin, to dynamic
the stick-slip crack penetration
instability is a volume and subsequent
distortion healing
initiated [173].
in the dieSharkskin
capillary, is
mostflow
where commonly
rate and observed
pressureinoscillate,
highly entangled linear polymers
and the extrudate surfacewith sufficiently
alternates narrowbetween
periodically molecular
weight distribution; amplitude and wavelength of this small periodic surface distortion increase with
throughput rate [127]. Increasing the capillary diameter while maintaining the throughput reduces
shear stress and thereby diminishes sharkskin formation.
Polymers that exhibit sharkskin typically also show a discontinuity known as stick-slip or
oscillating melt fracture (“bambooing”, Figure 9b) when the shear stress exceeds a second critical
Materials 2020, 13, x FOR PEER REVIEW 16 of 32
Materials 2020, 13, 4298 16 of 32

value [173]. In contrast to sharkskin, the stick-slip instability is a volume distortion initiated in the
die capillary,
relatively where
smooth flow rate andand
(compression) pressure
distortedoscillate, and theportions
(relaxation) extrudate surface Stick-slip
[128,170]. alternatescorresponds
periodically
between relatively smooth (compression) and distorted (relaxation) portions
to periodic transitions between weak and strong wall slip, as a result of sudden disentanglement [128,170]. Stick-slip
of
corresponds to periodic transitions between weak and strong wall slip, as a
the polymer molecular chains in the bulk from chains attached to the capillary wall (cohesive failure), result of sudden
disentanglement
sustained of the polymer
by an interaction molecular
between chains in
compression of the
the bulk
melt from
in thechains attached
reservoir to theofcapillary
upstream the die
wall (cohesive failure), sustained by an interaction between compression
and flow through the capillary [127,128,174–176]. Although the melt has only a small of the melt in thedegree
reservoir
of
compressibility, the large volume ratio between reservoir and capillary results in a pressure differencea
upstream of the die and flow through the capillary [127,128,174–176]. Although the melt has only
small degree
which of compressibility,
is sufficient the large volume
to sustain this oscillation ratio
[173]. The betweenperiod
oscillation reservoir and capillary
increases with theresults
volumeinofa
pressure
the difference
reservoir and with which
the is sufficient
L/D ratio oftothe
sustain
die, asthis oscillation
longer [173].result
capillaries The oscillation
in higher period increases
pressures in the
with the volume of the reservoir and with the L/D ratio of the die, as longer capillaries
reservoir [128]. Such flow instabilities can be counteracted with processing aids like fluoropolymers result in higher
pressures
that promote in the reservoir
slippage [128]. Such flow instabilities can be counteracted with processing aids like
[127].
fluoropolymers that promote slippage [127].

a b c
Figure 9. Illustration
Figure 9. Illustration of
of the
the development
development of
of (a)
(a) sharkskin,
sharkskin, (b)
(b) stick-slip
stick-slip (“bambooing”),
(“bambooing”), and
and (c)
(c) gross
gross
melt fracture (“corkscrewing”). By way of illustration, the polymer melt is represented in yellow.
melt fracture (“corkscrewing”). By way of illustration, the polymer melt is represented in yellow.

At very high throughput so-called gross melt fracture can occur, which affects the entire
At very high throughput so-called gross melt fracture can occur, which affects the entire cross-
cross-section of the extrudate, and originates from the acceleration of the pressurized melt in the
section of the extrudate, and originates from the acceleration of the pressurized melt in the
contraction upstream of the die capillary [170,174,177,178]. A spiraling of the melt flow in the
contraction upstream of the die capillary [170,174,177,178]. A spiraling of the melt flow in the
converging die entry can lead to helical extrudates (aka “corkscrewing”, Figure 9c) [172,174]. At even
converging die entry can lead to helical extrudates (aka “corkscrewing”, Figure 9c) [172,174]. At even
higher throughputs, the entrance instability becomes chaotic (aperiodic), involving true rapture and
higher throughputs, the entrance instability becomes chaotic (aperiodic), involving true rapture and
leading to a very rough filament [174]. All entangled polymer melts, also those not showing sharkskin
leading to a very rough filament [174]. All entangled polymer melts, also those not showing sharkskin
or slip-stick, are limited in throughput by the development of gross melt fracture [173]. By streamlining
or slip-stick, are limited in throughput by the development of gross melt fracture [173]. By
the die inlet or by increasing the capillary length, the amplitude of the distortion can be reduced,
streamlining the die inlet or by increasing the capillary length, the amplitude of the distortion can be
but the critical shear stress for fracture is unchanged [172].
reduced, but the critical shear stress for fracture is unchanged [172].
Another undesired spinning instability is the so-called draw resonance, which is a periodic
Another undesired spinning instability is the so-called draw resonance, which is a periodic
undulation of the cross-section area that starts at a critical draw-down ratio where the mass flow rate
undulation of the cross-section area that starts at a critical draw-down ratio where the mass flow rate
between die exit and take-up godet is not constant anymore, although process conditions are being
between die exit and take-up godet is not constant anymore, although process conditions are being
maintained constant [156,171,179]. To accommodate this mass flow variation at constant take-up speed,
maintained constant [156,171,179]. To accommodate this mass flow variation at constant take-up
small fluctuations in the fiber cross-section produce oscillations in the filament tension, which, on their
speed, small fluctuations in the fiber cross-section produce oscillations in the filament tension, which,
part, amplify the fluctuations [157]. Even when the rate of mass entering the region between die exit
on their part, amplify the fluctuations [157]. Even when the rate of mass entering the region between
and take-up godet is constant, the rate of mass leaving it is not controlled, because only the take-up
die exit and take-up godet is constant, the rate of mass leaving it is not controlled, because only the
speed is regulated, and not the filament diameter [143]. In consequence, a thinning-out of one part
take-up speed is regulated, and not the filament diameter [143]. In consequence, a thinning-out of
of the melt strand is compensated by the thickening of another part, resulting in undulations of the
one part of the melt strand is compensated by the thickening of another part, resulting in undulations
cross-section. This self-sustaining resonance is more likely to develop when the filament is quenched
of the cross-section. This self-sustaining resonance is more likely to develop when the filament is
in water near the spinneret to realize isothermal thinning.
quenched in water near the spinneret to realize isothermal thinning.
The critical draw-down ratio depends on polymer properties, extrusion and spinning temperature,
The critical draw-down ratio depends on polymer properties, extrusion and spinning
filament cross-section area, and the distance between spinneret and water bath [145]. Cooling and
temperature, filament cross-section area, and the distance between spinneret and water bath [145].
extension thickening have a stabilizing effect, and draw resonance can be prevented when a constant
Cooling and extension thickening have a stabilizing effect, and draw resonance can be prevented
tension, rather than a constant take-up velocity, is applied to the filament [157].
when a constant tension, rather than a constant take-up velocity, is applied to the filament [157].

6. Bicomponent Melt-Spinning

6.1. Objective of Bicomponent Spinning

Materials 2020, 13, x FOR PEER REVIEW 17 of 32

Bicomponent melt-spinning offers the possibility to achieve polymeric filaments with

extraordinary properties
Materials 2020, 13, 4298 like ultra-fineness, light-guidance or electrical conductivity. 17 ofHere,
32 two
polymers of different chemical and/or physical nature are extruded from one spinneret to form a
single filament, with the
6. Bicomponent goal to combine materials in elaborate fiber cross-sections [8]. The process
Melt-Spinning
of melt-spinning bicomponent filaments requires polymers with well-balanced processing
6.1. Objective of Bicomponent Spinning
temperatures and viscosities, and a good understanding of spin pack design and adhesion/bonding
between theBicomponent
two components [180].offers
melt-spinning Although this process
the possibility to achieveispolymeric
technologically rather
filaments with challenging, the
extraordinary
properties like ultra-fineness, light-guidance or electrical conductivity. Here, two polymers of different
range of bicomponent fibers and their applications has considerably grown since their launch in the
chemical and/or physical nature are extruded from one spinneret to form a single filament, with the goal
1960s [181].
to combine materials in elaborate fiber cross-sections [8]. The process of melt-spinning bicomponent
Thefilaments
main objective
requires of bicomponent
polymers melt-spinning
with well-balanced is to exploit
processing capabilities
temperatures not existing
and viscosities, and a in either
polymergood
alone, as advantageous
understanding mechanical,
of spin pack design andphysical or chemical
adhesion/bonding properties
between of two materials
the two components [180]. can be
combined in one fiber, expanding the range of possible applications [182,183]. As the two
Although this process is technologically rather challenging, the range of bicomponent fibers and polymers
their
applications has considerably grown since their launch in the 1960s [181].
can influence each other’s thinning and solidification behavior along the spinline, the molecular
The main objective of bicomponent melt-spinning is to exploit capabilities not existing in either
structurepolymer
development of both components
alone, as advantageous can beormutually
mechanical, physical affectedof [184].
chemical properties Depending
two materials can be on the
characteristics
combined ofinthe
onedifferent polymers,
fiber, expanding bicomponent
the range fibers are
of possible applications predominately
[182,183]. commercialized
As the two polymers can as
bondinginfluence
elements eachinother’s
thermobonded
thinning and nonwoven
solidification fabrics, as self-crimping
behavior along fibers
the spinline, the to achieve
molecular structuretextured
yarn, or as fibers with the surface functionality of special polymers and additives at reduced
development of both components can be mutually affected [184]. Depending on the characteristics of cost
the different polymers, bicomponent fibers are predominately commercialized as bonding elements in
[142,185,186].
thermobonded nonwoven fabrics, as self-crimping fibers to achieve textured yarn, or as fibers with the
surface functionality of special polymers and additives at reduced cost [142,185,186].
6.2. Cross-Section Geometries
6.2. Cross-Section Geometries
The three main cross-section geometries of bicomponent fibers are core-sheath, side-by-side, and
The three main cross-section geometries of bicomponent fibers are core-sheath, side-by-side,
multiple cores configurations like segmented pie and islands-in-the-sea (Figure 10) [34]. As most
and multiple cores configurations like segmented pie and islands-in-the-sea (Figure 10) [34]. As most
thermoplastic polymers
thermoplastic can be
polymers canapplied
be appliedtotoclad
cladaa core which
core which provides
provides the requested
the requested tensile tensile
strength,strength,
the core-sheath approach
the core-sheath enables
approach a variety
enables a varietyofof surfaces while
surfaces while maintaining
maintaining majormajor fiber
fiber and and textile
textile
properties [12]. Core-sheath types are commonly used as binder fibers for nonwovens, with a
properties [12]. Core-sheath types are commonly used as binder fibers for nonwovens, with a standard
standardpolymer
polymer as core
as core and a and a low softening-point
low softening-point polymer as polymer as sheath
sheath [182,187]. When[182,187]. When applied in
applied in nonwoven
production, the core-sheath fibers are heated to a temperature high enough to cause the sheath to
nonwoven production, the core-sheath fibers are heated to a temperature high enough to cause the
soften; consequently they will adhere to one another and stabilize the fabric [182].
sheath to soften; consequently they will adhere to one another and stabilize the fabric [182].

a b c d
Figure 10. Typical cross-sections of bicomponent fibers: (a) core-sheath, (b) side-by-side, (c) segmented
Figure 10. Typical cross-sections of bicomponent fibers: (a) core-sheath, (b) side-by-side, (c)
pie, (d) islands-in-the-sea. By way of illustration, the two fiber-forming polymers are represented in
segmented pie, (d) islands-in-the-sea. By way of illustration, the two fiber-forming polymers are
yellow and red, respectively.
represented in yellow and red, respectively.
Side-by-side bicomponent fibers are predominantly produced from two polymers that undergo
Side-by-side bicomponent
differential shrinkage: fibers are
after thermal predominantly
treatment or relaxation,produced from
the filaments curltwo polymers
up and that undergo
develop crimp
contraction, which can be used to design self-crimping yarns applied in voluminous products [188,189].
differential shrinkage: after thermal treatment or relaxation, the filaments curl up and develop crimp
Segmented pie and islands-in-the-sea configurations are mainly used to produce microfibers that are
contraction,
smallerwhich can than
in diameter be used to design
those obtained self-crimping
by conventional yarns applied
melt-spinning in voluminous
[190]. Segmented pie fibers areproducts
[188,189].
spunSegmented pie andpolymers
from two incompatible islands-in-the-sea configurations
that adhere poorly are mainly
and split into microfibers used toto produce
when subjected
microfibers that are
mechanical smaller
stress in while
[142,191], diameter than thosefibers
islands-in-the-sea obtained bymicrofibrils
consist of conventionalthat aremelt-spinning
embedded in [190].
Segmented pie fibers are spun from two incompatible polymers that adhere poorly and split into
a dissolvable polymer matrix which will be removed in a follow-up process [12].

microfibers when subjected to mechanical stress [142,191], while islands-in-the-sea fibers consist of
microfibrils that are embedded in a dissolvable polymer matrix which will be removed in a follow-
up process [12].

6.3. Spin Pack Design

When spinning bicomponent fibers, the polymers are extruded individually and kept separate
 Materials 2020, 13, 4298 18 of 32

6.3. Spin Pack Design

Materials 2020, 13, x FOR PEER REVIEW 18 of 32
When spinning bicomponent fibers, the polymers are extruded individually and kept separate up
to the spin pack, where the melt flows meet and exit together through the spinneret to form a filament
melts flow whichtogether,
consists of the interface
non-mixed dynamics
components considerably
that affect [34].
touch at the interface behavior
When and performance
two polymer melts of the
process, flow
and together,
all sortstheof interface
interfacedynamics
instabilities can occur
considerably affect[192].
behavior and performance of the process,
Depending on the position where the molten polymers are supposed to merge, spinnerets for
and all sorts of interface instabilities can occur [192].
bicomponentDepending
fibers areonclassified
the position aswhere
follows. In the by
the molten far most
polymers commontosingle
are supposed merge,die type (Figure
spinnerets for 11a),
bicomponent fibers are classified as follows. In the by far most common single die type (Figure 11a),
two pressurized polymer melts meet within the spinneret under laminar condition, which prevents
two pressurized polymer melts meet within the spinneret under laminar condition, which prevents
mixing of the two
mixing flows
of the two [34].
flows Smaller spin-packs
[34]. Smaller spin-packswith
with shorter
shorterresidence time,higher
residence time, higher hole
hole density and
density
larger number
and largerof multiple
number ofcoresmultiple cancores
be realized by etching
can be realized stacked
by etching plates
stacked to create
plates thethemelt
to create meltchannels
[144]. In channels
the second,
[144].less prominent
In the second, lessmultiple
prominent die type (Figure
multiple 11b), the
die type (Figure polymer
11b), melts
the polymer meet
melts meetjust at the
spinneret exit: this geometry is complex to realize, but it enables an exact positioning of the core
just at the spinneret exit: this geometry is complex to realize, but it enables an exact positioning of the
core polymer within the sheath, and it lessens rheological disparities between the two components [34].
polymer within the sheath, and it lessens rheological disparities between the two components [34].

a b
Figure 11. Two schematic examples of core-sheath bicomponent spinnerets: (a) single die and
Figure 11. Two schematic
(b) multiple examples
die. By way of core-sheath
of illustration, bicomponent
the core and sheath spinnerets:
polymer melts (a) single
are represented die and (b)
in red and
multipleyellow,
die. By way of illustration, the core and sheath polymer melts are represented in red and
respectively.
yellow, respectively.
7. Applications and Specialty Melt-Spun Fibers

7. Applications and Specialty Melt-Spun Fibers

7.1. Overview
For apparel use, melt-spun filaments are usually converted into threads resembling yarns made of
7.1. Overview
natural fibers [160]. As a first step, a filament bundle is crimped and cut or torn into short fibers with
lengths of several centimeters. These staple fibers are then converted into yarns by ring, open-end or
For air-jet
apparel use, melt-spun filaments are usually converted into threads resembling yarns made
spinning, and finally woven or knitted to get the desired textile fabrics.
of natural fibers [160]. As
For technical a first step,
applications, a filament
man-made fibersbundle
are spun is and
crimped
used asand cut or tornwhich
multifilaments, into short
are fibers
with lengths
superiorof in
several centimeters.
regularity and strengthThese staple
compared fibers
to staple are
fiber thenFor
yarns. converted into yarns
special applications like by ring, open-
fishing
end or air-jet spinning, and finally woven or knitted to get the desired textile fabrics.
lines, brushes, artificial hair, hook-and-loop, filtration or silk-screen printing, monofilaments come into
Forplay.
technical applications, man-made fibers are spun and used as multifilaments, which are
Due to their regularity and circular cross-sections, they are favored for precision fabrics.
High-performance melt-spun filaments are crucial for an immense number of technical applications.
superiorTable
in regularity and strength compared to staple fiber yarns. For special applications like
5 summarizes categories of technical textiles, exemplary applications, and the most common polymers
fishing lines,
used tobrushes, artificialfibers
produce respective hair,[193].
hook-and-loop,
Thanks to their filtration orproduction,
cost-efficient silk-screen printing,
nonwovens monofilaments
account for
come into the play.
highestDue to of
tonnage their regularity
technical and An
textiles [194]. circular
efficientcross-sections, theynonwovens
alternative to produce are favored is to for
drawprecision
fabrics. the filaments in the spinning process with high-speed air, and to deposit them randomly to form a fabric
High-performance melt-spun filaments are crucial for an immense number of technical
(spun-bond or melt-blown nonwoven).

applications. Table 5 summarizes categories of technical textiles, exemplary applications, and the
most common polymers used to produce respective fibers [193]. Thanks to their cost-efficient
production, nonwovens account for the highest tonnage of technical textiles [194]. An efficient
alternative to produce nonwovens is to draw the filaments in the spinning process with high-speed
air, and to deposit them randomly to form a fabric (spun-bond or melt-blown nonwoven).

Table 5. Technical textiles: Classification [193], applications and the three most common polymer
Materials 2020, 13, 4298 19 of 32

Table 5. Technical textiles: Classification [193], applications and the three most common polymer
classes for respective melt-spun fibers (indicated with +).

Application Field Examples Polyester Polyamide Polyolefin

Agriculture and horticulture (crop protection, fertilization),
Agrotech +
forestry, landscape gardening
Buildtech Textile architecture (membrane construction), scaffolding + +
Clothtech Functional garments and shoes + + +
Geotech Geotextiles (civil engineering, road & railroad construction) + +
Hometech Domestic textiles (furnishing, carpets, drapery) + + +
Indutech Filtration, silk-screen printing, lifting, conveying, fishery + + +
Medtech Medical and hygiene products + + +
Automobiles (tire cord, belts, airbags, carpets, upholstery,
Mobiltech + + +
insulation), railways, aircraft, ships
Oekotech Recycling, waste disposal, environmental protection + +
Packtech Packaging, carrier bags, ribbons + +
Protech Protective clothing (safety workwear), property protection + +
Sports apparel, swimsuits, parachutes, climbing ropes,
Sporttech + +
racket strings, artificial turf

7.2. Microfibers
Standard multifilaments range from 10 to 40 µm in diameter of the single filament, which in case
of PET corresponds to a linear density of 0.1–1.7 tex (mg/m). A microfiber can be defined as a filament
with a linear density below 0.1 tex. Finest directly melt-spun and drawn filaments go down to 5 µm
(0.03 tex in case of PET). Ultra-fine fibers with diameters below 1 µm are produced in two steps: First,
a multiple core bicomponent fiber is melt-spun, consisting of two incompatible polymers [34]. In a
subsequent step, the two components are separated. In the case of a segmented pie configuration
(Figure 10c), filaments of different polymers are split by mechanical means, while the sea (matrix) of
island-in-the-sea fibers (Figure 10d) is dissolved to bare the island filaments. This second approach is
ecologically disputable when solvents are needed, thus water-soluble matrix polymers are considered
as sea material [195,196]. One of the first applications of ultra-fine fibers was synthetic leather called
Alcantara® , followed by undergarments, sportswear and cleaning cloth. Owing to their high specific
surface area, microfiber fabrics have excellent wicking and particle capture properties. Fabrics made
from microfibers are very soft and flexible, inherently wind-proof thanks to their high fiber density,
yet still easily permeable to water vapor (perspiration) [34].

7.3. Bioresorbable Fibers for Medical Applications

Resorbable fibers, mainly produced from biopolyesters like PGA, PLA, PCL and their copolymers,
are prevailingly used as implants in the medical sector, with the advantage that they do not need to be
removed by a second surgery [197]. Requirements are that the fibers and their degradation products
show no toxic, inflammatory, immunogenic, carcinogenic or thrombogenic response, and that the fibers
can be sterilized [198]. Main applications are surgical sutures, bone fixation devices, tissue engineering
scaffolds, vascular grafts, temporary barriers and drug delivery devices [198]. The release rate of drug
delivery fibers can be controlled by drug content, fiber diameter and polymer biodegradation [115].
Rate and degree of biodegradation depend on the polymer’s hydrophobicity, composition and degree
of crystallinity; biopolymers degrade faster in the amorphous phase [77]. While PLA and PGA mainly
degrade by chemical hydrolysis into acidic by-products, PCL and PHB are usually degraded by
enzymatic hydrolysis [199,200]. PLA, PGA and their copolymers are widely used for tissue engineering
applications; PCL and PHB, on the other hand, are more attractive for long-term implants, due to their
hydrophobicity and low degradation rate [201].

7.4. Antimicrobial Fibers

An antimicrobial agent can either kill certain types of bacteria and fungi (biocide), or inhibit their
growth [138]. In garments, antimicrobial agents can prevent unpleasant odors and staining caused by
bacteria and fungi, which are fed by human sweat and sebum, as well as lubricants, auxiliaries and
7.4. Antimicrobial Fibers
An antimicrobial agent can either kill certain types of bacteria and fungi (biocide), or inhibit their
growth [138]. In garments, antimicrobial agents can prevent unpleasant odors and staining caused
by bacteria
Materials and
2020, 13, fungi, which are fed by human sweat and sebum, as well as lubricants, auxiliaries
4298 20 of 32
and dirt [202]. Healthcare applications to protect customers against pathogenic microorganisms
include hospital wear, wound care products and sterile bandages (traumatic, surgical and burn
dirt [202]. Healthcare applications to protect customers against pathogenic microorganisms include
wound infections) [203]. In addition, industrial fabrics used for awnings, screens, tents, tarpaulins,
hospital wear, wound care products and sterile bandages (traumatic, surgical and burn wound
ropes and similar products need protection from rotting and mildew as they are exposed to weather
infections) [203]. In addition, industrial fabrics used for awnings, screens, tents, tarpaulins, ropes and
[202].
similar products need protection from rotting and mildew as they are exposed to weather [202].
Some metals (silver, copper, zinc, gold, tin, mercury) and metal oxides (copper oxide, zinc oxide)
Some metals (silver, copper, zinc, gold, tin, mercury) and metal oxides (copper oxide, zinc oxide)
show antimicrobial properties, preferentially in the form of nanoparticles, since nanosizing increases
show antimicrobial properties, preferentially in the form of nanoparticles, since nanosizing increases
both reaction rate and contact area; their antimicrobial behavior is based on an oligodynamic effect,
both reaction rate and contact area; their antimicrobial behavior is based on an oligodynamic
whose mechanism is not yet fully understood [138]. Silver nanoparticles (AgNPs) are the most
effect, whose mechanism is not yet fully understood [138]. Silver nanoparticles (AgNPs) are the
effective broad-spectrum antibacterial agents, and respectively doped polymers found wide
most effective broad-spectrum antibacterial agents, and respectively doped polymers found wide
acceptability in medical and healthcare applications due to their excellent physicochemical and
acceptability in medical and healthcare applications due to their excellent physicochemical and
biological properties [204–206]. Parida et al. [207] found a solventless route to produce melt-spinnable
biological properties [204–206]. Parida et al. [207] found a solventless route to produce melt-spinnable
AgNP-polymer composites by in-situ thermal reduction of silver precursors during extrusion.
AgNP-polymer composites by in-situ thermal reduction of silver precursors during extrusion.
7.5. Conductive Fibers
7.5. Conductive Fibers
Conductive fibers can have a variety of functions, like antistatic protection, electromagnetic
Conductive fibers can have a variety of functions, like antistatic protection, electromagnetic shielding
shielding and conductivity in electronic applications. Electrically conductive polymeric fibers are
and conductivity in electronic applications. Electrically conductive polymeric fibers are produced by
produced by dispersing conductive agents in polymer melts, by depositing carbon or metallic
dispersing conductive agents in polymer melts, by depositing carbon or metallic coatings onto fiber surfaces,
coatings onto fiber surfaces, or by incorporating hydrophilic comonomers [208]. Intrinsically
or by incorporating hydrophilic comonomers [208]. Intrinsically conductive polymers (ICPs) exist, e.g.,
conductive polymers (ICPs) exist, e.g., PAC, PPy, PANI, PTh, PPV, PPP, PF and PEDOT: PSS, and
PAC, PPy, PANI, PTh, PPV, PPP, PF and PEDOT: PSS, and their conductivity can be tailored by doping via
their conductivity can be tailored by doping via oxidation or reduction [209,210]. However, todays
oxidation or reduction [209,210]. However, todays ICPs are not apt for melt-spinning due to poor stability,
ICPs are not apt for melt-spinning due to poor stability, tenacity and processability, and reports on
tenacity and processability, and reports on melt-spinning are limited to blends of conductive polymers
melt-spinning are limited to blends of conductive polymers with melt-spinnable polymers
with melt-spinnable polymers [209,211,212].
[209,211,212].
Antistatic fibers are required to prevent electrostatic charging by friction, thus preventing harmful
Antistatic fibers are required to prevent electrostatic charging by friction, thus preventing
discharge and adherence of particulates. In melt-spinning, the most convenient approach to overcome
harmful discharge and adherence of particulates. In melt-spinning, the most convenient approach to
the intrinsic resistivity of man-made fibers is to add carbon black in high concentration to the matrix
overcome the intrinsic resistivity of man-made fibers is to add carbon black in high concentration to
polymer. Since fibers with fillers have a reduced tenacity, antistatic fibers are usually melt-spun as
the matrix polymer. Since fibers with fillers have a reduced tenacity, antistatic fibers are usually melt-
bicomponent filaments to ensure sufficient tensile strength (Figure 12) [213].
spun as bicomponent filaments to ensure sufficient tensile strength (Figure 12) [213].

a b c

Figure 12.
Figure 12. Exemplary
Exemplary cross-sections
cross-sections of
of antistatic
antistaticbicomponent
bicomponentfibers:
fibers:a)(a)
concentric core-sheath,
concentric b)
core-sheath,
sandwich side-by-side, c) unequal side-by-side. By way of illustration, the pristine polymer is
(b) sandwich side-by-side, (c) unequal side-by-side. By way of illustration, the pristine polymer is
representedin
represented inyellow,
yellow,and
andthe
theblack
blackparts
partsdepict
depictthe
theantistatic
antistaticcomponent.
component.

7.6. Optical Fibers

7.6. Optical Fibers
Due to their mechanical flexibility and cost-efficiency, polymer optical fibers (POFs) are an
Due to their mechanical flexibility and cost-efficiency, polymer optical fibers (POFs) are an
attractive alternative to glass fibers [214]. An optical fiber transmits light along its axis by total internal
attractive alternative to glass fibers [214]. An optical fiber transmits light along its axis by total
reflection at the interface between a core and a sheath (cladding), where the refractive index of the
internal reflection at the interface between a core and a sheath (cladding), where the refractive index
core has to be higher than that of the cladding [215]. Common POF core materials are amorphous
of the core has to be higher than that of the cladding [215]. Common POF core materials are
polymers like PMMA, PS, PCs or COPs, with PMMA having the lowest attenuation [66,69]. Based on
amorphous polymers like PMMA, PS, PCs or COPs, with PMMA having the lowest attenuation
their relatively low refractive index, fluoropolymers are typically utilized as cladding material [216].
[66,69]. Based on their relatively low refractive index, fluoropolymers are typically utilized as
A widespread POF manufacturing technique is heat-drawing from a preform, well-known from
cladding material [216].
conventional glass fiber production [217,218]. While this process is discontinuous, bicomponent
melt-spinning enables the continuous fabrication of POFs [34]. Sohn and Park [219] proposed
graded-index POFs utilizing the diffusion of low molecular weight, high refractive index polymers
in extruding PMMA bicomponent fibers with the help of a long capillary die. The relatively low
processing temperatures even enable doping with luminescent dyes, which enables illuminating
and light harvesting applications [220]. Despite their relatively high attenuation, POFs can be
conventional glass fiber production [217,218]. While this process is discontinuous, bicomponent melt-
spinning enables the continuous fabrication of POFs [34]. Sohn and Park [219] proposed graded-
index POFs utilizing the diffusion of low molecular weight, high refractive index polymers in
extruding PMMA bicomponent fibers with the help of a long capillary die. The relatively low
processing
Materials 2020,temperatures
13, 4298 even enable doping with luminescent dyes, which enables illuminating 21 and
of 32
light harvesting applications [220]. Despite their relatively high attenuation, POFs can be
advantageous in textile applications where only short-distance light delivery, but high flexibility and
advantageous in textile applications where only short-distance light delivery, but high flexibility and
good processability are required [216]. Apart from signal transmission and illumination, POFs also
good processability are required [216]. Apart from signal transmission and illumination, POFs also
find applications in sensing, where the electronic equipment can be kept at a remote place free of
find applications in sensing, where the electronic equipment can be kept at a remote place free of
electromagnetic noise [221].
electromagnetic noise [221].
7.7.
7.7. Hollow
Hollow and
and Liquid-Core
Liquid-Core Fibers
Fibers
Hollow
Hollow melt-spun
melt-spun fibers
fibers areare mainly
mainly used
used inin thermal
thermal insulation
insulation products
products [12],
[12], but
but they
they also
also have
have
specialized applications in fluid separation [222,223]. To produce hollow
specialized applications in fluid separation [222,223]. To produce hollow fibers in a simple fibers in a simple way, a
way,
spinneret with several separated arc slits is used, where the polymer melt flows
a spinneret with several separated arc slits is used, where the polymer melt flows through and merges through and merges
at
at the
the die exit to
die exit to form
form aa tubular
tubular formform [224–226].
[224–226]. However,
However, withwith such
such spinnerets
spinnerets flow flow or
or weld
weld lines
lines
cannot
cannot be prevented. In order to achieve a more uniform and robust fiber, a spinneret with annular
be prevented. In order to achieve a more uniform and robust fiber, a spinneret with annular
co-flow
co-flow channel
channel can
can be
be applied,
applied, where
where thethe polymer
polymer melt melt is
is spun
spun through
through the
the annulus,
annulus, while
while aa lumen
lumen
fluid (air, nitrogen or CO 2) is injected through the inner capillary [227,228].
fluid (air, nitrogen or CO2 ) is injected through the inner capillary [227,228].
Based
Based on
on the
the same
same principle,
principle, Hufenus
Hufenus et et al.
al. [229]
[229] designed
designed aa special
special co-extrusion
co-extrusion line line that
that enables
enables
the
the pilot-scale production of liquid-filled polymeric fibers (Figure 13). The ability to produce aa
pilot-scale production of liquid-filled polymeric fibers (Figure 13). The ability to produce
continuous
continuous liquid-core
liquid-core fiber
fiber isis attractive
attractive since
since post-filling
post-filling ofof aa fine hollow filament
fine hollow filament would
would become
become
increasingly slow and uneconomic at extended lengths [230]. Liquids in the
increasingly slow and uneconomic at extended lengths [230]. Liquids in the core of a man-made filament core of a man-made
filament
can provide can unprecedented
provide unprecedented
propertiesproperties
regardingregarding
damping, damping, flame retardancy,
flame retardancy, perfumingperfuming
and many
and many other applications, without compromising mechanical
other applications, without compromising mechanical performance, dyeability or washability performance, dyeability or
[231].
washability [231].

High pressure
syringe pump Melt
pump

Screw extruder

Figure 13. Schematic of liquid-core fiber production. By way of illustration, polymer and liquid are
Figure 13. Schematic of liquid-core fiber production. By way of illustration, polymer and liquid are
represented in yellow and blue, respectively.
represented in yellow and blue, respectively.
8. Concluding Remarks
8. Concluding Remarks
The impressive success story of polymers has historically been kindled by the demand for
new The impressive
fibers. success story
The development ofoffilaments
polymersishas historically
strongly been kindled
intertwined by the demand
with research topics for
suchnew
as
fibers. The development of filaments is strongly intertwined with research
polymer synthesis and processing, multicomponent concepts, functionalization, medical and technicaltopics such as polymer
synthesis
applications,andor processing, multicomponent
internet of things. concepts, functionalization,
The goal of melt-spinning medicalin and
is to create anisotropy technical
thermoplastic
applications, or internet of things. The goal of melt-spinning is to create anisotropy
polymers, and the outcome are fibers that are high-performance, low-price, very durable and can be in thermoplastic
polymers,
produced at and thescale.
large outcomeTheirarequasi
fibers that are high-performance,
one-dimensional nature is thelow-price,
origin for very durable
a variety and can be
of applications,
produced at large scale. Their quasi one-dimensional nature is the origin for a variety
and the resulting textiles are both strong and flexible. However, due to the overall success of polymers, of applications,
and
their the resulting
mainly textilessourcing,
fossil-based are bothand strong and flexible.
humankind’s However,disposal
inappropriate due tohabits,
the overall
man-madesuccess of
fibers
polymers, their mainly fossil-based sourcing, and humankind’s inappropriate
are increasingly perceived as a global challenge in terms of resources, sustainability and waste disposal habits, man-
made fibers areDespite
management. increasingly perceived
its utmost as a global
importance, thischallenge in termsthe
topic is beyond of resources,
scope of thesustainability and
present review.
waste management.
Nevertheless, Despite
continuous its to
efforts utmost
develop importance,
new typesthis topic is beyond
of sustainable polymers,the fibers
scope and
of the present
textiles are
review. Nevertheless, continuous efforts
definitely necessary for a prosperous future. to develop new types of sustainable polymers, fibers and
textiles are definitely necessary for a prosperous future.
Author Contributions: Conceptualization, R.H.; writing—original draft preparation, R.H.; writing—review and
editing, R.H., Y.Y., M.D. and T.K.; visualization, R.H. All authors have read and agreed to the published version of
the manuscript.
Funding: This research received no external funding.
Acknowledgments: The authors thank Klaus Bender (EMS Chemie), Max Kurt (Monosuisse), Luzius Berger
(Serge Ferrari Tersuisse) and Bernd Blech (Trevira) for their valuable comments.
Materials 2020, 13, 4298 22 of 32

Conflicts of Interest: The authors declare no conflict of interest.

Glossary
as-spun filament filament spun and solidified without drawing & annealing
birefringence measure of molecular orientation in polymers
bobbin (spool) plastic or cardboard tube on which filaments are wound
die (nozzle) orifice to eject a polymer solution or melt as coherent stream
die swell relaxation and expansion of a polymer stream leaving the die
draw-down ratio (DDR) ratio between die exit velocity and take-up velocity
draw ratio (DR) ratio between speeds of take-up godet and winder
filament continuous fiber, typically spun as multiple filaments
fully drawn yarn (FDY) highly oriented filament(s) melt-spun with integrated drawing
temperature where an amorphous material’s state changes from hard to
glass-transition temperature (Tg )
viscous
godet (roller, galette) revolving cylinder for heating and drawing of filaments
tapered chamber to hold and dispense feed material (polymer granulate,
hopper (funnel)
chips)
filament(s) melt-spun at low speed to be post-processed by drawing and
low oriented yarn (LOY)
texturizing
melting temperature (Tm ) temperature where a crystalline material’s state changes from solid to liquid
stress-induced, abrupt decrease in filament cross-sectional area, relevant for
necking
molecular orientation and crystallization
partially oriented yarn (POY) partially oriented filament(s) to be post-processed by drawing & texturizing
liquid applied to reduce electrostatic effects and facilitate processing of
spin finish
filaments
equipment comprising multiple of dies to form filaments from a polymer
spinneret
solution or melt
filaments cut or torn into short fibers for yarn spinning or nonwoven
staple fibers
production
thermo-mechanical process to impart crimp and bulkiness to man-made
texturizing
filaments (draw textured yarn, DTY)
linear density (mass per unit length) of fibers or yarns, with unit “tex” in the
yarn count (titer)
SI system (1 tex = 1 mg/m)
Abbreviations
COP cyclo olefin polymer
HDPE high-density polyethylene
LCP liquid-crystal polymer
LDPE low-density polyethylene
P3HB poly-3-hydroxybutyrate
P4HB poly-4-hydroxybutyrate
PA 6 polyamide 6
PA 6.6 polyamide 6.6
PAC polyacetylene
PANI polyaniline
PBAT polybutylene adipate terephthalate
PBT polybutylene terephthalate
PC polycarbonate
PCL polycaprolactone
PEDOT:PSS poly(3,4-ethylenedioxithiophene) polystyrene sulfonate
PEE poly(ether ester)
PEEK polyetheretherketone
PEF polyethylene furanoate
PEI polyetherimide
PEN polyethylene naphthalate
Materials 2020, 13, 4298 23 of 32

PET polyethylene terephthalate

PF polyfluorene
PGA polyglycolide
PHA polyhydroxyalkanoate
PHBH polyhydroxybutyrate-co-hydroxyhexanoate
PHBV polyhydroxybutyrate-co-hydroxyvalerate
PLA polylactic acid
PMMA polymethylmethacrylate
PP polypropylene
PPP poly(p-phenylene)
PPS polyphenylene sulfide
PPV poly(p-phenylene vinylene)
PPy polypyrrole
PS polystyrene
PTFE polytetrafluoroethylene
PTh polythiophene
PTT polytrimethylene terephthalate
PU polyurethane
PVDF polyvinylidene fluoride
PVF polyvinyl fluoride
TPO thermoplastic polyolefin elastomer
TPU thermoplastic polyurethane
UHMWPE ultra-high molecular weight polyethylene

References
1. Kauffman, G.B. Rayon: The First Semi-Synthetic Fiber Product. J. Chem. Educ. 1993, 70, 887–893. [CrossRef]
2. Spear, B. Let there be light! Sir Joseph Swan and the incandescent light bulb. World Pat. Inf. 2013, 35, 38–41.
[CrossRef]
3. DuPont. Available online: https://www.dupont.com/about/our-history.html (accessed on 31 July 2020).
4. SRF. Available online: https://www.srf.ch/kultur/wissen/kunstfaser-perlon-nazi-deutschlands-antwort-auf-
nylon (accessed on 31 July 2020).
5. Jewkes, J.; Sawers, D.; Stillerman, R. The Sources of Invention; Palgrave Macmillan: London, UK, 1969.
6. Sauter, D.W.; Taoufik, M.; Boisson, C. Polyolefins, a Success Story. Polymers 2017, 9, 185. [CrossRef] [PubMed]
7. Ziabicki, A. Fundamentals of Fibre Formation: The Science of Fibre Spinning and Drawing; John Wiley & Sons:
Hoboken, NJ, USA, 1976.
8. Fourné, F. Synthetic Fibers: Machines and Equipment, Manufacture, Properties; Hanser: Munich, Germany, 1999.
9. Walczak, Z.K. Processes of Fiber Formation; Elsevier: Amsterdam, The Netherlands, 2002.
10. Beyreuther, R.; Vogel, R. Spinnability of polymer melts: A complex problem in basic research. Int. Polym. Process.
1996, 11, 154–158. [CrossRef]
11. Sen, K. Polypropylene fibres. In Manufactured Fibre Technology; Gupta, V.B., Kothari, V.K., Eds.;
Chapman & Hall: London, UK, 1997; pp. 457–479.
12. Jaffe, M.; East, A.J. Polyester Fibers. In Handbook of Fiber Chemistry; Lewin, M., Ed.; CRC Press: Boca Raton,
FL, USA, 2007; pp. 1–29.
13. Reese, G. Polyester Fibers: Fiber Formation and End-Use Applications. In Modern Polyesters: Chemistry and
Technology of Polyesters and Copolyesters; Scheirs, J., Long, T.E., Eds.; John Wiley & Sons Ltd.: Hoboken, NJ,
USA, 2003.
14. Wagner, J.R.; Mount, E.M.; Giles, H.F. Extrusion: The Definitive Processing Guide and Handbook, 2nd ed.;
William Andrew: Norwich, NY, USA, 2005.
15. Rosato, D.V.; Schott, N.R.; Rosato, D.V.; Rosato, M.G. Plastics Engineering, Manufacturing and Data Handbook;
Kluwer Academic Publishers: New York, NY, USA, 2001.
16. Perepelkin, K.E. The effect of the liquid and gas phase transitions on the extrusion stability in man-made
fibre and film processes. Fibre Chem. 1972, 3, 115–123. [CrossRef]
Materials 2020, 13, 4298 24 of 32

17. Prevorsek, D.C.; Tirpak, G.A.; Harget, P.J.; Reimschuessel, A.C. Effects of thermal contraction on structure
and properties of PET fibers. J. Macromol. Sci. Part B 1974, 9, 733–759. [CrossRef]
18. Mukhopadhyay, S.K. Manufacturing, properties and tensile failure of nylon fibres. In Handbook of Tensile
Properties of Textile and Technical Fibres; Bunsell, A.R., Ed.; Woodhead Publishing: Cambridge, UK, 2009;
pp. 197–222.
19. Sattler, H.; Schweizer, M. Fibers, 5. Polyester Fibers. In Ullmann’s Encyclopedia of Industrial Chemistry;
Wiley-VCH: Hoboken, NJ, USA, 2011.
20. Ouederni, M. Polyolefin Compounds and Materials: Fundamentals and Industrial Applications. In Polyolefins
in Textiles and Nonwovens; Al-Ali AlMa’adeed, M., Krupa, I., Eds.; Springer International Publishing: Cham,
Switzerland, 2016; pp. 231–245.
21. Niaounakis, M. Biopolymers: Processing and Products; William Andrew Publishing: Oxford, UK, 2015.
22. East, A.J. The structure of polyester fibers. In Handbook of Textile Fibre Structure; Eichhorn, S.J., Hearle, J.W.S.,
Jaffe, M., Kikutani, T., Eds.; Woodhead Publishing: Cambridge, UK, 2009; Volume 1, pp. 181–231.
23. Mochizuki, M. Synthesis, properties and structure of polylactic acid fibres. In Handbook of Textile Fibre
Structure; Eichhorn, S.J., Hearle, J.W.S., Jaffe, M., Kikutani, T., Eds.; Woodhead Publishing: Cambridge, UK,
2009; Volume 1, pp. 257–275.
24. Hearle, J.W.S. Thermally and chemically resistant fibres: Structure and properties. In Handbook of Textile Fibre
Structure; Eichhorn, S.J., Hearle, J.W.S., Jaffe, M., Kikutani, T., Eds.; Woodhead Publishing: Cambridge, UK,
2009; Volume 2, pp. 450–457.
25. Domininghaus, H. Die Kunststoffe und ihre Eigenschaften, 6th ed.; Springer: Berlin/Heidelberg, Germany, 2005.
26. Van Krevelen, D.W.; te Nijenhuis, K. Properties of Polymers: Their Correlation with Chemical Structure;
Their Numerical Estimation and Prediction from Additive Group Contributions, 4th ed.; Elsevier: Amsterdam,
The Netherlands, 2009.
27. Osswald, T.A.; Menges, G. Materials Science of Polymers for Engineers, 3rd ed.; Carl Hanser: Cincinnati, OH,
USA, 2012.
28. Takasaki, M.; Ito, H.; Kikutani, T. Structure Development of Polylactides with Various d-Lactide Contents in
the High-Speed Melt Spinning Process. J. Macromol. Sci. Part B 2003, 42, 57–73. [CrossRef]
29. Anton, A.; Baird, B.R. Polyamides, Fibers. In Encyclopedia of Polymer Science and Technology; Mark, H.F., Ed.;
John Wiley & Sons: Hoboken, NJ, USA, 2001; Volume 3, pp. 584–618.
30. Vasanthan, N. Polyamide fiber formation: Structure, properties and characterization. In Handbook of Textile
Fibre Structure; Eichhorn, S.J., Hearle, J.W.S., Jaffe, M., Kikutani, T., Eds.; Woodhead Publishing: Cambridge,
UK, 2009; Volume 1, pp. 232–256.
31. Deopura, B.L. Polyamide fibers. In Polyesters and Polyamides; Deopura, B.L., Alagirusamy, R., Joshi, M.,
Gupta, B., Eds.; Woodhead Publishing: Cambridge, UK, 2008.
32. Yan, Y.; Gooneie, A.; Ye, H.; Deng, L.; Qiu, Z.; Reifler, F.A.; Hufenus, R. Morphology and Crystallization of
Biobased Polyamide 56 Blended with Polyethylene Terephthalate. Macromol. Mater. Eng. 2018, 303, 1800214.
[CrossRef]
33. Morales-Gámez, L.; Soto, D.; Franco, L.; Puiggalí, J. Brill transition and melt crystallization of nylon 56:
An odd–even polyamide with two hydrogen-bonding directions. Polymer 2010, 51, 5788–5798. [CrossRef]
34. Hufenus, R.; Yan, Y.; Dauner, M.; Yao, D.; Kikutani, T. Bicomponent Fibers. In Handbook of Fibrous Materials;
Hu, J., Kumar, B., Lu, J., Eds.; Wiley-VCH: Weinheim, Germany, 2020; Volume 1, pp. 281–313.
35. Mitsubishi Gas Chemical. Available online: https://www.mgc.co.jp/eng/products/ac/nmxd6/index.html
(accessed on 31 July 2020).
36. Akro-Plastic. Available online: https://akro-plastic.com/compound-overview/akromid-t/ (accessed on
31 July 2020).
37. Militky, J. The chemistry, manufacture and tensile behaviour of polyester fibers. In Handbook of Tensile
Properties of Textile and Technical Fibres; Bunsell, A.R., Ed.; Woodhead Publishing: Cambridge, UK, 2009;
pp. 223–314.
38. Chuah, H.H. Poly(trimethylene terephthalate). In Encyclopedia of Polymer Science and Technology;
Mark, H.F., Ed.; John Wiley & Sons: Hoboken, NJ, USA, 2001; Volume 3, pp. 544–558.
39. Sakellarides, S.L. Poly(ethylene naphthalate) (PEN). In Encyclopedia of Polymer Science and Technology;
Mark, H.F., Ed.; John Wiley & Sons: Hoboken, NJ, USA, 2004; Volume 11, pp. 88–114.
Materials 2020, 13, 4298 25 of 32

40. Chen, P.; Kotek, R. Advances in the Production of Poly(ethylene naphthalate) Fibers. Polym. Rev. 2018, 48,
392–421.
41. Mather, R.R. The structure of polyolefin fibres. In Handbook of Textile Fibre Structure; Eichhorn, S.J.,
Hearle, J.W.S., Jaffe, M., Kikutani, T., Eds.; Woodhead Publishing: Cambridge, UK, 2009; Volume 1,
pp. 276–304.
42. Malkan, S.R. Improving the use of polyolefins in nonwovens. In Polyolefin Fibres; Ugbolue, S.C.O., Ed.;
Woodhead Publishing: Cambridge, UK, 2017; pp. 285–311.
43. Ward, I.M.; Lemstra, P.J. Production and properties of highmodulus and high-strength polyethylene
fibres. In Handbook of Textile Fibre Structure; Eichhorn, S.J., Hearle, J.W.S., Jaffe, M., Kikutani, T., Eds.;
Woodhead Publishing: Cambridge, UK, 2009; Volume 1, pp. 352–393.
44. Toyobo. Available online: https://www.toyobo-global.com/seihin/dn/tsunooga/index.html (accessed on
31 July 2020).
45. Horrocks, A.R.; McIntosh, B. Chemically resistant fibres. In High-Performance Fibres; Hearle, J.W.S., Ed.;
Woodhead Publishing: Cambridge, UK, 2001; pp. 259–280.
46. Gangal, S.V.; Brothers, P.D. Perfluorinated Polymers, Perfluorinated Ethylene–Propylene Copolymers.
In Encyclopedia of Polymer Science and Technology; Mark, H.F., Ed.; John Wiley & Sons: Hoboken, NJ, USA, 2010.
47. Frick, A.; Sich, D.; Heinrich, G.; Stern, C.; Schlipf, M. Classification of New Melt-Processable PTFE:
Comparison of Emulsion—And Suspension-Polymerized Materials. Macromol. Mater. Eng. 2012, 297,
329–341. [CrossRef]
48. Seo, K.S. Rheology and Processing of Thermotropic Liquid Crystalline Polymers. In Thermotropic Liquid
Crystal Polymers: Thin-film Polymerization, Characterization, Blends and Applications; Chung, T.-S., Ed.;
Technomic Publishing: Lancaster, UK, 2001; pp. 219–256.
49. Chen, B.-K.; Tsay, S.-Y.; Chen, J.-Y. Synthesis and properties of liquid crystalline polymers with low Tm and
broad mesophase temperature ranges. Polymer 2005, 46, 8624–8633. [CrossRef]
50. Sloan, F. Liquid crystal aromatic polyester-arylate (LCP) fibers: Structure, properties, and applications.
In Structure and Properties of High-Performance Fibers; Bhat, G., Ed.; Woodhead Publishing: Oxford, UK, 2017;
pp. 113–140.
51. Cheng, S.Z.D.; Li, F.; Li, C.Y.; McCreight, K.W.; Yoon, Y.; Harris, F.W. Fibers from Liquid Crystalline Polymers.
In Structure Formation in Polymeric Fibers; Salem, D.R., Ed.; Carl Hanser Publishers: Munich, Germany, 2001;
pp. 247–295.
52. Yamamoto, Y.; Nakagawa, J. The structure and properties of high-modulus, high-tenacity Vectran™
fibres. In Handbook of Textile Fibre Structure; Eichhorn, S.J., Hearle, J.W.S., Jaffe, M., Kikutani, T., Eds.;
Woodhead Publishing: Cambridge, UK, 2009; Volume 1, pp. 413–428.
53. Kuraray. Available online: https://www.kuraray.com/products/vectran (accessed on 31 July 2020).
54. Otaigbes, J.U.; Madbouly, A. The processing, structure and properties of elastomeric fibers. In Handbook
of Textile Fibre Structure; Eichhorn, S.J., Hearle, J.W.S., Jaffe, M., Kikutani, T., Eds.; Woodhead Publishing:
Cambridge, UK, 2009; Volume 1, pp. 325–351.
55. Abraham, T.; McMahan, C. Thermoplastic Elastomers: Fundamentals and Applications. In Rubber
Compounding: Chemistry and Applications; Rodgers, B., Ed.; Marcel Dekker: New York, NY, USA, 2004;
pp. 163–238.
56. Jing, L. Elastic Fibers. In Handbook of Fibrous Materials; Hu, J., Kumar, B., Lu, J., Eds.; Wiley-VCH: Weinheim,
Germany, 2020; Volume 1, pp. 335–359.
57. Fibre2Fashion. Available online: https://www.fibre2fashion.com/industry-article/1/a-new-process-of-
producing-spandex-yarns (accessed on 31 July 2020).
58. Datta, J.; Kasprzyk, P. Thermoplastic polyurethanes derived from petrochemical or renewable resources:
A comprehensive review. Polym. Eng. Sci. 2018, 58, E14–E35. [CrossRef]
59. Hu, J.; Lu, J.; Zhu, Y. New Developments in Elastic Fibers. Polym. Rev. 2008, 48, 275–301. [CrossRef]
60. Spiridonov, P.; Lambrinos, E.; Peng, Z. Extrusion of monofilaments of thermoplastic elastomers. Synth. Met.
2005, 152, 61–64. [CrossRef]
61. Casey, P.; Chen, H.; Poon, B.; Bensason, S.; Menning, B.; Liu, L.; Hu, Y.; Hoenig, W.; Gelfer, M.; Dems, B.; et al.
Polyolefin Based Crosslinked Elastic Fiber: A Technical Review of DOW XLA™ Elastic Fiber Technology.
Polym. Rev. 2008, 48, 302–316. [CrossRef]
Materials 2020, 13, 4298 26 of 32

62. Leal, A.A.; Best, J.P.; Rentsch, D.; Michler, J.; Hufenus, R. Spectroscopic elucidation of structure-property
relations in filaments melt-spun from amorphous polymers. Eur. Polym. J. 2017, 89, 78–87. [CrossRef]
63. Kasai, N.; Kakudo, M. X-Ray Diffraction by Macromolecules; Kodansha Ltd.: Tokyo, Japan; Springer:
Berlin/Heidelberg, Germany, 2005.
64. Chung, C.I. Extrusion of Polymers: Theory and Practice, 3rd ed.; Carl Hanser Verlag: Munich, Germany, 2019.
65. Leal, A.A.; Mohanty, G.; Reifler, F.A.; Michler, J.; Hufenus, R. Mechanical response of melt-spun amorphous
filaments. Sci. Technol. Adv. Mater. 2014, 15, 35016. [CrossRef]
66. Reifler, F.A.; Hufenus, R.; Krehel, M.; Zgraggen, E.; Rossi, R.M.; Scherer, L.J. Polymer optical fibers for textile
applications—Bicomponent melt spinning from cyclic olefin polymer and structural characteristics revealed
by wide angle X-ray diffraction. Polymer 2014, 55, 5695–5707. [CrossRef]
67. Ebewele, R.O. Polymer Science and Technology; CRC Press: Boca Raton, FL, USA, 2000.
68. Zia, Q.; Androsch, R.; Radusch, H.-J. Effect of the structure at the micrometer and nanometer scales on the
light transmission of isotactic polypropylene. J. Appl. Polym. Sci. 2010, 117, 1013–1020. [CrossRef]
69. Zaremba, D.; Evert, R. Materials, chemical properties and analysis. In Polymer Optical Fibres; Bunge, C.-A.,
Gries, T., Beckers, M., Eds.; Woodhead Publishing: Cambridge, UK, 2017; pp. 153–186.
70. Avinc, O.; Khoddami, A. Overview of Poly(lactic acid) (PLA) Fibre. Fibre Chem. 2009, 41, 391–401. [CrossRef]
71. Tokiwa, Y.; Calabia, B.P. Biodegradability and biodegradation of poly(lactide). Appl. Microbiol. Biotechnol.
2006, 72, 244–251. [CrossRef] [PubMed]
72. Södergård, A.; Inkinen, S. Production, Chemistry and Properties of Polylactides. In Biopolymers—New
Materials for Sustainable Films and Coatings; Plackett, D., Ed.; John Wiley & Sons: Chichester, UK, 2011;
pp. 43–63.
73. Tsuji, H. Poly(lactide) Stereocomplexes: Formation, Structure, Properties, Degradation, and Applications.
Macromol. Biosci. 2005, 5, 569–597. [CrossRef] [PubMed]
74. Roungpaisan, N.; Takarada, W.; Kikutani, T. Development of Polylactide Fibers Consisting of Highly Oriented
Stereocomplex Crystals Utilizing High-Speed Bicomponent Melt Spinning Process. J. Fiber Sci. Technol. 2019,
75, 119–131. [CrossRef]
75. Takasaki, M.; Ito, H.; Kikutani, T. Development of Stereocomplex Crystal of Polylactide in High-Speed Melt
Spinning and Subsequent Drawing and Annealing Processes. J. Macromol. Sci. Part B 2003, 42, 403–420.
[CrossRef]
76. Azimi, B.; Nourpanah, P.; Rabiee, M.; Arbab, S. Poly (∈-caprolactone) Fiber: An Overview. J. Eng. Fibers Fabr.
2014, 9, 155892501400900309. [CrossRef]
77. Kwon, G.S.; Furgeson, D.Y. Biodegradable polymers for drug delivery systems. In Biomedical Polymers;
Jenkins, M., Ed.; Woodhead Publishing: Cambridge, UK, 2007; pp. 83–110.
78. Gupta, B.; Ray, G.A.R. Preparation of poly(ε-caprolactone)/poly(ε-caprolactone-co-lactide) (PCL/PLCL) blend
filament by melt spinning. J. Appl. Polym. Sci. 2012, 123, 1944–1950. [CrossRef]
79. Hinüber, C.; Häussler, L.; Vogel, R.; Brünig, H.; Heinrich, G.; Werner, C. Hollow fibers made from a
poly(3-hydroxybutyrate)/poly-ε-caprolactone blend. Express Polym. Lett. 2011, 5, 643–652. [CrossRef]
80. Meng, Q.; Hu, J. Study on poly(ε-caprolactone)-based shape memory copolymer fiber prepared by bulk
polymerization and melt spinning. Polym. Adv. Technol. 2008, 19, 131–136. [CrossRef]
81. Pal, J.; Kankariya, N.; Sanwaria, S.; Nandan, B.; Srivastava, R.K. Control on molecular weight reduction of
poly(ε-caprolactone) during melt spinning-A way to produce high strength biodegradable fibers. Mater. Sci.
Eng. C 2013, 33, 4213–4220. [CrossRef]
82. Mochizuki, M.; Nakayama, K.; Qian, R.; Jiang, B.-Z.; Hirami, M.; Hayashi, T.; Masuda, T.; Nakajima, A.
Studies on the biodegradable poly(hexano-6-lactone) fibers 1. Structure and properties of drawn
poly(hexano-6-lactone) fibers (Technical Report). Pure Appl. Chem. 1997, 69, 2567–2576. [CrossRef]
83. Charuchinda, A.; Molloy, R.; Siripitayananon, J.; Molloy, N.; Sriyai, M. Factors influencing the small-scale
melt spinning of poly(ε-caprolactone) monofilament fibres. Polym. Int. Sci. 2003, 52, 1175–1181. [CrossRef]
84. Krishnanand, K.; Deopura, B.L.; Gupta, B. Determination of intrinsic birefringence values of polycaprolactone
filaments. Polym. Int. 2012, 62, 49–53. [CrossRef]
85. Perret, E.; Reifler, F.A.; Gooneie, A.; Chen, K.; Selli, F.; Hufenus, R. Structural response of melt-spun
poly(3-hydroxybutyrate) fibers to stress and temperature. Polymer 2020, 197, 122503. [CrossRef]
86. Pillai, C.K.S.; Sharma, C.P. Review Paper: Absorbable Polymeric Surgical Sutures: Chemistry, Production,
Properties, Biodegradability, and Performance. J. Biomater. Appl. 2010, 25, 291–366. [CrossRef] [PubMed]
Materials 2020, 13, 4298 27 of 32

87. Muffly, T.M.; Tizzano, A.P.; Walters, M.D. The history and evolution of sutures in pelvic surgery. J. R. Soc. Med.
2011, 104, 107–112. [CrossRef] [PubMed]
88. Ikada, Y.; Tsuji, H. Biodegradable polyesters for medical and ecological applications. Macromol. Rapid Commun.
2000, 21, 117–132. [CrossRef]
89. Saigusa, K.; Takarada, W.; Kikutani, T. Improvement of the Mechanical Properties of Poly(Glycolic Acid)
Fibers Through Control of Molecular Entanglements in the Melt Spinning Process. J. Macromol. Sci. Part B
2020, 59, 399–414. [CrossRef]
90. Saigusa, K.; Saijo, H.; Yamazaki, M.; Takarada, W.; Kikutani, T. Influence of carboxylic acid content and
polymerization catalyst on hydrolytic degradation behavior of Poly(glycolic acid) fibers. Polym. Degrad. Stab.
2020, 172, 109054. [CrossRef]
91. Jiang, L.; Wolcott, M.P.; Zhang, J. Study of Biodegradable Polylactide/Poly(butylene adipate-co-terephthalate)
Blends. Biomacromolecules 2006, 7, 199–207. [CrossRef]
92. Witt, U.; Müller, R.J.; Deckwer, W.D. Biodegradation behavior and material properties of aliphatic/aromatic
polyesters of commercial importance. J. Environ. Polym. Degrad. 1997, 5, 81–89. [CrossRef]
93. Shi, X.; Ito, H.; Kikutani, T. Characterization on mixed-crystal structure and properties of poly(butylene
adipate-co-terephthalate) biodegradable fibers. Polymer 2005, 46, 11442–11450. [CrossRef]
94. Manvi, P.K.; Beckers, M.; Mohr, B.; Seide, G.; Gries, T.; Bunge, C.-A. Polymer fiber-based biocomposites for
medical sensing applications. In Materials for Biomedical Engineering; Grumezescu, V., Grumezescu, A.M., Eds.;
Elsevier: Amsterdam, The Netherlands, 2019; pp. 57–88.
95. Nakajima, H.; Dijkstra, P.; Loos, K. The Recent Developments in Biobased Polymers toward General
and Engineering Applications: Polymers that are Upgraded from Biodegradable Polymers, Analogous to
Petroleum-Derived Polymers, and Newly Developed. Polymers 2017, 9, 523. [CrossRef] [PubMed]
96. Leja, K.; Lewandowicz, G. Polymer biodegradation and biodegradable polymers-A review. Pol. J. Environ. Stud.
2010, 19, 255–266.
97. Freier, T. Biopolyesters in Tissue Engineering Applications. Adv. Polym. Sci. 2006, 203, 1–61.
98. Sudesh, K.; Abe, H.; Doi, Y. Synthesis, structure and properties of polyhydroxyalkanoates: Biological polyesters.
Prog. Polym. Sci. 2000, 25, 1503–1555. [CrossRef]
99. Zinn, M.; Witholt, B.; Egli, T. Occurrence, synthesis and medical application of bacterial polyhydroxyalkanoate.
Adv. Drug Deliv. Rev. 2001, 53, 5–21. [CrossRef]
100. Chen, G.Q.; Wu, Q. The application of polyhydroxyalkanoates as tissue engineering materials. Biomaterials
2005, 26, 6565–6578. [CrossRef]
101. Bonartsev, G.A.; Myshkina, V.L.; Nikolaeva, D.A.; Kevbrina, M.V.; Kallistova, A.Y.; Gerasin, V.A.; Iordanskii, A.L.;
Nozhevnikova, A.N. Aerobic and Anaerobic Microbial Degradation of Poly-β-Hydroxybutyrate Produced
by Azotobacter chroococcum. Appl. Biochem. Biotechnol. Part A Enzyme Eng. Biotechnol. 2003, 109, 285–302.
[CrossRef]
102. Iwata, T.; Doi, Y. Crystal structure and biodegradation of aliphatic polyester crystals. Macromol. Chem. Phys.
1999, 200, 2429–2442. [CrossRef]
103. Keshavarz, T.; Roy, I. Polyhydroxyalkanoates: Bioplastics with a green agenda. Curr. Opin. Microbiol. 2010,
13, 321–326. [CrossRef]
104. Pan, P.; Inoue, Y. Polymorphism and isomorphism in biodegradable polyesters. Prog. Polym. Sci. (Oxf.) 2009,
34, 605–640. [CrossRef]
105. Yokouchi, M.; Chatani, Y.; Tadokoro, H.; Teranishi, K.; Tani, H. Structural studies of polyesters: 5.
Molecular and crystal structures of optically active and racemic poly(β-hydroxybutyrate). Polymer 1973, 14,
267–272. [CrossRef]
106. Lenz, R.W.; Marchessault, R.H. Bacterial Polyesters: Biosynthesis, Biodegradable Plastics and Biotechnology.
Biomacromolecules 2005, 6, 1–8. [CrossRef] [PubMed]
107. Hufenus, R.; Reifler, F.A.; Fernández-Ronco, M.P.; Heuberger, M. Molecular orientation in melt-spun
poly(3-hydroxybutyrate) fibers: Effect of additives, drawing and stress-annealing. Eur. Polym. J. 2015, 71,
12–26. [CrossRef]
108. Vogel, R.; Voigt, D.; Tändler, B.; Gohs, U.; Haussler, L.; Brünig, H. Melt Spinning of Poly(3-hydroxybutyrate)
for Tissue Engineering Using Electron-Beam-Irradiated Poly(3-hydroxybutyrate) as Nucleation Agent.
Macromol. Biosci. 2008, 8, 426–431. [CrossRef]
Materials 2020, 13, 4298 28 of 32

109. Tanaka, T.; Yabe, T.; Teramachi, S.; Iwata, T. Mechanical properties and enzymatic degradation of
poly[(R)-3-hydroxybutyrate] fibers stretched after isothermal crystallization near Tg. Polym. Degrad. Stab. 2007,
92, 1016–1024. [CrossRef]
110. Furuhashi, Y.; Imamura, Y.; Jikihara, Y.; Yamane, H. Higher order structures and mechanical properties of
bacterial homo poly(3-hydroxybutyrate) fibers prepared by cold-drawing and annealing processes. Polymer
2004, 45, 5703–5712. [CrossRef]
111. Schmack, G.; Jehnichen, D.; Vogel, R.; Tändler, B. Biodegradable fibers of poly(3-hydroxybutyrate) produced
by high-speed melt spinning and spin drawing. J. Polym. Sci. Part B Polym. Phys. 2000, 38, 2841–2850.
[CrossRef]
112. Gordeyev, S.A.; Nekrasov, Y.P. Processing and mechanical properties of oriented poly(β-hydroxybutyrate)
fibers. J. Mater. Sci. Lett. 1999, 18, 1691–1692. [CrossRef]
113. Tanaka, T.; Fujita, M.; Takeuchi, A.; Suzuki, Y.; Uesugi, K.; Ito, K.; Fujisawa, T.; Doi, Y.; Iwata, T. Formation of
Highly Ordered Structure in Poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate] High-Strength Fibers.
Macromolecules 2006, 39, 2940–2946. [CrossRef]
114. Yamamoto, T.; Kimizu, M.; Kikutani, T.; Furuhashi, Y.; Cakmak, M. The Effect of Drawing and Annealing
Conditions on the Structure and Properties of Bacterial Poly (3-hydroxybutyrate-co-3 hydroxyvalerate)
Fibers. Int. Polym. Process. 1997, 12, 29–37. [CrossRef]
115. Hufenus, R.; Reifler, F.A.; Maniura-Weber, K.; Spierings, A.; Zinn, M. Biodegradable Bicomponent
Fibers from Renewable Sources: Melt-Spinning of Poly (lactic acid) and Poly[(3-hydroxybutyrate)-co-
(3-hydroxyvalerate)]. Macromol. Mater. Eng. 2012, 297, 75–84. [CrossRef]
116. Bond, E.B. Fiber spinning behavior of a 3-hydroxybutyrate/3-hydroxyhexanoate copolymer. Macromol. Symp.
2003, 197, 19–32. [CrossRef]
117. Kabe, T.; Hongo, C.; Tanaka, T.; Hikima, T.; Takata, M.; Iwata, T. High tensile strength fiber of
poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] processed by two-step drawing with intermediate
annealing. J. Appl. Polym. Sci. 2015, 132. [CrossRef]
118. Kaneka. Available online: http://www.kaneka.be/documents/PHBH-brochure-11-2017.pdf (accessed on
31 July 2020).
119. Qin, Q.; Takarada, W.; Kikutani, T. Fiber Structure Development of PHBH through Stress-Induced
Crystallization in High-Speed Melt Spinning Process. J. Fiber Sci. Technol. 2017, 73, 49–60. [CrossRef]
120. Guo, K.; Martin, D.P. Poly-4-hydroxybutyrate (P4HB) in Biomedical Applications and Tissue Engineering.
In Biodegradable Polymers: New Biomaterial Advancements and Challenges; Chu, C.C., Ed.; Nova Science:
Hauppauge, NY, USA, 2015; Volume 2, pp. 199–231.
121. Martin, D.P.; Williams, S.F. Medical applications of poly-4-hydroxybutyrate: A strong flexible absorbable
biomaterial. Biochem. Eng. J. 2003, 16, 97–105. [CrossRef]
122. Subramanian, M.N. Plastics Additives and Testing; Scrivener Publishing: Salem, MA, USA, 2013.
123. Stloukal, P.; Jandikova, G.; Koutný, M.; Sedlarik, V. Carbodiimide additive to control hydrolytic stability and
biodegradability of PLA. Polym. Test. 2016, 54, 19–28. [CrossRef]
124. Wypych, G. Handbook of Nucleating Agents; ChemTec Publishing: Toronto, ON, Canada, 2016.
125. Rizvi, S.Q.A. Dispersants. Chemistry and Applications. In Lubricant Additives; Rudnick, L.R., Ed.; CRC Press:
Boca Raton, FL, USA, 2017; pp. 45–65.
126. Gooneie, A.; Simonetti, P.; Salmeia, K.A.; Gaan, S.; Hufenus, R.; Heuberger, M.P. Enhanced PET processing with
organophosphorus additive: Flame retardant products with added-value for recycling. Polym. Degrad. Stab.
2019, 160, 218–228. [CrossRef]
127. Migler, K.B. Sharkskin Instability in Extrusion. In Polymer Processing Instabilities; Hatzikiriakos, S.G.,
Migler, K.B., Eds.; Marcel Dekker: New York, NY, USA, 2005; pp. 121–159.
128. Georgiou, G. Stick-Slip Instability. In Polymer Processing Instabilities; Hatzikiriakos, S.G., Migler, K.B., Eds.;
Marcel Dekker: New York, NY, USA, 2005; pp. 161–206.
129. Tolinski, M. Additives for Polyolefins, 2nd ed; William Andrew Publishing: Oxford, UK, 2015.
130. Salmeia, K.A.; Gaan, S.; Malucelli, G. Recent Advances for Flame Retardancy of Textiles Based on Phosphorus
Chemistry. Polymers 2016, 8, 319. [CrossRef]
131. Lewin, M.; Weil, E.D. Mechanisms and modes of action in flame retardancy of polymers. In Fire Retardant
Materials; Horrocks, A.R., Price, D., Eds.; Woodhead Publishing: Cambridge, UK, 2001; pp. 31–68.
Materials 2020, 13, 4298 29 of 32

132. Marcilla, A.; Beltrán, M. Mechanisms of Plasticizers Action. In Handbook of Plasticizers; Wypych, G., Ed.;
ChemTec Publishing: Toronto, ON, Canada, 2017; pp. 119–134.
133. Gooneie, A.; Hufenus, R. Hybrid Carbon Nanoparticles in Polymer Matrix for Efficient Connected Networks:
Self-Assembly and Continuous Pathways. Macromolecules 2018, 51, 3547–3562. [CrossRef]
134. Kotal, M.; Bhowmick, A.K. Polymer nanocomposites from modified clays: Recent advances and challenges.
Prog. Polym. Sci. 2015, 51, 127–187. [CrossRef]
135. Fu, K.; Padbury, R.; Toprakci, O.; Dirican, M.; Zhang, X. 13—Conductive textiles. In Engineering of
High-Performance Textiles; Miao, M., Xin, J.H., Eds.; Woodhead Publishing: Cambridge, UK, 2018; pp. 305–334.
136. Stoppa, M.; Chiolerio, A. Wearable Electronics and Smart Textiles: A Critical Review. Sensors 2014, 14,
11957–11992. [CrossRef] [PubMed]
137. Meng, F.; Lu, W.; Li, Q.; Byun, J.-H.; Oh, Y.; Chou, T.-W. Graphene-Based Fibers: A Review. Adv. Mater. 2015,
27, 5113–5131. [CrossRef]
138. Deng, Y.; Si, Y.; Sun, G. Fibrous Materials for Antimicrobial Applications. In Handbook of Fibrous Materials;
Hu, J., Kumar, B., Lu, J., Eds.; Wiley-VCH: Weinheim, Germany, 2020; Volume 2, pp. 927–951.
139. Toray. Available online: https://www.sportstextiles.toray/exhibition/21fw/images/leaflet/leaflet_bodyshell.
pdf (accessed on 31 July 2020).
140. Rauwendaal, C. Understanding Extrusion, 3rd ed.; Hanser: Munich, Germany, 2018.
141. Barmag, O. Available online: https://www.oerlikon.com/manmade-fibers/en/solutions-technologies/gear-
metering-pumps/manmade-fiber-applications/ (accessed on 31 July 2020).
142. Yang, H.H. Polyamide Fibers. In Handbook of Fiber Chemistry; Lewin, M., Ed.; CRC Press: Boca Raton, FL,
USA, 2007; pp. 31–137.
143. Tadmor, Z.; Gogos, C.G. Principles of Polymer Processing, 2nd ed.; John Wiley & Sons: Hoboken, NJ, USA, 2006.
144. Hagewood, J. Technologies for the manufacture of synthetic polymer fibers. In Advances in Filament Yarn
Spinning of Textiles and Polymers; Zhang, D., Ed.; Woodhead Publishing: Cambridge, UK, 2014; pp. 48–71.
145. Zhu, M.-F.; Yang, H.H. Polypropylene Fibers. In Handbook of Fiber Chemistry; Lewin, M., Ed.; CRC Press:
Boca Raton, FL, USA, 2007; pp. 139–260.
146. Gupta, V.B.; Bhuvanesh, Y.C. Basic principles of flow during fibre spinning. In Manufactured Fibre Technology;
Gupta, V.B., Kothari, V.K., Eds.; Chapman & Hall: London, UK, 1997; pp. 31–66.
147. Kikutani, T.; Radhakrishnan, J.; Sato, M.; Okui, N.; Takaku, A. High-speed Melt Spinning of PET.
Int. Polym. Process. 1996, 11, 42–49. [CrossRef]
148. Miyata, K.; Ito, H.; Kikutani, T.; Okui, N. Effect of Liquid Isothermal Bath in High-Speed Melt Spinning of
Poly(ethylene 2,6-naphthalene dicarboxylate). Sen’i Gakkaishi 1998, 54, 661–671. [CrossRef]
149. Avci, H.; Kotek, R.; Toliver, B. Controlling of threadline dynamics via a novel method to develop ultra-high
performance polypropylene filaments. Polym. Eng. Sci. 2015, 55, 327–339. [CrossRef]
150. Najafi, M.; Avci, H.; Kotek, R. High-performance filaments by melt spinning low viscosity nylon 6 using
horizontal isothermal bath process. Polym. Eng. Sci. 2015, 55, 2457–2464. [CrossRef]
151. Peacock, A.J.; Calhoun, A. Polymer Chemistry: Properties and Applications; Carl Hanser Verlag: Munich,
Germany, 2006.
152. Tomka, J.G. Textile Fibres. In Comprehensive Polymer Science and Supplements; Allan, G., Ed.; Pergamon Press:
London, UK, 1989; Volume 2, pp. 487–510.
153. Spruiell, J.E. Structure Formation During Melt Spinning. In Structure Formation in Polymeric Fibers; Salem, D.R.,
Ed.; Carl Hanser Verlag: Munich, Germany, 2001; pp. 5–93.
154. Bessey, W.; Jaffe, M. Solid State Processing of Fibers. In Solid Phase Processing of Polymers; Ward, I.M.,
Coates, P.D., Dumoulin, M.M., Eds.; Hanser: Munich, Germany, 2000; pp. 85–119.
155. Gupta, V.B. Melt-spinning processes. In Manufactured Fibre Technology; Gupta, V.B., Kothari, V.K., Eds.;
Chapman & Hall: London, UK, 1997; pp. 67–97.
156. Jung, H.W.; Hyun, J.C. Fiber spinning and film blowing instabilities. In Polymer Processing Instabilities:
Control and Understanding; Hatzikiriakos, S.G., Migler, K.B., Eds.; Marcel Dekker Series: New York, NY, USA,
2004; Volume 102, pp. 321–382.
157. Larson, R.G. Instabilities in viscoelastic flows. Rheol. Acta 1992, 31, 213–263. [CrossRef]
158. Kikutani, T. Fiber Formation Technology for Polymers Accomplished Technology and Future Direction of
Synthetic Fibers. Sen’i Gakkaishi 1998, 54, P37–P42. [CrossRef]
Materials 2020, 13, 4298 30 of 32

159. Radhakrishnan, J.; Gupta, V.B. Characterization of the network in nonbirefringent flow-drawn poly(ethylene
terephthalate) films. J. Macromol. Sci. Part B 1993, 32, 243–259. [CrossRef]
160. Chatterjee, A. Continuous Filament and Texturised Synthetic Yarns. In Textile and Clothing Design Technology;
Cassidy, T., Goswami, P., Eds.; CRC Press: Boca Raton, FL, USA, 2017; pp. 57–86.
161. Eichhorn, S.J.; Hearle, J.W.S.; Jaffe, M.; Kikutani, T. Handbook of Textile fibre Structure: Fundamentals and
Manufactured Polymer Fibres; Woodhead Publishing: Cambridge, UK, 2009.
162. Masuda, M.; Takarada, W.; Kikutani, T. Effect of the Control of Polymer Flow in the Vicinity of Spinning
Nozzle on Mechanical Properties of Poly(ethylene terephthalate) Fibers. Int. Polym. Process. 2010, 25,
159–169. [CrossRef]
163. Salem, D.R. Structure Formation During Drawing of Flexible Chain Polymers. In Structure Formation in
Polymeric Fibers; Salem, D.R., Ed.; Carl Hanser Verlag: Munich, Germany, 2001; pp. 118–184.
164. Kikutani, T. Structure development in synthetic fiber production. In Handbook of Textile Fibre Structure;
Eichhorn, S.J., Hearle, J.W.S., Jaffe, M., Kikutani, T., Eds.; Woodhead Publishing: Cambridge, UK, 2009;
Volume 1, pp. 157–180.
165. Sumesh, P.; Mathur, T.; Agarwal, U.S. Simulation of polyester melt spinning with axial quench for increasing
productivity. J. Appl. Polym. Sci. 2010, 116, 2541–2547. [CrossRef]
166. Bobeth, W. Textile Faserstoffe: Beschaffenheit und Eigenschaften; Springer: Berlin/Heidelberg, Germany, 1993.
167. Loy, W. Chemiefasern für technische Textilprodukte: Standardtypen, Modifikationen, Einsatzgebiete; Deutscher Fachverlag:
Frankfurt, Germany, 2008.
168. Ziabicki, A.; Kawai, H. High-Speed Fiber Spinning: Science and Engineering Aspects; Krieger Publishing: Malabar,
FL, USA, 1991.
169. Nakajima, T. Advanced Fiber Spinning Technology; Woodhead Publishing: Cambridge, UK, 1994.
170. Hatzikiriakos, S.G.; Migler, K.B. Overview of Processing Instabilities. In Polymer Processing Instabilities;
Hatzikiriakos, S.G., Migler, K.B., Eds.; Marcel Dekker: New York, NY, USA, 2005; pp. 1–12.
171. Denn, M.M. Fifty years of non-Newtonian fluid dynamics. AIChE J. 2004, 50, 2335–2345. [CrossRef]
172. Baird, D.G.; Collias, D.I. Polymer Processing: Principles and Design, 2nd ed.; John Wiley & Sons: Hoboken, NJ,
USA, 2014.
173. Denn, M.M. Polymer Melt Processing: Foundations in Fluid Mechanics and Heat Transfer; Cambridge University
Press: Cambridge, UK, 2008.
174. Dealy, J.M.; Kim, S. Gross Melt Fracture in Extrusion. In Polymer Processing Instabilities; Hatzikiriakos, S.G.,
Migler, K.B., Eds.; Marcel Dekker: New York, NY, USA, 2005; pp. 207–236.
175. Lenk, R.S. A unified concept of melt flow instability during extrusion. J. Appl. Polym. Sci. 1978, 22, 1781–1785.
[CrossRef]
176. Ziabicki, A. Effects of Molecular Weight on Melt Spinning and Mechanical Properties of High-Performance
Poly(ethylene Terephthalate) Fibers. Text. Res. J. 1996, 66, 705–712. [CrossRef]
177. Denn, M.M. Extrusion instabilities and wall slip. Annu. Rev. Fluid Mech. 2001, 33, 265–287. [CrossRef]
178. Migler, K.B.; Son, Y.; Qiao, F.; Flynn, K. Extensional deformation, cohesive failure, and boundary conditions
during sharkskin melt fracture. J. Rheol. 2002, 46, 383–400. [CrossRef]
179. Yoo, H.J. Draw resonance in polypropylene melt spinning. Polym. Eng. Sci. 1987, 27, 192–201. [CrossRef]
180. Leal, A.A.; Neururer, O.A.; Bian, A.; Gooneie, A.; Rupper, P.; Masania, K.; Dransfeld, C.; Hufenus, R.
Interfacial interactions in bicomponent polymer fibers. Polymer 2018, 142, 375–386. [CrossRef]
181. Tippetts, E. Fiber Engineering to Meet End Use Requirements1. Text. Res. J. 1967, 37, 524–533. [CrossRef]
182. The Society of Fiber Science and Technology. High-Performance and Specialty Fibers: Concepts, Technology and
Modern Applications of Man-Made Fibers for the Future; Springer: Tokyo, Japan, 2016.
183. Hufenus, R.; Affolter, C.; Camenzind, M.; Reifler, F.A. Design and Characterization of a Bicomponent
Melt-Spun Fiber Optimized for Artificial Turf Applications. Macromol. Mater. Eng. 2013, 298, 653–663.
[CrossRef]
184. Kikutani, T.; Arikawa, S.; Takaku, A.; Okui, N. Fiber structure formation in high-speed melt spinning of
sheath-core type bicomponent fibers. Sen’I Gakkaishi 1995, 51, 408–415. [CrossRef]
185. Houis, S.; Schreiber, F.; Gries, T. Fiber Table: Bicomponent fibers (Part 1). Chem. Fibers Int. 2008, 58, 38–45.
186. Houis, S.; Schreiber, F.; Gries, T. Fiber Table: Bicomponent fibers (Part 2). Chem. Fibers Int. 2008, 58, 158–165.
187. Jeffries, R. Bicomponent Fibres; Merrow Publishing: Watford, UK, 1971.
Materials 2020, 13, 4298 31 of 32

188. Oh, T.H. Melt spinning and drawing process of PET side-by-side bicomponent fibers. J. Appl. Polym. Sci.
2006, 101, 1362–1367.
189. Prahsarn, C.; Klinsukhon, W.; Roungpaisan, N.; Srisawat, N. Self-crimped bicomponent fibers containing
polypropylene/ethylene octene copolymer. Mater. Lett. 2013, 91, 232–234. [CrossRef]
190. Robeson, L.M.; Axelrod, R.J.; Vratsanos, M.S.; Kittek, M.R. Microfiber formation: Immiscible polymer blends
involving thermoplastic poly(vinyl alcohol) as an extractable matrix. J. Appl. Polym. Sci. 1994, 52, 1837–1846.
[CrossRef]
191. Prahsarn, C.; Matsubara, A.; Motomura, S.; Kikutani, T. Development of Bicomponent Spunbond Nonwoven
Webs Consisting of Ultra-fine Splitted Fibers. Int. Polym. Process. 2008, 23, 178–182. [CrossRef]
192. Mitsoulis, E. Secondary Flow Instabilities. In Polymer Processing Instabilities; Hatzikiriakos, S.G., Migler, K.B., Eds.;
Marcel Dekker: New York, NY, USA, 2005; pp. 43–71.
193. Techtextil Messe Frankfurt. Available online: https://techtextil.messefrankfurt.com/frankfurt/de/profil.html
(accessed on 31 July 2020).
194. Zhang, D. Available online: https://www.nonwovens-industry.com/issues/2008-03/view_features/the-
evolving-roles-of-nonwovens-in-technical-/ (accessed on 31 July 2020).
195. Dauner, M.; Funk, A.; Rieger, C.; Hoss, M.; Planck, H. Entwicklung von Textilien aus schmelzgesponnenen 1 µm
Super Mikrofilamenten; 22. Stuttgarter Kunststoff-Kolloquium: Stuttgart, Germany, 2011.
196. Rieger, C.; Funk, A.; Hoss, M.; Dauner, M.; Plank, H. Special fiber structures through bicomponent technology.
Chem. Fibers Int. 2010, 3, 162–163.
197. Ranadajen, S.; Anand, S.C.; Rigby, A.J. Textiles for healthcare and medical applications. In Handbook of
Technical Textiles, 2nd ed.; Woodhead Publishing: Cambridge, UK, 2016; pp. 135–168.
198. Gajjar, C.R.; King, M.W. Resorbable Fiber-Forming Polymers for Biotextile Applications; Springer: New York, NY,
USA, 2014.
199. Banerjee, A.; Chatterjee, K.; Madras, G. Enzymatic degradation of polymers: A brief review. Mater. Sci. Technol.
2014, 30, 567–573. [CrossRef]
200. Azevedo, H.S.; Reis, R.L. Understanding the Enzymatic Degradation of Biodegradable Polymers and
Strategies to Control Their Degradation Rate. In Biodegradable Systems in Tissue Engineering and Regenerative
Medicine; Reis, R.L., Román, J.S., Eds.; CRC Press: Boca Raton, FL, USA, 2005; pp. 177–201.
201. Song, R.; Murphy, M.; Li, C.; Ting, K.; Soo, C.; Zheng, Z. Current development of biodegradable polymeric
materials for biomedical applications. Drug Des. Dev. Ther. 2018, 12, 3117–3145. [CrossRef] [PubMed]
202. Nayak, R.; Padhye, R. Antimicrobial finishes for textiles. In Functional Finishes for Textiles; Paul, R., Ed.;
Woodhead Publishing: Cambridge, UK, 2015; pp. 361–385.
203. Bonaldi, R.R. Functional finishes for high-performance apparel. In High-Performance Apparel; McLoughlin, J.,
Sabir, T., Eds.; Woodhead Publishing: Cambridge, UK, 2018; pp. 129–156.
204. Le Ouay, B.; Stellacci, F. Antibacterial activity of silver nanoparticles: A surface science insight. Nano Today
2015, 10, 339–354. [CrossRef]
205. Durán, N.; Durán, M.; De Jesus, M.B.; Seabra, A.B.; Favaro, W.J.; Nakazato, G. Silver nanoparticles: A new
view on mechanistic aspects on antimicrobial activity. Nanomed. Nanotechnol. Biol. Med. 2016, 12, 789–799.
[CrossRef] [PubMed]
206. Chernousova, S.; Epple, M. ChemInform Abstract: Silver as Antibacterial Agent: Ion, Nanoparticle, and Metal.
Angew. Chem. Int. Ed. 2013, 52, 1636–1653. [CrossRef] [PubMed]
207. Parida, D.; Simonetti, P.; Frison, R.; Bülbül, E.; Altenried, S.; Arroyo, Y.; Balogh-Michels, Z.; Caseri, W.;
Ren, Q.; Hufenus, R.; et al. Polymer-assisted in-situ thermal reduction of silver precursors: A solventless
route for silver nanoparticles-polymer composites. Chem. Eng. J. 2020, 389, 123983. [CrossRef]
208. Schindler, W.D.; Hauser, P.J. Chemical Finishing of Textiles; Woodhead Publishing: Cambridge, UK, 2004.
209. Li, Y. Conducting Polymers. In Organic Optoelectronic Materials; Li, Y., Ed.; Springer: Cham, Switzerland,
2015; pp. 23–50.
210. Pham, T.; Bechtold, T. Conductive Fibers. In Handbook of Fibrous Materials; Hu, J., Kumar, B., Lu, J., Eds.;
Wiley-VCH: Weinheim, Germany, 2020; Volume 1, pp. 233–262.
211. Kim, B.; Koncar, V.; Devaux, E.; Dufour, C.; Viallier, P. Electrical and morphological properties of PP and PET
conductive polymer fibers. Synth. Met. 2004, 146, 167–174. [CrossRef]
212. Mirabedini, A.; Foroughi, J.; Wallace, G.G. Developments in conducting polymer fibres: From established
spinning methods toward advanced applications. RSC Adv. 2016, 6, 44687–44716. [CrossRef]
Materials 2020, 13, 4298 32 of 32

213. Hufenus, R.; Gooneie, A.; Sebastian, T.; Simonetti, P.; Geiger, A.; Parida, D.; Bender, K.; Schäch, G.; Clemens, F.
Antistatic Fibers for High-Visibility Workwear: Challenges of Melt-Spinning Industrial Fibers. Materials
2020, 13, 2645. [CrossRef]
214. Argyros, A. Structure, properties and characteristics of optical fibres. In Handbook of Textile Fibre Structure;
Eichhorn, S.J., Hearle, J.W.S., Jaffe, M., Kikutani, T., Eds.; Woodhead Publishing: Cambridge, UK, 2009;
Volume 2, pp. 458–484.
215. Bunge, C.A.; Beckers, M.; Lustermann, B. Basic principles of optical fibres. In Polymer Optical Fibres;
Bunge, C.-A., Gries, T., Beckers, M., Eds.; Woodhead Publishing: Cambridge, UK, 2017; pp. 47–118.
216. Kremenáková, D.; Militky, J.; Mishra, R. Fibers for Optical Textiles. In Handbook of Fibrous Materials; Hu, J.,
Kumar, B., Lu, J., Eds.; Wiley-VCH: Weinheim, Germany, 2020; Volume 2, pp. 593–648.
217. Beckers, M.; Schlüter, T.; Vad, T.; Gries, T.; Bunge, C.A. An overview on fabrication methods for polymer
optical fibers. Polym. Int. 2015, 64, 25–36. [CrossRef]
218. Ziemann, O.; Krauser, J.; Zamzow, P.E.; Daum, W. POF Handbook: Optical Short Range Transmission Systems,
2nd ed.; Springer: Berlin/Heidelberg, Germany, 2008.
219. Sohn, I.-S.; Park, C.-W. Diffusion-Assisted Coextrusion Process for the Fabrication of Graded-Index Plastic
Optical Fibers. Ind. Eng. Chem. Res. 2001, 40, 3740–3748. [CrossRef]
220. Jakubowski, K.; Huang, C.-S.; Gooneie, A.; Boesel, L.F.; Heuberger, M.; Hufenus, R. Luminescent solar
concentrators based on melt-spun polymer optical fibers. Mater. Des. 2020, 189, 108518. [CrossRef]
221. Ishizawa, H. Optical Fibers. In Handbook of Fibrous Materials; Hu, J., Kumar, B., Lu, J., Eds.; Wiley-VCH:
Weinheim, Germany, 2020; Volume 1, pp. 391–410.
222. Sonnenschein, M.F. Hollow fiber microfiltration membranes from poly (ether ether ketone) (PEEK). J. Appl.
Polym. Sci. 1999, 72, 175–181. [CrossRef]
223. Demeuse, M.T. Production and applications of hollow fibers. In Handbook of Textile Fibre Structure;
Eichhorn, S.J., Hearle, J.W.S., Jaffe, M., Kikutani, T., Eds.; Woodhead Publishing: Cambridge, UK,
2009; Volume 2, pp. 485–499. Available online: https://www.sciencedirect.com/science/article/pii/
B9781845697303500159 (accessed on 25 September 2020).
224. Oh, T.H.; Lee, M.S.; Kim, S.Y.; Shim, H.J. Studies on melt-spinning process of hollow fibers. J. Appl. Polym. Sci.
1998, 68, 1209–1217. [CrossRef]
225. Takarada, W.; Ito, H.; Kikutani, T.; Okui, N. Studies on high-speed melt spinning of noncircular cross-section
fibers. I. Structural analysis of As-spun fibers. J. Appl. Polym. Sci. 2001, 80, 1575–1581. [CrossRef]
226. Rwei, S.P. Formation of hollow fibers in the melt-spinning process. J. Appl. Polym. Sci. 2001, 82, 2896–2902.
[CrossRef]
227. Huang, Q.; Seibig, B.; Paul, D. Polycarbonate hollow fiber membranes by melt extrusion. J. Membr. Sci. 1999,
161, 287–291. [CrossRef]
228. De Rovère, A.; Shambaugh, R.L. Melt-spun hollow fibers: Modeling and experiments. Polym. Eng. Sci. 2001,
41, 1206–1219. [CrossRef]
229. Hufenus, R.; Gottardo, L.; Leal, A.A.; Zemp, A.; Heutschi, K.; Schuetz, P.; Meyer, V.R.; Heuberger, M.
Melt-spun polymer fibers with liquid core exhibit enhanced mechanical damping. Mater. Des. 2016, 110,
685–692. [CrossRef]
230. Leal, A.A.; Naeimirad, M.; Gottardo, L.; Schuetz, P.; Zadhoush, A.; Hufenus, R. Microfluidic behavior in
melt-spun hollow and liquid core fibers. Int. J. Polym. Mater. 2016, 65, 451–456. [CrossRef]
231. Hufenus, R.; Heuberger, M.; Leal, A.A. Multifunctional liquid-core melt-spun filaments. Chem. Fibers Int.
2018, 68, 181–182.

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