Polylacticacidfiber Anoverview

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Poly(lactic acid) fiber: An overview
Article in Progress in Polymer Science · April 2007

DOI: 10.1016/j.progpolymsci.2007.01.005
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Prog. Polym. Sci. 32 (2007) 455–482

www.elsevier.com/locate/ppolysci
Poly(lactic acid) fiber: An overview

Bhuvanesh Guptaa,, Nilesh Revagadea, Jöns Hilbornb
a
Department of Textile Technology, Indian Institute of Technology, New Delhi-110016, India
b
Polymer Chemistry Programme, Ångström Laboratory, University of Uppsala, S-75121 Uppsala, Sweden
Received 9 July 2005; received in revised form 15 January 2007; accepted 15 January 2007
Available online 30 January 2007
Abstract
Poly(lactic acid) (PLA) has generated great interest as one of the most innovative materials being developed for a wide
range of applications. The polymer is thermoplastic and biodegradable, which makes it highly attractive for biological and
medical applications. It can be transformed by spinning into filaments for subsequent fabrication of desirable textile
structures. Spinning may be accomplished by various routes, each with its merits and demerits. The medical applications of
this polymer arise from its biocompatibility: the degradation product, lactic acid, is metabolically innocuous. The fibers
may be fabricated into various forms and may be used for implants and other surgical applications such as sutures. Tissue
engineering is the most recent domain where poly(lactic acid) is being used and is found to be one of the most favorable
matrix materials. The present article presents a critical review on the production of poly(lactic acid) fiber by various
methods, along with correlations between structure and properties of the fibers. The applications of these fibers in various
domains are also discussed.
r 2007 Elsevier Ltd. All rights reserved.
Keywords: Poly(lactic acid); Fiber; Spinning; Applications
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
2. Chemistry of lactic acid and poly(lactic acid) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
3. Spinning of poly(lactic acid) fiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
3.1. Melt spinning of poly(lactic acid) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
3.1.1. Thermal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
3.1.2. Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
3.1.3. Birefringence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
3.1.4. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
3.2. Dry spinning of poly(lactic acid) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
3.2.1. Thermal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
3.2.2. Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469
3.2.3. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
Corresponding author.
E-mail address: [email protected] (B. Gupta).
0079-6700/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2007.01.005
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456 B. Gupta et al. / Prog. Polym. Sci. 32 (2007) 455–482
3.3. Wet spinning of PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472

3.4. Dry-jet-wet spinning of poly(lactic acid) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
3.5. Electrospinning of poly(lactic acid) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
4. Applications of poly(lactic acid) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
4.1. Commodity applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
4.2. Medical applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
4.2.1. Sutures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
4.2.2. Pharmaceutical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
4.2.3. Implants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
4.2.4. Tissue engineering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
1. Introduction surface chemistry are all crucial in medical applica-

tions, successful efforts are being made to tailor
Recent advances in biodegradable polymers have PLA with specific architectural characteristics [2,8].
been spurred by intense interest in biomedical It is the L-lactic acid which provides polymer with
applications [1,2]. Biodegradable polymers break high mechanical strength and thus has an edge over
down in physiological environments by macromo- the DL-form. Moreover, the degradation products of
lecular chain scission into smaller fragments, and polylactides are nontoxic which enhances practical
ultimately into simple stable end-products [3]. The applications in biomedicine [1,9]. PLA is currently
degradation may be due to aerobic or anaerobic being commercialized for a wide spectrum of
microorganisms, or biologically active processes applications. The polymer was first obtained by
(e.g. enzyme reactions) or passive hydrolytic clea- Carothers in 1932 as a low molecular weight
vage [4,5,7]. The last two decades of polymer product by heating lactic acid in vacuum [10].
technology have seen a sharp rise in the develop- Although the initial work did not produce a high
ment and commercial marketing of such new molecular weight polymer, DuPont was awarded a
materials [6]. Cargill Inc. has been the company patent for a process to produce high molecular
most active in the development of poly(lactic acid) weight materials [11]. The commercialization of the
(polylactide, PLA). After 9 years of lactic acid and polymer for the bioabsorbable high strength suture
poly(lactic acid) development, Cargill Dow poly- VICRYL was taken up by Ethicon in 1972. This
mers LLC was created in 1997 as a joint venture of suture is a copolymer of glycolic acid and lactic acid
Cargill and the Dow Chemical company. Commer- in 90:10 ratio and undergoes relatively fast hydro-
cial production of PLA by the new company started lytic cleavage of the backbone ester linkage under
in 2002. The polymer products are finding an alkaline or acidic conditions [12,13]. The hydrolysis
enormous number of applications in technologically
important fields. Table 1
The use of synthetic degradable polyesters in Natural and synthetic biodegradable polymers [4,7]
surgery as suture materials and bone fixation
devices has three decades of history [6]. Degradable Polymer Chemical nature Base
polyesters derived from three monomers, lactide, Polysaccharides Ether linkage Natural
glycolide and caprolactone, are commonly used Proteins Amide linkage Natural
clinically. They are characterized by degradation Nucleic acids Nucleotides Natural
times ranging from days to years, depending on Polyesters O C CH2 Synthetic
formulation and initial molecular weight. Table 1 O
illustrates various natural and synthetic biodegrad- Polyanhydrides Synthetic
O
able polymers [4,5,7]. Polylactide (PLA) is one of
the most promising biodegradable polymers owing C R C O
to its mechanical property profile, thermoplastic n
processibility and biological properties, such as Poly(ureas) Synthetic

RNCONR
biocompatibility and biodegradability. In spite of
n
the fact that the surface morphology, porosity and
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B. Gupta et al. / Prog. Polym. Sci. 32 (2007) 455–482 457
is accelerated by in-situ formation of carboxyl end

groups. This polymer in combination with other
comonomers, such as caprolactone or glycolic acid,
has produced interesting materials that could
provide requisite behavior and performance as
biomaterials. In most of the biodegradable compo-
sites, PLA is one of the important moieties. Recent
studies are primarily directed to the development of
materials by blending with other biodegradable Fig. 1. Optical isomers of lactic acid [14,15].
polymers, such as chitosan, polycaprolactone and
polyethylene oxide. The idea is to have a matrix
with degradation behavior, biological performance
Petrochemical feedstock Ethylene
and morphology appropriate for specific applica-
tions, such as prosthetic devices, implants, vascular
Oxidation
grafts, catheters, sutures and ligament repair mate-
rials. Tissue engineering is the most recent innova-
tive domain where these biodegradable materials Lactonitrile Acetaldehyde
provide surfaces that promote the regeneration and HCN
reconstruction of human organs. The constant
efforts of cell biologists, materials scientists and
engineers are creating a bright future for this racemic dl-lactic acid (optically inactive)
polymer as a biomaterial.
2. Chemistry of lactic acid and poly(lactic acid)

Amorphous Polylactic acid
The chemistry of PLA involves the processing
and polymerization of lactic acid monomer. Lactic Fig. 2. Petrochemical route to lactic acid [14,15].
acid HOCH3CHCOOH is a simple chiral molecule
which exists as two enantiomers, L- and D-lactic acid
(Fig. 1), differing in their effect on polarized light. biological lactic acid, the lactic acid produced is
The L isomer rotates the plane of polarized light exclusively (499.5%) the L-isomer [14,15], which is
clockwise, the D isomer rotates it counterclockwise. one reason favoring production from renewable
The optically inactive D, L or meso form is an sources rather than petrochemicals [18]. At present,
equimolar (racemic) mixture of D and L isomers Cargill Dow Polymers operates the world’s largest
[14,15]. Lactic acid is produced in mammalian PLA production unit.
muscles during glycogenolysis and is involved in Polymerization of lactic acid to high molecular
the Kreb’s cycle through pyruvic acid and acetyl- weight PLA can be achieved in two ways (Fig. 3):
CoA [16]. Lactic acid is easily prepared in high yield
by fermentation of molasses or potato starch or of (1) Direct condensation—which involves solvents
dextrose from corn [1]. under high vacuum.
Lactic acid is produced commercially by fermen- (2) Formation of the cyclic dimer intermediate
tation, as just mentioned, or via petrochemical (lactide)—which is solvent free.
feedstocks. The petrochemical route to lactic acid is
shown in Fig. 2. The lactic acid produced by this In direct condensation, solvent is used under high
route is the optically inactive racemic mixture of L vacuum and temperatures for the removal of water
and D enantiomers. The petrochemical scheme of produced in the condensation. This approach was
monomer production was prevalent until about used by Carothers and still used by Mitsui Chemi-
1990 when a more economic fermentation approach cals. The resultant polymer is a low to intermediate
was developed. Today the most popular route is molecular weight material, which can be used as is,
fermentation, in which corn starch is converted into or coupled with isocyantes, epoxides or peroxide to
lactic acid by bacterial fermentation using an produce a range of molecular weights [14,15]. In the
optimized strain of Lactobacillus [17]. Like all solvent-free process, a cyclic intermediate dimer,
ARTICLE IN PRESS
Fig. 3. Synthesis of polylactic acid [14].
commonly referred to as lactide (Fig. 3), is produced bacterial fermentation of glucose obtained from
and purified by distillation. Catalytic ring-opening corn have led to a dramatic reduction in manufac-
polymerization of the lactide intermediate results turing cost of lactic acid [15]. More and more
in PLA with controlled molecular weight [19,20]. companies, e.g. Cargill Dow Polymer LLC, Shi-
By controlling residence time and temperatures madzu Corp, Mitsui Chemicals, Musashino Co. are
in combination with catalyst type and concentra- now producing PLA-targeting markets for packa-
tion, it is possible to control the ratio and sequence ging materials, films, textile fibers, along with
of D- and L-lactic acid units in the final polymer pharmaceutical products [2,15,18].
[14–16]. PLA has several advantages: it is biocompatible
Since, lactic acid is a chiral molecule, the and biodegradable, and can be readily broken down
stereochemistry of PLA may be tailored to fit thermally by hydrolysis. It is available from renew-
requirements. It is the stereoregularity that makes able agricultural resources. This latter circumstance
poly(L-lactic acid) a highly crystalline polymer [21]. also helps to improve the farm economy. There is
Monomer dyads in the PLA chain may contain reduction in carbondioxide emissions in comparison
identical stereocenters (L:L or D:D) or enantiomeric with conventional petroleum based commodity
stereocenters (L/D). With special catalysts isotactic plastics because it helps by fixation of significant
and syndiotactic content with different enantio- quantities of carbondioxide. The most important
metric units can be controlled. Fully amorphous ability of PLA is that one can tailor its physical
materials can be made by the inclusion of relatively properties by material modifications [17,18,22]. The
high D content (420%) whereas highly crystalline polymer is relatively hard, with the glass transition
material is obtained when the D content is low temperature in the range 60–70 1C and melting at
(o2%) [15,18,22,23]. Recent advances in the 170–180 1C. Some of physical characteristic of PLA
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Table 2
Properties of PLLA [24]
Property Units Condition Value
Degree of crystallinity Xc % L-PLA 0–37

Density r g/cm3 Amorphous 1.248
Single crystal 1.290
Heat of fusion DHf KJ/mol L-PLA complete crystalline 146
L-PLA fiber
As-extruded 2.5
After hot drawing 6.4
Heat capacity Cp J/K/g L-PLA with
Mv ¼ 5300 0.60
Mv ¼ (0.2–6.91) 105 0.54
Glass transition temperature K 326–337
Melting point K 418–459
Decomposition temperature K 500–528
Swelling in water % pH 7 buffer 2
Intrinsic viscosity (Z) in chloroform at 25 1C dl/g 3.8–8.2
Radiation resistance G value Under nitrogen
Co60 in benzene solution, 30 1C Chain scission 26.5
Cross linking 4.5
In water Chain scission
Cross linking 23.0
6.5
IR peaks cm1
OH (alcohol/carboxylic) 3700–3450
–C ¼ O 1750–1735
–COO 1600–1580
C-O 1200–1000
CH 950–700
are listed in Table 2. In this review, our focus is on removed by thermal evaporation while in wet
production of textile fibers and their applications. spinning the coagulation of the polymer is carried
out in another fluid that is compatible with the
3. Spinning of poly(lactic acid) fiber spinning solvent but is not itself a solvent for the
polymer [25]. Comprehensive data on PLA fiber
The transformation of PLA into textile structures spinning are presented in Table 3.
is complicated and depends on structural changes in
the polymer during processing. Extrusion of the 3.1. Melt spinning of poly(lactic acid)
polymer into monofilament and multifilament may
be achieved by melt spinning, dry spinning, wet Melt spinning of PLA was one of the first
spinning, and by dry-jet-wet spinning. There are methods used to produce fibers. Various research
distinct features of each of these processes that are groups have studied the melt spinning of PLA fibers
subsequently reflected in fiber properties. Owing to under various processing conditions. For instance,
the thermoplastic nature of PLA, it is possible to Eling et al. [1] reported melt spinning of poly
melt the polymer under reasonable conditions. Its (L-lactic acid) (PLLA) with molecular weight below
conversion to fiber by melt spinning usually has 3 105. The polymer was extruded at 185 1C
advantages over wet spinning; i.e. it is a solvent-free through a capillary with a diameter of 1 mm and
process and provides a more economical and length of 10 mm. The take-up speed for the melt
ecofriendly route. Production speeds are normally spun fibers was 25–35 cm/min. Hot drawing of the
higher than in solution spinning. Sometimes, how- fibers was then carried out in an electric tube
ever, melt spinning is not possible, either because furnace 500 mm in length with input speed 20 mm/
the polymer degrades while melting or the melt is min. The investigations of Cicero et al. [22,23]
thermally unstable. In dry spinning, solvents are illustrate two-step melt spinning of PLA fibers.
ARTICLE IN PRESS
Table 3
Comprehensive data on PLA fiber spinning
Year Workers Type of spinning Process highlight
1966 Kulkarni et al. [96] Wet spinning Not available

1972 Schneider [37] Melt spinning Fiber with 0.69 GPa tensile strength reported
1982 Eling et al. [1] Melt spinning/dry spinning Dry spun fibers show better properties compare to melt
spinning
1984 Hyon et al. [30] Melt spinning Tensile strength up to 0.7 GPa
1984 Leenslag et al. [41] Dry spinning Addition of camphor and polyurethanes to spinning
dope
1987 Leenslag et al. [33] Dry spinning Two-stage process to produce fiber with tenacity
2.1 GPa
1987 Eenink et al. [47] Dry-wet phase inversion Hollow PLA fibers prepared without post- spinning
spinning process process and used for drug delivery system
1988 Gogolewski et al. [42] Dry spinning Tensile strength up to 1.2 GPa
1989 Postema et al. [39] Dry spinning Drawing carried out at low deformation rates in the
liquid state of polymer
1990 Postema et al. [37] Dry spinning Morphology of fiber altered by varying applied
ambient temperature
1990 Postema et al. [38] Dry spinning Influence of extrusion speed and winding speed on fiber
properties reported
1992 Dauner et al. [97] Melt spinning Tensile strength up to 0.4 GPa
1993 Penning et al. [9] Melt spinning/Dry Absorbable fibers developed from L-lactide copolymers
spinning
1993 Witte et al. [48] Dry-wet phase- inversion Hollow PLA fibers prepared without post- spinning
spinning process process and used for drug delivery system
1994 Horacek et al. [34] Dry spinning Continuous two-stage process
1994 Horacek et al. [35] Dry spinning Discontinuous two-stage process
1994 Horacek et al. [36] Dry spinning Precipitant vapors used for spinning
1994 Tsuji et al. [46] Wet spinning/Dry spinning Ethanol used as nonsolvent in coagulation bath.
Tensile strength of wet-spun fibers very low.
Stereocomplex formation between enantiomeric
poly(lactic acid)s
1997 Fambri et al. [16] Melt spinning Two stage process i.e. spinning and hot drawing
1998 Mezghani et al. [28] Melt spinning Maximum take up speed achieved – 5000 m/min
1999 Schmack et al. [2] Melt spinning High speed spinning and spin drawing
2001 Cicero [23] Melt spinning Continuous two-step melt melt spinning process
2001 Yuan et al. [26] Melt spinning Two-step process (melt extrusion and hot draw)
2002 Cicero et al. [31] Melt spinning Two-step melt spinning process
2002 Kenawy et al. [53] Electrospinning Fibers electrospun from chloroform solutions
containing a small amount of methanol to solubilize
drug
2003 Nelson et al. [98] Wet spinning One stage process without post-spinning operations
2003 Gupta et al. [49,50] Dry-jet-wet spinning PLA fiber with tensile strength 0.6 GPa developed by
two-stage process
2004 Schmack et al. [27] Melt spinning High speed melt spinning of various grades of
polylactides
2005 You et al. [99] Electrospinning Fabrication of nanofiber matrices. Optimum solution
concentration for fiber formation 5 wt%
Textile grade PLA with a 98:02 ratio of L:D Fambri et al. [16] reported melt spinning of PLLA
stereochemical centers (with Mn ¼ 47600 and with viscosity average molecular weight Mv 33,000.
Mw ¼ 98500) was dried at 82 1C to reduce the water Prior to extrusion, the polymer was dried at 50 1C
level to 100 ppm or below. The molten, pressurized under vacuum for 48 h. Monofilament 1 mm in
polymer was extruded through a spinneret and diameter was spun from a single-screw extruder
quenched in a water bath. The melt draw-ratio was under an inert atmosphere at take-up speeds
kept constant at 40. The take-up speed was varied ranging from 1.8 to 20 m/min. The as-spun fibers
from 7.5 to 60 ft/min. were drawn at 160 1C using a hot plate drawing
ARTICLE IN PRESS
Table 4
Decrease of the viscosity average molecular weights of PLLA during fiber preparation [26]
Raw materials Powder materials As-spun fibers Hot-drawn fibers
Mv3 M3
v Decrease (%) M3
v Decrease (%) M3
v Decrease (%) Die temperature (1C)
495 398 19.5 216 45.7 197 9.1 220

147 63.2 138 5.9 230
124 69.0 113 8.6 240
305 265 13.1 161 39.0 166 3.0 210
157,300 40.6 143,800 8.6 220
112,200 57.6 118,600 5.7 230
263 221 15.8 108 50.5 110 0.7 210
107 51.8 107 0.3 220
106 52.2 113 6.6 230
apparatus. Yuan et al. [26] prepared PLLA fibers by and hot drawing (ca. 9.1%). The degradation of
a two-step melt spinning process. Dried PLLA was PLA is due to hydrolytic cleavage of the ester
pulverized and melt spinning was carried out with a linkage by water molecules and depolymerization
laboratory single-screw extruder. Temperatures processes [27].
ranging from 200 to 240 1C were used in three Pulverization of raw polymer is a mechanical
zones of the extruder, The as-spun fibers were process in which polymer can be degraded by heat
collected at a rate of 3.2 m/min on a sandblasted and shear forces. The higher the crystallinity of the
glass drum and subsequently drawn under nitrogen polymer, the more energy is needed and the greater
at 120 1C in a hot-drawing apparatus at a feed is the degradation. To minimize the decrease in
velocity of 0.26 m/min and a take-up velocity of molecular weight in melt extrusion, dried PLLA has
1.09 m/min. An additional 10 min of heat treatment to be used. It is observed that the higher the original
in nitrogen at 120 1C yielded the final hot-drawn molecular weight of PLLA, the greater is the
fibers. decrease in molecular weight during melt extrusion.
It has been observed that significant changes
occur in the molecular weight of the polymer during 3.1.1. Thermal properties
the spinning and post-spinning operations [23,26]. Thermal characteristics of the PLA are important
Some data on degradation of PLA during spinning criteria in some applications. The thermal properties
were reported for different molecular weights may be determined by differential scanning calori-
processed under various conditions. Degradation metry (DSC), thermogravimetric analysis (TGA)
reactions have been thought to involve thermohy- and dynamic mechanical analysis (DMA). A typical
drolysis, depolymerization, intermolecular and cyc- DSC scan of PLA is presented in Fig. 4. The glass
lic oligomerization, and/or transesterification. transition temperature Tg around 60–70 1C is
Nearly all these degradation processes occur during followed by melting behavior between 150
the extrusion process and are independent of drying and170 1C. Quite often a small exothermic region
conditions [23]. Accordingly, if the degradation is immediately above Tg indicates the effect of
hydrolytic, it must originate from the residual water physical aging, where cold crystallization takes
level of approximately 100 ppm. Under these con- place. Furthermore, two melting peaks separated
ditions a greater loss is expected for higher by a few degrees are sometimes seen as a distinct
molecular weight materials. shoulder on the low temperature side of the melting
The viscosity average molecular weight of PLLA peak. Similar observations were reported by Fambri
dropped sharply during pulverization and melt et al. [16] and Mezghani and Spruiell [28]. Tg and
extrusion but decreased only slightly during hot the melting temperature Tm depend strongly on
drawing. As recorded in Table 4, the degradation molecular weight. Both Tg and Tm increase with
during melt extrusion was about 39.0–69.0%—far molecular weight and reach constant values beyond
more than during pulverization (about 13.1–19.5%) molecular weight 20,000. Jamshidi et al. [29]
ARTICLE IN PRESS
40
Heat Flow Endo Up
30
% Crystallinity
20
BR
10 LN
30 60 90 120 150 180 210

Temperature °C 0
0 1 2 3 4 5 6 7 8 9
Fig. 4. DSC thermogram of a fiber drawn to DR ¼ 6 [22]. Draw ratio
Fig. 5. Crystallinity versus draw ratio for linear and branched

PLA [31].
Table 5
DSC data for PLA fiber [22]
DR Tg (1C) Tm (1C) Crystallinity Cold-draw

Cicero et al. [31] investigated the crystallization
(%) temperature behavior of linear and branched PLA (96:04 L:D
(1C) PLA) Branching was obtained by reactive extrusion
of PLA with a peroxide. The crystallinity as
1 61.7 162.2 0 93
estimated from the DSC thermograms was found
2 61.9 165.1 0 86
3 63.5 164.0 32 82 to increase with DR, reaching a maximum of 35%
4 65.5 161.9 24 77 in both structures. However, the crystallinity
5 67.0 160.6 34 75 reached a plateau at DR ¼ 3 in the branched
6 67.7 161.2 47 73 polymer as compared to DR ¼ 5 for the un-
7 70.2 162.1 49 72
branched sample (Fig. 5). Quiescent crystallization
8 68.7 162.9 51 71
in DSC demonstrates that branched polymer
crystallizes more rapidly than linear polymer. The
greater crystallinity at lower DR for the branched
reported a maximum Tg of 57 1C for high molecular material is the result of intrinsically faster crystal-
weight PLA. It is important to note that Tg is lization kinetics and higher viscosity induced
influenced by the degree of crystallinity in PLA; a stresses for the same DR, thereby facilitating greater
relatively high Tg of 68 1C for highly crystalline PLA stress-induced crystallinity [18].
was reported by Hyon et al. [30]. In another study, Cicero et al. [31] investigated
Melt spinning involves heating the polymer to the the crystalline morphology of PLA by X-ray
required melt viscosity and subsequent extrusion as diffraction and atomic force microscopy. Drawing
monofilament, where the fiber structure is governed causes orientation of molecular chains, and then
by take-up speed, drawing temperature and draw crystallization sets in where the microfibrils are
ratio. Proper values of these variables are required to aligned along the fiber axis during drawing. Cicero
optimize the tensile properties of the fiber. There are et al. proposed a representation of the molecular
considerable changes in Tg, Tm and crystallinity, structure of PLA (Fig. 6) where the alignment of
depending on the draw ratio [22]. As is evident from microfibers along the fiber axis is determined by the
Table 5, the Tg is increased from 61.7 to 68.7 while draw ratio. As the DR increases, the tendency of
crystallinity reaches 51% at a DR of 8. It is clear that microfibrils to align along the fiber axis increases.
lower temperatures and higher DRs increase crystal- The crystalline and amorphous regions form stacks
linity. The Tg determined from DSC tends to be within the microfibrils and the interfibrillar region is
different from the value from DMTA. The difference, populated by amorphous chains.
which can be as much as 20 1C, results from the Fambri et al. [16] performed DSC scans from 0 to
unconstrained fiber in DSC measurements, which can 230 1C with a heating rate of 10 1C/min. During the
relax before Tg is reached. Relaxation is inhibited in first scan, two crystallization peaks were detected,
DMTA, where fibers are slightly strained. whose areas decreased with the fiber collection rate.
ARTICLE IN PRESS
Microfibrils
Skin
Intrafibrillar area
Fiber
Crystallites
Amorphous
(Disordered)
regions
Intrafibrillar area
Microfibrils
Fig. 6. Supramorphological model for two-step, melt-spun PLA [31].
Table 6
DSC analysis of as-spun and hot-drawn PLLA fibers[26]
Samples Die temperature (1C) As-spun fibers Hot drawn fibers
Tg (1C) Tm (1C) Crystallinity (%) Tm (1C) Crystallinity (%) Draw ratio

a
PLLA 220 64.2 176.2 22.9 172.7 61.9 4.71
230 63.0 177.2 18.6 171.0 64.2 4.75
240 63.2 176.8 16.6 169.1 61.8 4.77
PLLAb 210 65.7 176.8 20.4 172.3 63.6 5.50

220 64.4 176.5 19.6 171.0 60.4 4.66
230 61.9 177.7 18.9 168.7 61.7 5.35
PLLAc 210 66.4 177.0 18.0 168.0 50.6 5.18
220 65.9 176.5 17.3 168.2 51.9 5.11
230 64.1 176.5 17.3 169.4 61.0 5.89
a
Mv 103 ¼ 495.
b
Mv 103 ¼ 305.
c
Mv 103 ¼ 263.
Fibers collected at rates 1.8–3 m/min were almost crystallinities of 16.5–22.8% while hot-drawn fibers
amorphous (4.7–6.0% crystallinity), whereas fibers exhibited higher crystallinities of 50.3–63.7%.
collected at 5 and 10 m/min showed crystallinities of Schmack et al. [2] observed that DSC scans of
29.9% and 37.5%, respectively. The difference can high-speed spun filaments show a glass transition
be mainly related to better efficiency of cooling by range between 52 and 54 1C, a cold crystallization
the nitrogen flux at the die exit at lower fiber speeds. and a melting peak (Fig. 7). Fibers spun at 1000 m/
At the same time, Yuan et al. [26] performed DSC min remain noncrystalline during spinning.
scans from 0 to 240 1C as shown in Table 6. The Tg, Crystallization takes place only during the heating
and exothermic crystallization peaks were detected in DSC. With increasing spinning velocity above
in the DSC thermograms of as-spun fibers. How- 2500 m/min, partial crystallization of the fiber takes
ever, only the melting peaks appeared with hot- place already during spinning, whereas the con-
drawn fibers. The as-spun fibers showed low tribution from the cold crystallization in DSC is
ARTICLE IN PRESS
2.0
1.5
Heat Flow [ W/g]

1.0 v = 5000 m/min
v = 4000 m/min
v = 3000 m/min
0.5 v = 2000 m/min
v = 1000 m/min
0.0
60 80 100 120 140 160 180

Temperature (°C)
Fig. 7. DSC scans of high-speed spun fibers [2].
2.0 creases. The ‘‘D’’ content in the fiber has the

dominant influence on crystallization and mechan-
1.5 ical properties. A maximum tensile strength of
Heat Flow (W/g)
300 MPa and modulus of 6.8 GPa were achieved.
1.0 3.1.2. Morphology

DR = 6 Polymer processing conditions influence the fiber
0.5 DR = 5 morphology significantly [26]. When the spinning
DR = 4 temperature is increased, the surface of the filament
becomes smoother, whereas at lower temperatures,
0.0
the surface is observed to be quite rough. Indeed,
60 80 100 120 140 160 180
some particles evidencing nonuniform melting of
Temperature °C
polymer are seen on the surface. After hot drawing,
Fig. 8. DSC scans of spin-drawn fibers [2]. the fiber surface is quite smooth.
3.1.3. Birefringence
reduced and its beginning also shifts toward lower Birefringence has been employed to study fiber
temperatures. The degree of crystallinity tends to orientation [2]. It is observed that high-speed spun
increase with increasing spinning speeds. The PLA fibers (Fig. 9) tend to have relatively low
increase of crystallization observed between 3000 birefringence as compared to polyamide (PA) and
and 5000 m/min may be due to the usual orientation PET fibers. The birefringence increases slightly with
initiated crystallization in spinning. increasing spinning speed. Above 3500 m/min, a
Scans of spin-drawn fibers (Fig. 8) show almost decline can be seen; but since the crystallinity is low,
no cold crystallization during heating in DSC above the change is not pronounced. Spin-drawn filaments
the glass transition range. The crystalline fraction in are more birefringent than high-speed spun PLA
fibers is increased by the process of drawing and fibers because they are more crystalline.
simultaneous thermal fixation (heat setting), thus
avoiding cold crystallization during heating in DSC. 3.1.4. Mechanical properties
The addition of a small amount (1–8%) D-lactic acid Mechanical properties reflect the cumulative
to PLA alters the physical properties of the polymer effects of molecular weight, orientation of molecular
[27]. The filament prepared at high spinning speeds chains and crystallinity that develop during draw-
of 2500–5000 m/min exhibits high levels of orienta- ing, but chain branching architecture has little effect
tion and ultimate crystallinity. As the take up speed on mechanical properties. Cicero et al. [18] reported
is increased, the cold crystallization shifts to higher for both branched and linear PLA, that the modulus
temperature and the crystallinity, in general, in- increases monotonically with DR up to a plateau
ARTICLE IN PRESS
value (Fig. 10). Although, the values for the strength increased linearly with collection speed up
branched material are generally a little higher than to 128 and 209 MPa, respectively. The strain at
those of the linear material, the difference is not break decreased rapidly at first from 580% (at
significant. Branching, therefore, appears to have no 1.8 m/min) to 94% (at 5 m/min) and then slowly to
impact on modulus. Fambri et al. [16] discussed the 60% (at 10 m/min) and 23% (at 20 m/min). A low
effect of various spinning parameters on mechanical modulus of 7 GPa for fiber collected at 1.8 m/min
properties of the fiber. A direct consequence of both was due to premature fracture induced by an
crystallinity development and cross-section reduc- inhomogeneous temperature distribution in the fiber
tion during extrusion is the modification of mechan- during spinning. Data on mechanical properties for
ical properties as the combined effect of partial various collection speeds are given in Table 7. It is
alignment of polymer chains, crystallization and evident that high strength PLA fibers can be
predrawing phenomena. Even if crystallinity does produced with balanced crystallizability and draw-
not monotonically increase with the collection rate, ability by extrusion and hot drawing.
the increase in orientation of the amorphous phase Molecular weight has a pronounced effect on
affects and to some extent improves fiber mechan- mechanical properties of the fiber. It is observed
ical properties. The tensile modulus increased from that melt spun PLA fibers with molecular weights of
2.8 to 4.1 GPa, reaching an almost constant value 1.8 105 and 2.6 105 reached maximum tensile
for higher collection rates, whereas yield stress and properties at a drawing temperature of about 110 1C
and draw ratio of 8 [1]. The fiber sample with
Mv ¼ 1.8 105 had a tensile strength at break of
DR 0.5 GPa, an initial modulus of 6 GPa and an
3.5 4.0 4.5 5.0 5.5 6.0 6.5 elongation at break of 25%. The sample with
0.03000 Mv ¼ 2.6 105 had a tensile strength at break of
0.48 GPa an initial modulus of 7 GPa and an
0.02000
Table 7
Δη
Mechanical properties of fibers obtained with different collection

conditions and drawn at 1601C[16]
0.01000
Collection Tensile Yield Tensile Strain at
speed modulus strength strength break
(m/min) (GPa) (GPa) (GPa) (%)
0.00000
0 1000 2000 3000 4000 5000 6000 1.8 7.070.9 0.2170.04 0.6670.04 24.572.1
V ( m/min) 5 9.271.7 0.2970.18 0.8770.11 18.771.9
10 9.070.4 0.2270.01 0.6370.06 17.771.6
Fig. 9. Birefringence as a function of take-up velocity and draw 20 8.171.3 0.1570.02 0.4170.08 18.072.4
ratio [2].
3
BR
Modulus (GPa)
LN
1
0 1 2 3 4 5 6 7 8 9
Draw Ratio
Fig. 10. Modulus as a function of draw ratio [18].

ARTICLE IN PRESS
elongation at break of 20%. The maximum tensile Table 9

strength at break found for both samples are lower Tensile properties of hot-drawn PLLA fibers [26]
than those found by Schneider [32] for PLLA with Sample Draw Die Tensile Ultimate Ultimate
Mv ¼ 2.0 104 (0.5 GPa) and Mv ¼ 1.8 105 ratio tempera- modulus strength elongation
(0.7 GPa). The difference in the tensile strength ture (1C) (GPa) (MPa) (%)
may be due to different experimental procedures as,
PLLAa 4.71 220 5.2270.24 535770 39.273.3
for instance, the melt spinning and drawing, as well
4.75 230 4.7470.25 488757 55.677.7
as to the tensile testing conditions [1]. 4.77 240 4.5870.14 412727 65.479.3
Yuan et al. [26] carried out melt spinning of
PLLAb 5.50 210 4.9670.43 484786 40.876.6
PLLA fiber of three different viscosity average 4.66 220 4.4770.31 480784 51.377.2
molecular weights. The effect of the molecular 5.35 230 3.8870.27 332734 57.877.9
weight of the raw materials and the melt extrusion
PLLAc 5.18 210 4.4670.11 365740 66.8710.3
temperature on the tensile properties of fibers was
5.11 220 4.1270.36 400755 73.6713.1
studied. The tensile moduli of the as-spun PLA 5.89 230 4.4370.53 415750 67.377.8
fibers were in the range of 1.2–2.4 GPa and these
moduli were raised to 3.6–5.4 GPa after the hot Samples a, b, c, as in Table 6.
drawing. The tensile modulus was higher when the
original molecular weight was higher or when the
extrusion temperature was lower. As shown in from the spin line surface to the surrounding
Tables 8 and 9, the ultimate strength of the as-spun medium.
fibers were in the range of 42–103 MPa. After hot Leenslag et al. [33] produced high strength fibers
drawing, the values were raised dramatically to by dry spinning and subsequent hot drawing from
300–600 MPa. The data in Table 9 show that hot- polymer solutions in chloroform/toluene mixtures
drawn fibers of PLLA with the highest molecular near the theta temperature where PLA adopts an
weight had the highest tensile modulus of 5.22 GPa interrupted helical conformation [33]. The spinning
and the highest ultimate strength of 535 MPa. solutions were prepared by dissolving PLA in
chloroform and subsequently adding toluene with-
out mechanical stirring. Before extrusion, the PLA
3.2. Dry spinning of poly(lactic acid) solutions were conditioned in the piston-cylinder
apparatus at 70 1C (PLLA/toluene at 90 1C) for 3 h
Very few studies have been reported on dry and the fibers were extruded through a stainless steel
spinning of PLA. In this process, a polymer dope is conical die. The distance between the die and the
extruded into a thermally insulated chamber where bobbin was maintained as required. The as-spun
the solvent is removed by flash vaporization, fibers were then dried to constant weight on the
diffusion within the spin line and mass transfer bobbins at room temperature. Hot drawing was
carried out in a heated double-wall glass tube to
Table 8
obtain fiber with good tensile properties.
Tensile properties of as-spun PLLA fibers [26]
Table 10 indicates solvent–nonsolvent composi-
Sample* Die Tensile Ultimate Ultimate tions that have been established for producing
temperature modulus Strengthy elongation porous fibers by dry spinning [35]. Solvent, being
(1C) (GPa) (MPa) (%)
the more volatile component, evaporates quickly
PLLAa 220 2.1570.22 95.477.9 395740 and the nonsolvent causes coagulation of a porous
230 2.3270.15 79.378.5 435754 structure. Horocek and Kalisek [34] prepared PLA
240 1.7670.56 60.9717.1 4.1970.45 fibers by a continuous dry spinning-hot drawing
PLLAb 210 2.0470.15 60.7717.1 293785 process. They dissolved the polymer in a chloro-
220 2.2470.24 71.97 9.3 440754
230 2.0270.26 66.077.0 1057163
form/cyclohexane mixture and spun the solution at
PLLAc 210 1.8170.29 50.678.5 8.9674.43 ambient temperature through an orifice (0.5 7 mm)
220 2.1570.18 50.878.5 74.8791.5 with an extrusion speed of 6.5 cm/min. The filament
230 2.1970.08 53.2711.2 33.4739.6 was continuously led on to a steel drum in 1 30 cm
*Samples a, b, c, as in Table 6.
drawing tube at the drawing temperature of
y
The entries for the ultimate elongation and its uncertainty for 110–190 1C, and the hot-drawn fiber was collected
samples b230, c220 and c230 are as given in Ref. [26]. on another drum. The resulting fibers had an
ARTICLE IN PRESS
Table 10
Spinning solutions [35]
Concentration of Nonsolvent Boiling point of Volume ratio Tensile strength (Gpa)

PLLA (g/ml)a nonsolvent (1C) CHCl3:nonsolvent
0.133 Pure CHCl3 0.41

0.113 Ethanol 78.3 7:3 0.16
0.113 Cyclohexane 80.7 7:3 0.19
0.140 Methanol 65.0 7:9 0.28
0.126 Acetone 56.5 7.7:2.5 0.32
a
Chloroform was used as the solvent in all cases.
average mechanical strength of 0.7 GPa and porous Table 11

morphology. The solvent composition played an Heat of fusion of the as-spun fibers, maximum draw ratio,
diameter of drawn fiber and tensile strength of PLLA filament,
important role in establishing the fiber morphology.
spun from 4 wt % solutions in chloroform/toluene (40/60) into
As the cyclohexane content in the chloroform–cy- surroundings at various temperatures [37]
clohexane mixture increased, phase separation oc-
curred more rapidly and tensile strength decreased, Ambient Heat of Draw Fiber Tensile
irrespective of the heat setting temperature. temperature fusion (J/g) ratio diameter strength
(1C) (mm) (GPa)
Although, the surface skin was slightly porous, the
core did not coagulate as rapidly and was very 9 48.8 12 27 1.3
porous. This was evident at a chloroform–cyclohex- 20 44.6 14 23 1.5
ane composition of 60:40 where a hollow fiber 22 41.2 13 21 1.8
25 54.8 13 17 2.2
structure was created.
30 45.6 14 22 1.9
In another discontinuous process for fiber forma- 37 53.5 13 19 1.8
tion, Horacek et al. [35] spun the solution at 45 34.9 12 26 1.4
laboratory temperature through an orifice 60 49.3 13 28 1.1
(0.28 7 cm) with an extrusion speed of 42.2 cm/m
into beaker 50 cm below. After reaching constant
weight by drying, the filament was drawn in a produced high strength PLA fibers by dry spinning
1 30 cm tube at drawing temperatures of 90, 125 and hot drawing. The spinning solutions were
and 165 1C. As the data in Table 10 indicate, higher prepared by dissolving PLA in chloroform. After
volatility of the nonsolvent generally favors better 1 week, some of the chloroform was evaporated and
tensile strength. toluene was added to the solutions without mechan-
In another variation [36], the precipitant was not ical stirring. The solutions were homogenized by
part of the polymer solution. Instead, a nonsolvent, standing for 2 weeks. It was not possible to dissolve
such as methanol, ethanol, or petroleum ether, the polymer directly into the chloroform/toluene
formed a vapor in the chamber. PLA fibers were mixture.
prepared by spinning in the vapor precipitant and The ambient temperature at the spin line has a
were subsequently hot drawn. PLA was dissolved in profound influence on the physical characteristics of
chloroform and was spun at laboratory temperature the filament. The tensile strength increased with
through an orifice. The filament was led up through increasing temperature up to 25 1C and then
a glass tube and collected on a steel drum. The decreased drastically [37]. A maximum tensile
precipitant vapor was introduced at the bottom of strength of 2.2 GPa was achieved (see Table 11). It
the tube in a gentle stream of argon. After 48 h in a is the solidification process that determines fiber
drawing tube at 90 1C, the fibers were hot drawn to structure and physical properties. At high tempera-
a maximum draw ratio (lmax) at an entrance speed ture, the flash evaporation of the solvent (chloro-
of 8.3 cm/min. Petroleum ether, by virtue of its form) is accelerated and then solidification (phase
high vapor concentration, behaves like a liquid separation) impedes sliding of the molecular chains
precipitant. As a result, a skin layer was formed and and chain reorientation where topological defects
then a porous inner layer. Postema et al. [37–39] are numerous.
ARTICLE IN PRESS
The extrusion speed and winding speed play a ability. The DHf vs. toluene volume fraction (f)
dominant role in the development of fiber structure curve exhibits a pronounced maximum. PLA fibers
and fiber characteristics. Increasing extrusion speed dry-spun from chloroform/toluene 40/60 (v/v) were
leads to higher orientation and enhanced crystal- found to have the highest initial crystallinity
lization [16]. Postema et al. [37–39] observed no (53.4%) and lmax ¼ 20 when hot drawn. In general,
correlation between the extrusion speed and the fiber drawability appeared to improve with increas-
crystallinity of the fiber, and that tensile strength ing heat of fusion of the as-spun filaments. This
decreased with increasing extrusion rate. Although study confirms that DHf can be regarded as a
high deformation rates may lead to significant chain relative measure of the concentration of chain
scission, this was not a factor in these studies as the entanglements [33]. The rate of solidification did
molecular weight of the polymer was not affected by not influence the overall crystallinity of the fila-
the extrusion rate [40]. Southern and Ballmann [40] ments (Table 11). Measurements of crystallinity by
propose that the loss in tensile properties may be the DSC revealed heats of fusion between 34.9 and
outcome of flow instabilities, which lead to the 54.8 J/g with no correlation with ultimate tensile
voiding and cavitation resulting in anisotropic strength [37] (Table 11). DSC measurements on the
structure, and hence to inferior fiber properties. as spun-fibers indicated a reduction of the heat of
Leenslag et al. [41] obtained PLA fibers with a fusion at higher winding speeds (Table 12). This
loosened fibrillar structure by solution spinning reduction may be correlated with the number of
from a good solvent (chloroform) in the presence of entanglements and topological constraints [38].
various additives. Spinning was carried out at room Melting endotherms of dry-spun PLA fiber from
temperature with chloroform as the solvent. Poly- trichloromethane solution are presented in Fig. 11.
mer concentrations were in the range 10–18% (w/v). Endotherm 1 was recorded for the as-spun fiber.
Toluene, camphor, a copolymer poly(L-lactide)- Endotherms 2, 3 and 4 represent the fibers drawn at
polyurethane, and commercial medical grade poly- 200 1C to different draw ratios. The tensile strength
urethane were used as additives at concentrations, of the fibers was 0.1, 0.5, 0.8 and 1.2 GPa for fibers
respectively, of 30% (v/v), 20% (w/w), and 5% 1, 2, 3 and 4, respectively. The broad melting
(w/w) for both polyurethanes. No orientation or endotherm of the as-spun fiber is transformed into a
degradation was introduced during the spinning of high, narrow melting peak seen for all the hot-
the fiber. Hot drawing was carried out in an electric drawn fibers. The broad shoulder on the high-
tube furnace 300 mm in length up to draw ratios temperature side of the endotherms, which almost
6–30 with input velocity 2 cm/min. Gogolewski and disappeared when the fibers used for DSC measure-
Pennings [42] also reported solution spinning of ments were cut into small 2–3 mm pieces, is mainly
PLLA fibers in solvents, such as dichloromethane due to a delayed randomization of the melt. On the
and trichloromethane. Polymer concentrations were other hand, it should be noted that the heat of
in the range 1–20% w/v. Filaments were collected fusion increases considerably upon hot drawing, as
on a glass drum at a speed at 0.02–1.0 m/min. No is illustrated by Table 13. The DHf value for as-
orientation was introduced by spinning. extruded fibers was 34.0 J/g, while after hot drawing
Unlike melt spinning, the molecular chain degra- at 200 1C to a lmax of 20 the heat of fusion
dation in dry spinning is effectively controlled. If amounted to 89 J/g. Fischer et al. [44] calculated
any degradation at all occurs, it may be during
polymer dissolution, particularly in solvents like
Table 12
chloroform. The moisture ordinarily present in Heats of fusion and maximum draw ratios of as-spun PLLA
chloroform is sufficient to cause chain scission and Fibers [38]a
may eventually lead to degradation in molecular
weight as high as 23% after 1 week in solution [43]. Vwind (m/min) DH (J/g) lmax (hot draw)
However, a careful check on degradation is possible 10 45.0 16
by using chloroform dried over P2O5. 20 40.1 13
30 36.1 13
3.2.1. Thermal properties 60 34.4 10
80 27.2 9
Leenslag and Pennings [33] observed strong
182 21.8 9
correlation among solvent composition, heat of
a
fusion DHf of as-spun filaments and their draw- Extrusion speed: 30 m/min.
ARTICLE IN PRESS
9
1
Pitch (10-4m)
2
Endo
3
3
4
0
0 5 10 15 20
120 140 160 180 200
T (°C) Extrusion speed (10-2m.min-1)
Fig. 11. Melting endotherms of PLLA fibers. (1) as-spun fiber Fig. 12. Effect of spinning rate on helical pitch of as-spun PLLA
(fibers 2, 3, 4 drawn at 200 1C to l ¼ 10, 15, 20 respectively [42]). fibers [41].
Table 13 The spinning rate also has a crucial impact on

Heat of fusion (DHf) of PLLA Fibers with Mv ¼ 6.0 105, spun fiber morphology. A regular spiraling distortion of
from 5% solution in trichloromethane, varying in tensile strength the extrudate is observed on the fiber surface.
(TS) [42]
Increasing the spinning rate via the pressure applied
TS (GPa) Initial Draw ratio Diameter DHf (J g1) to the polymer solution, also increases the pitch of
modulus ( 104 m) the helical distortion. As shown in Fig. 12, the
helical pitch of the as-spun PLA fibers is a linear
1.2 15 20 0.35 89.0
1.1 14 19 0.39 83.6 function of the spinning rate [41].
1.0 12 18 0.44 76.0 Gogolewski and Pennings [42] observed that the
0.8 10 16 0.59 70.6 morphology of poly(L-lactide) fibers produced by
0.6 9 10 1.10 67.2 dry spinning from dichloromethane or trichloro-
0.5 8 8 1.32 65.5
methane solutions at room temperature depends to
a great extent on polymer concentration. The fibers
obtained from 2% solutions were flat and exhibited
that the heat of fusion for fully crystalline poly a smooth surface while the fibers spun from 10% to
(L-lactide) should be 93.7 J/g. Thus, hot drawing 20% solutions were cylindrical and had a character-
under optimum conditions gives rise to an extension istic ‘‘structured’’ surface. This surface structuriza-
of the crystallites which can probably be correlated tion may very well be due to melt fracture, a
with the tensile strength, as is indicated by the data phenomenon that has been observed for a number
summarized in Table 13. of polymers and is related to flow instabilities in the
spinning die arising from the elastic character of
3.2.2. Morphology polymer melts and solutions. Owing to the influence
The morphology of fiber is significantly affected of elasticity on flow behavior, the fiber turned out to
by the precipitant vapor. The structure of as-spun be regularly ‘coarse threaded’. For a given polymer
fiber in petroleum ether vapor as precipitant is concentration, the pitch of the thread decreased on
characterized by an irregular skin and porous inner increasing the pressure applied to the polymer
part due to very fast phase separation. In ethanol solution. Even hot drawing at high draw ratios
vapor, phase separation rate is very slow, which does not completely remove the surface structure.
gives a surface similar to that of dry-spun fiber. The Fiber stretching causes an extension of the pitch of
fiber spun in methanol vapor as a precipitant has no the helix, indicating that drawing does not proceed
apparent skin; the surface is perforated and the fiber by neck formation. Between the helical pitch lines
shape is regular [36]. the surface of the fiber appears to be rather smooth
ARTICLE IN PRESS
and fibrillated, as may be seen by scanning electron creases linearly with the reciprocal molecular
micrographs (SEMs). Hot drawing does not lead weight.
to a full reorganization at the molecular level The plot in Fig. 14 of tensile strength as a
but, a strong ‘memory effect’ occurs that is likely function of drawing temperature exhibits a max-
associated with remnants of chain entangle- imum value of 2.0 GPa after drawing at 188 1C to a
ment [42]. maximum draw ratio of 13. The low values of draw
ratio leading to excellent fiber properties indicate
3.2.3. Mechanical properties that although the entanglements are mobile enough
The composition and nature of the solvent play to slip into newly created disordered domains,
an interesting role in the morphological develop- disentangling is impeded by the rapid formation of
ment of the fiber and its mechanical properties. The fibrillar crystals between entanglement-rich domains
tenacity of PLLA fiber spun from 4% (w/v) polymer [39]. The tensile strength is dependent on an
solutions in various chloroform/toluene mixtures optimum drawing temperature, which in turn
and then hot-drawn to different l at 204 1C is shown depends on the molecular weight of the material.
in Table 14. The tensile strength sb of the fiber The maximum tensile strength was found after
depends on the chloroform/toluene composition, drawing at temperatures in the range 197–200 1C for
with a maximum of 2.1 GPa at a toluene volume fibers with molecular weights above 4.0 105, while
fraction ftol of 0.6 [33]. However, fibers spun from for the fibers with molecular weight in the range
trichloromethane attained higher tensile strengths 1.2–3.5 105, the maximum in the tensile strength
and moduli than those of similar initial molecular was reached at 175–180 1C. The reason is probably
weight spun from toluene [42]. that in lower molecular weight polymer, the higher
The effect of polymer molecular weight on the drawing temperature causes disordering and refold-
ultimate tensile properties of the fiber is of obvious ing of the chains into poor crystals with a lower
importance. As molecular weight increases, the melting temperature. Thus, it seems that increasing
complexity of the entanglement network also the drawing temperature above an optimum value
increases, hampering partial disentangling of the results in flow drawing rather than hot drawing, and
chains during dissolution and/or hot drawing. Less could lead to poorly oriented fibrillar crystals [42].
entanglement in the transient polymeric network The ultimate tensile strength of fibers appears to be
during drawing enables proper alignment and dependent on the ambient temperature during
extension of high molecular weight chains. There- spinning, which is usually set from 9 to 60 1C.
fore, in dry spinning of high-MW flexible polymer, Postema et al. [37] obtained a maximum tensile
solidification (gelation) of the polymer should strength of 2.2 GPa after hot drawing filaments
preferably take place near the onset of coil overlap spun at 25 1C. At lower and higher ambient
in order to minimize the entanglement density in the temperatures the ultimate tensile strength decreased
filaments produced [33]. Fig. 13 represents the drastically. The deformation rate in the drawing
tensile strength of fibers from both toluene and tube had no effect on strength of filaments spun
trichloromethane solutions. The tensile strength is at low and high ambient temperatures except near
independent of molecular weight in the range 25 1C. This suggests that during spinning in sur-
1.8–3.0 105, beyond which tensile strength in- roundings above or below an optimal temperature,
Table 14
Typical properties of PLLA fibers (Mv ¼ 9 105) spun at 60 1C from various solvents (mixtures) and hot-drawn at 204 1C to lmax [33]
Solvent composition sb (GPa) E (GPa) e (%) lmax Cross sectional area 1010 (m2)
Chloroform (f) Toluene (f)
1 0 0.75 9 20 5 11
0.5 0.5 1.45 10 23 10.5 3.45
0.4 0.6 2.10 16 23 20 1.36
0.3 0.7 1.40 11 23 14.5 2.67
0 1 1.05 10.5 23 13.5 4.21
ARTICLE IN PRESS
1.2 1
1.4 2
1.0
1.2 3
0.8
Stress (GPa)
TS (GPa)
1.0 0.6
4
0.4
0.8
0.2
0.6
0 5 10 15
Strain (%)
0.4
0 2 4 6 8 Fig. 15. Stress–strain dependence for PLLA fibers with
Mv ¼ 6.0 105 spun from polymer solution in trichloromethane
106/MV
and drawn at 20 1C to different draw ratios: (1) 20, (2) 18, (3) 14,
(4) 10. (- - -) for fiber spun at 110 1C from toluene and hot-drawn
Fig. 13. Dependence of tensile strength on reciprocal molecular
at 200 1C to lmax ¼ 18 [42].
weight for PLLA fibers spun from 5% polymer solution in
trichloromethane ( — ) and toluene (- - -). Both types of fibers
were hot-drawn under optimum drawing conditions [42].
toluene [42]. It can be seen that for the same draw
ratio, fibers spun from the solution of PLA in the
good solvent exhibit better tensile properties than
2.0 obtained from toluene, a poor solvent. It is
Ven = 1.25 cm/min
conceivable that this marked difference in strength
Tensile strength (GPa)
1.6 may be related to the fact that in good solvent the

more expanded coil will contain fewer topological
1.2
irregularities, such as intramolecularly entangled
chain portions, than the polymer dissolved in the
poor solvent. The initial modulus is the same for all
0.8 draw ratios, but the strain at which the inflection
point occurs increases with l. Essentially, one can
0.4 distinguish two slopes in stress–strain curves. This
may be associated with a possible change in
0 structure of the crystalline domains when PLLA is
180 190 200 210 subjected to stress, similar to observations on
Drawing Temperature (°C) poly(butylene terephthalate) reported by Brereton
et al. [45]. Polyesters are known to exhibit a solid-
Fig. 14. Tensile strength of PLLA fibers hot-drawn at different
state transition from the p-helical crystalline
temperatures to the maximal draw ratio using an entrance
velocity of 1.25 cm/min in a tube-drawing process [39]. structure to the b-crystalline structure in which the
chains assume an extended planar zigzag conforma-
tion [42].
Spinneret design has a substantial effect on fiber
heterogeneous filaments are formed (possibly due to properties. During extrusion, breakup of the mole-
rapid phase separation) that leads to weak fibers cular network causes flow instabilities. Extension of
after hot drawing [37]. the molecular network over the sharp edges inside
Fig. 15 shows the stress–strain dependence for the orifice, combined with the acceleration of the
PLA fibers spun from a solution of the polymer in solution at that point, might cause a rupture of
trichloromethane and also from a solution in the solution structure. Additionally, adsorption of
ARTICLE IN PRESS
polymer chains on the wall of die may originate precipitating bath or a series of baths of increasing
topological constraints that are most likely the precipitant concentration. This perhaps represents
reason for the decrease in the tensile strength after the most critical element in the solvent spinning
hot drawing. Both entanglements the orifice dia- process because, during its short residence time in
meter and reduction of the entrance angle will result the coagulation bath, the fiber forms and its
in a smaller velocity gradient in the orifice and thus structure takes shape as a result of complex
may reduce partial crystallization and rupturing of interactions of numerous factors: the particular
the molecular network due to phase separation. solvent, polymer, temperature, and nonsolvents
The hot drawing of PLA filament has been used, as well as flow variables, etc. Interactions
investigated by Postema and Pennings [39] at among these many variables produce the conditions
temperatures up to 180 1C and above 190 1C. In in which counterdiffusion of solvent and nonsolvent
the first case (up to 180 1C) the deformation takes and phase separation of the polymer take place.
place in the semicrystalline state of the polymer and Tsuji et al. [46] reported wet spinning of stereo-
in the latter case deformation proceeds in the complex PLA fiber. Chloroform solutions of PDLA
amorphous fluid state of the polymer. In all cases, and PLLA with a concentration of 5–10 g/dL were
drawing of PLA resulted in moderately good separately prepared and admixed in equimolar
mechanical properties and fiber with a tensile ratio. The coagulation was carried out into the first
strength of 2.2 GPa was achieved. This work seems coagulation bath containing a mixture of nonsol-
to demonstrate not only that the deformation rate is vent and solvent, ethanol/chloroform 10/3 (v/v), at
responsible for the ultimate mechanical properties 40 1C, and then further into the second coagulation
but also that harmonization of drawing temperature bath [ethanol/chloroform ¼ 10/1 (v/v)] at 20 1C to
and deformation rate is needed for every selected complete the desolvation, followed by winding of
molecular weight and molecular weight distribution the fiber. The apparatus for wet spinning is shown
in order to determine the correct drawing conditions in Fig. 16. The tensile strength of the wet-spun
leading to the ultimate mechanical properties [39]. complex fiber was very low and could not be drawn
at high temperatures. From SEM analysis it was
3.3. Wet spinning of PLA seen that the undrawn fiber surfaces are very
irregular; the undrawn wet-spun fiber has depres-
In wet spinning, the polymer solution, prepared sions with an average diameter of about 50 mm and
in a suitable solvent, is extruded as a fiber into a a large number of pores with various sizes ranging
coagulation bath containing a nonsolvent. The from sub-mm to 10 mm on its surface. The defective
limits of polymer concentration in the spinning structure of the wet spun fiber is probably due to the
solvent are determined by factors such as polymer rapid desolvation from the extruded dope during
solubility and solution spinning pressure limita- precipitation.
tions. The polymer concentration used for wet
spinning is lower than that in dry spinning, since 3.4. Dry-jet-wet spinning of poly(lactic acid)
the solution is spun at lower temperatures. The
spinneret is submerged in the liquid coagulation In wet spinning, the as-spun fiber always has voids
bath, and the emerging filaments are coagulated in a that cause deterioration of fiber properties: e.g. weak
Dope (5-8g/dl)
N2
EtOH/CHCl3(10/1)
20 °C
Winder
Second Coagulation Bath
Nozzle
EtOH/CHCl3(10/3) 40 °C
First Coagulation Bath
Fig. 16. Wet spinning apparatus [46].

ARTICLE IN PRESS
mechanical properties due to easy fibrillation and take-up speed, drawing temperature, and heat
low transparency. The formation of voids can be setting temperature. It was observed that the draw
held to a minimum by extruding the dope stream ratio had a significant influence on the crystallinity
from a dry jet, followed by coagulation as in and tensile strength of the fiber. A tenacity of
conventional wet spinning. This process is known 5.3 gpd (0.60 GPa) and modulus of 72 gpd (8.2 GPa)
as dry-jet-wet spinning. The dry jet gap is varied were achieved at a draw ratio of 8 (Fig. 18).
from 3 to 5 mm. Dry-jet-wet spinning allows stress
relaxation of polymer chains in the air gap of the 3.5. Electrospinning of poly(lactic acid)
orientation produced in the spinneret, so that the
spun fiber is less oriented and more uniform than Electrospinning is another interesting technique
that from the immersed jet. This permits orientation for spinning PLA (and other polymers). The process
by subsequent drawing and gives fibers with higher offers an excellent opportunity for designing the
tenacity. surface morphology and porosity of the fiber to
Dry-jet-wet spinning of PLA fiber is the least provide the most appropriate interface for biome-
studied technique. Eenink et al. [47] reported dical applications [51,52]. The process may be
spinning of hollow PLA fibers by a phase-inversion considered as a variation of electrospraying, gov-
spinning process. The dry-wet phase-inversion erned by solution viscosity, applied voltage and
spinning process is schematically shown in Fig. 17. current. Polymer from a solution or melt can be
The as-spun hollow fibers, without post-spinning deposited as fibrous material by charging the liquid,
treatment, were used as drug delivery devices. The applying 5–30 kV and ejecting it through a nozzle
fibers were characterized with respect to molecular onto an oppositely charged grounded target. Fig. 19
weight, residual additive content, degree of crystal- shows schematically an electrospinning system
linity, and transition temperatures. It was found consisting of a high-voltage DC supply, a grounded
that no polymer degradation occurred during electrode, a nozzle system with diameter controls,
spinning from dioxane and chloroform solutions. and the target to which the spun fiber adheres.
Witte et al. [48] reported highly crystalline, Electrospinning is a simple way of producing
porous, hollow PLLA fibers spun by the dry-wet nano-size filament by properly controlling the
spinning process. The pore structure of the fibers polymer concentration and/or surface tension of
could be regulated by changing the spinning system the solution. The nozzle diameter can be in the
and spinning conditions. The spinning system range of 0.05 mm to a few microns. The fibers can be
PLLA-chloroform/toluene-methanol yielded fibers spun onto nonwoven structures which are porous
with a very open, porous structure. and have high surface area. This is where electro-
An extensive study of dry-jet-wet-spun PLA fiber spinning offers advantages over other, more con-
was reported by Gupta et al. [49,50] using chloro- ventional, processes [54,55]: the electrospun
form/methanol as the solvent/nonsolvent system. nonwoven structure provides scaffolding for tissue
The study was carried out by varying draw ratio, engineering [51].
Bore injection liquid reservoir Spinneret (enlarged)

Spinning solution reservoir
H Godet
First coagulation bath Second coagulation bath

F G
Fig. 17. Scheme of dry-wet spinning process [47].

ARTICLE IN PRESS
80 8 100
80
60 6
ELONGATION (%)
MODULUS (gpd)
TENACITY (gpd)
60
40 4
40
20 2
20
0 0 15
0 2 4 6 8 10 12
DRAW RATIO
Tenacity Elongation Modulus
Fig. 18. Effect of draw ratio on mechanical properties [49].
Syringe Needle The diversification of these applications is such that a

single polymer may prove useful in many applications
by simple modifications of its physico-chemical
Syringe pump
structure. In many cases the polymer can be blended
with other polymeric or nonpolymeric components to
achieve the desired behavior. Polylactic acid offers
Rotating and translating unique features of biodegradability, thermoplastic
HVDC grounded target
processibility and ecofriendliness that offer potential
applications as commodity plastics, as in packaging,
agricultural products and disposable materials. On the
other hand, the polymer also has a bright future for
Fig. 19. Schematic of electrospinning system [53]. applications in medicine, surgery and pharmaceuticals.
The fundamental polymer chemistry of PLA
The attraction of electrospinning lies in the fact allows control of certain fiber properties that make
that it is possible to incorporate specific agents and the fiber suitable for a wide variety of technical
substances in the polymer solution so that the spun textile fiber applications, especially for apparel and
fiber will contain these additives in the fiber matrix. performance apparel applications:
This approach offers development of nanofibers
incorporating bioactive agents. Scanning electron Low moisture absorption and high wicking,
microscopy of electrospun filament showed that fiber offering benefits for sports and performance
diameters of 3–6 mm had been achieved. Electrospin- apparel and products.
ning has been extended to the other polymer forms Low flammability and smoke generation.
such as poly(D, L lactic acid) and material with High resistance to ultraviolet light, a benefit for
defined porosity has been developed for pharmaceu- performance apparel as well as for outdoor
tical application [53]. The electrospinning of copoly- furniture and furnishings applications.
mer of lactic acid and glycolic acids was reported by Low index of refraction, which provides excellent
You et al. [99]. The structure showed good porosity color characteristics.
and reasonably good mechanical strength. Low density, making PLA fibers lighter in weight
than others.
4. Applications of poly(lactic acid) Fibers coming from an annually renewable re-
sources base that are readily melt-spun, offering
Biodegradable textiles are eliciting enormous inter- manufacturing advantages resulting in greater
est in various domains of technological importance. consumer choice.
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PLA finds applications in a variety of filament into various shapes. The apparel sector is very
and nonwoven structures (Table 15). These struc- promising. For example, the University of Tennes-
tures may be produced by a variety of spinning see (USA) has been active in work on spunlaid and
techniques and mechanical processing. The fiber meltblown nonwovens based on PLA. Kanebo Ltd
may be made into fabric by bonding, thermal (Japan) has produced a PLA fiber under the brand
bonding, carding, knitting and by weaving. The name LACTRONTM, which was exhibited in
versatility of the filament with respect to transfor- garments during the Nagano Olympics under the
mation into various shapes and morphology along umbrella of ‘‘Fashion for the Earth’’ [15]. The low
with good mechanical properties has led to its wide modulus of the fiber has been exploited for better
range of applications (Table 16). These areas range drape and feel of fabrics. A market for PLA has also
from apparel, furnishing and agricultural products developed in sportswear, especially as an inner
to the world of biomaterials and artificial organs. As wicking layer. For instance the French company,
already noted, PLA is an excellent material for Fiberweb, has disclosed webs and laminates made
medical applications because its degradation pro- of 100% PLA and extruded a range of melt-blown
duct, lactic acid, is fully biocompatible. and spunlaid PLA fabrics under the brand name
The special features and characteristics of PLA DeposaTM [56].
place this material at the top of the world of
technical textiles. Efforts are underway to secure 4.2. Medical applications
patent protection in areas where the polymer offers
unique performance characteristics. The medical textile industry is one of the most
diversified sectors representing the state-of-the-art
4.1. Commodity applications in designing and developing innovative materials
and devices that are redefining traditional ap-
The thermoplastic character of PLA is very useful proaches to human health care [57]. The attraction
in allowing transformation of the polymer materials lies in specialized polymer materials and engineered
structures dedicated to specific applications. This is
where the term ‘biotextile’ originated, signifying
Table 15 structures composed of textile fibers designed for
Various forms of PLA
use in specific biological environments (e.g. surgical
Monofilament implants, biomass reactors), where their perfor-
Multifilament mance, measured in terms of their biocompatibility
Trilobal BCF and biostability [58], depends on their interactions
Staple fiber
Bicomponent fiber
with cells and biological fluids. The applications of
Spun bonded nonwoven biotextiles range from pharmaceuticals to suture
Needle punched nonwoven materials, implantable matrices and organ recon-
Knitted structure struction.
Woven structure The medical applications of PLA rest upon its
Composite materials
biodegradability and the compatibility of the
degradation products with the human body. Indeed,
PLA is the prime example of a ‘‘biomaterial’’ with
Table 16 emerging multidimensional applications. Following
Applications of PLA
are the major applications of the polymer.
Apparel
Furnishings 4.2.1. Sutures
Fibers Surgical sutures are wound closure filaments
Agricultural products
Hygiene products
fabricated in various shapes. The basic requirement
Sports wear of sutures is that they hold tissues in place until
Sutures natural healing of a wound provides sufficient tissue
Braided prostheses strength. PLA has been approved by the Federal
Pharmaceuticals and drug release system Drug Administration (FDA, USA) for use as a
Support matrices
Scaffolds for tissue engineering
suture material because of features that offer crucial
advantages [59,60].
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An enormous literature is available on the 50

degradation behavior of PLA in vitro as well as in
vivo. Its degradation is significantly influenced by
40
the environment: e.g. water, air, pH, air, and
% crystallinities
temperature [4]. Associated with environment, the
30
chemical composition of the filament also plays an
important role in degradation. Tensile properties
20
are related to the degree of molecular orientation,
the molecular weight of the polymer, degree of
10
crystallinity and the glass transition temperature
[61]. The accessibility of the polymer material to the
external medium will be enhanced at low crystal- 0
0 20 40 60 80 100
linity [62]. As degradation proceeds, the polymer
Mol % glycolide in copolymer
becomes more hydrophilic, enhancing water uptake
and accelerating degradation. This characteristic Fig. 20. Percent crystallinity for glycolic acid/lactic acid
opens the way for exploiting preferential degrada- (GA/LA) copolymers as a function of composition determined
tion. by X-ray diffraction and differential scanning calorimety (DSC)
measurements [61].
The intrinsic properties of unmodified PLA, such
as its high crystallinity (ca. 40%) and rigidity and
slow degradation, put limits on its use as suture
material. For this reason, lactic acid is copolymer- (Vicryl) [64–66]. In an investigation of its degrada-
ized with other biodegradable monomers to achieve tion behavior it was observed that these suture
precisely defined properties required in the copoly- undergoes drastic loss of physical properties under
mer. The comonomer unit interferes with the aqueous medium in vitro. The results are indicative
regular alignment of molecular chains and hence of cleavage-induced crystallization during degrada-
impedes the formation of highly ordered regions. tion [65,66]. In this process, the amorphous chains
Glycolic acid is the most widely used monomer for undergo scission, which leads to increased chain
this purpose, and a copolymer with a 90:10 mole mobility and loss of tensile strength. Subsequently,
ratio of glycolic acid to lactic acid has been crystallites are formed from these short chains at
commercialized as Vicryl by Ethicon. This suture temperatures as low as ca.40 1C. The Tg of shorter
material has a higher degradation rate than PLA chains may fall significantly, owing to the plasticiza-
filament. It is important to note that the copoly- tion effect of absorbed water.
merization of lactic acid with a comonomer Sutures have been developed based on both
introduces significant changes in physical proper- poly(DL-lactic acid) and poly(L-lactic acid) [67].
ties. Crystallite formation is impeded and the glass The filaments were produced by melt spinning
transition temperature is lowered, depending on the carried out to get continuous filaments with a draw
amount of comonomer. The results in Fig. 20 show ratio of 4–12 so that appropriate strength would be
that the copolymer has a window of 24–66% achieved, i.e. 2.5 gpd under these spinning condi-
glycolic acid in which it is amorphous. Therefore, tions. The sutures were made by plying and twisting
a desired material may be tailored by copolymeriza- the filaments into 520 denier yarn. In vitro
tion with glycolide. This approach helps in produ- degradation was investigated in sodium hydroxide
cing sutures with the required initial mechanical solution at 25 1C. The degradation was extremely
strength to hold wound tissues together. At the high initially, as was evident from intrinsic viscosity
same time, the biological performance of the measurements. Surgical evaluation of the sutures
material must be maintained. was carried out by intramuscular implantation. The
Implanted PLA material undergoes degradation tissue reaction was like that to stainless steel and
and is reduced in weight by 63.2% within 168 days Dacron.
[63]. It has been estimated that complete decay The increase in crystallinity may in fact be due to
would need at least 1.5 years—an important the cumulative effect of the crystallization of
consideration for surgical applications. This con- fragmented chains and the loss of amorphous
sideration led to development of sutures based on regions by hydrolytic degradation. These results
polyglycolic acid (Dexon) and its copolymers are supported by in vivo studies of PLLA where an
ARTICLE IN PRESS
implantation period of 52 weeks leads to crystal- blends (50:50) was first investigated by Kenawy et
linity as high as 96% [68]. It was observed that the al. [53]. The advantage of the electrospun filament is
weight loss occurs from the beginning of the that a biomaterial with nanoscale fibers and
implantation for crystalline samples, but amor- designed porosity can be obtained. The drug
phous samples retain their original weight for up (tetracycline hydrochloride) was incorporated into
to 40 weeks. However, the intrinsic viscosity the PLA at the solution stage. The drug was
decreased right from the beginning for both crystal- solublized in methanol (it is insoluble in chloro-
line and amorphous samples. The crystalline mate- form) and then was added to the PLA solution in
rial showed molecular weight loss of about 70% chloroform. Electrospinning of the solution pro-
within 10 weeks. duced a sheet of nonwoven fabric. The filament
diameter could be controlled to 0.05 mm and a
4.2.2. Pharmaceutical nonwoven sheet of very low thickness could be
The biodegradability of PLA has inspired several obtained. The comparative release pattern of PEVA
studies on controlled drug delivery systems [69,70]. and its blend showed sustained release up to 120
Most systems have been based on the erosion of the days of the investigation as compared to the
drug-containing polymer, whereby the drug is instantaneous release of virgin PLA. This may be
released gradually by hydrolytic degradation and/ an attractive feature of PLA based blends where the
or morphological changes in the polymer. However, short term continuous release is needed.
other drug release systems have been developed
based on reservoir devices where the drug release 4.2.3. Implants
proceeds across a polymer membrane while the drug Poly(lactic acid) in both L and DL forms has
activity remains constant in the reservoir [71]. On proved effective as implants and supports in the
the basis of a similar concept, Eerink et al. [47] human body. The material characteristics of the
produced biodegradable hollow fiber from PLA by polymer may be altered controlling the molecular
dry-wet phase-inversion spinning from a PLLA- weight and the L/DL composition. The polymer may
PVP-dioxane spinning dope. The porous sponge- take 10 months to 4 years to degrade, depending on
like wall of the fibers was evident from SEM. The the microstructural factors such as chemical com-
internal and external wall surfaces remained cov- position, porosity and crystallinity that may influ-
ered by a skin ca. 0.3–0.4 mm thick. These hollow ence tensile strength for specific uses [72]. The
fibers were filled with Levonorgestrenol and the polymer has already shown favorable results in the
release behavior of the drug was studied. Constant fixation of fractures and osteotomies [73–75].
release of the hormone was maintained for a period PLA filaments in braided form have been used for
of 60 days. Obviously, the drug release pattern must ligament augmentation, in vivo, in subcutaneous
depend on the nature of the spinning dope, which rabbit tissue [70]. The tensile load-carrying capacity
determines the hollow fiber structure. The high of the implant was measured as a function of
release profiles reported by Eerink et al. are due to implantation time. The load capacity decreased
the porous skin layer, which offers low diffusion rapidly and was very low after 12 weeks of
resistance to the drug. It is very interesting that implantation. The elongation at break also showed
gamma irradiation of the filament leads to con- loss with implantation time. It is reported that the
siderable alteration in release behavior. The release maximum load bearing capacity of anterior cruciate
pattern showed that irradiation of the steroid-filled ligament is approximately 1400 N for dog [76]
hollow fiber enhances the release significantly; and 1900 N for sheep [77], and has been thought
irradiation of the fiber before filling it with steroid to be an important factor in the resistance of a
showed lower hormone release rate, but still higher structure to trauma in overloads. Considering that
than the unirradiated fiber. It seems that the tissues are subjected to 10–25% of the break-
irradiation might be having some adverse effect on ing loads under normal conditions, the braided
the hormone, which is reflected in the higher release structures show reasonable strength for ligament
of the hormone. This suggests that gamma irradia- applications.
tion might be used to modify PLLA hollow fiber,
either prior to or after the steroid filling. 4.2.4. Tissue engineering
The release of a drug from electrospun PLA, Organ failure and tissue loss are devastating
polyethylene-co-vinylacetate (PEVA) and their problems in human beings. The current approach to
ARTICLE IN PRESS
treatment is based on transplantation. However, PLA may be fabricated into various shapes (e.g.
tissue engineering is the most fascinating domain of filament, braided, knitted, nonwoven or film) as
medical technology where patients with organ required of the organ construction.
defects and malfunctions are treated by using their PLA filaments have been developed experimen-
own cells, grown on a polymer support so that a tally for regeneration of nerves in paralyzed patients
tissue part is regenerated from the natural cells. The [84]. Although nerves do not grow at all, it is,
great advantages of tissue engineering are that a however, possible to seed Schwann cells on a
donor is not required and there is no problem of polymer support and grow them. The approach
transplant rejection. adopted has been to join distal and proximal ends of
Tissue engineering is an interdisciplinary field that a nerve by an artificial segment which will allow the
applies the principles of life science and engineering Schwann cells to grow and fill the gap between the
to the development of biological substitutes that two ends. With the passage of time the support
aim to maintain, restore or improve tissue function. disappears and leaves behind a continuous channel
Although tissue engineering conjures up extreme of nerve cells. Adhesion of Schwann cells on virgin
visions of organs built from scratch in the labora- PLA surfaces is very limited, but plasma processing
tory, ready to be transplanted into desperately ill of PLA fiber is very effective in enhancing the
patients [78], the last two decades have seen adhesion. The plasma treatment introduces chemi-
extraordinary achievements in human organ recon- cal functionalities that can interact with poly-D-
struction based on tissue engineering. The innova- lysine and render the surface bioreceptive to cell
tive contributions of Vacanti and Langer in this field attachment.
are especially notable [79–81]. PLA microfibers have been evaluated for tissue
Initial developments were confined to the use of response using a rat-subcutaneous implantation by
biostable materials as scaffolds culturing cells that Sanders et al. [85]. The fiber diameter ranged from 4
were then harvested into tissue. More recently, to 15 mm, and it was observed that the capsule
biodegradable materials have found enormous thickness was much lower for the thin fiber.
interest as supports because of the fact that the Kellomäki et al. [86] studied the design and
support disappears from the transplantation site manufacturing of different bioabsorbable scaffolds
with the passage of time, leaving behind a perfect for guided bone regeneration and generation.
patch of the natural tissue. Among the various constructions, self-reinforced
The purpose of the scaffold is to act as an PLLA rods were used as a scaffolds for bone
extracellular matrix (ECM) where cells can adhere formation in muscle by free tibial periosteal grafts.
and grow, and thus to guide the development of The rods were manufactured by extrusion and die-
new, fully functional tissues [82]. The initial drawing techniques [77,79,80,86]. At 6 weeks after
requirement of the scaffold is to hold cells and implantation, new, histologically mature, bone had
tissues together in spite of partial degradation. This been generated in predesigned cylindrical form.
reflects the importance of mechanical strength in the Another device studied was a composite of poly-L,
initial stages; therefore, biological performance DL-lactide with LL/DL dimer ratio 70/30 (PLA 70) in
comes into the picture. Polymeric biodegradable thin plate form and poly-L,D lactide with an L/D
scaffolds combine advantages of synthetic and monomer ratio of 96/4 (PLA 96) in mesh form. The
natural materials. The physical properties of syn- PLA 96 was melt spun to 4-ply multifilament with
thetic polymers, such as mechanical strength and an individual filament diameter of 80–90 mm. Then
degradation rate, can be manipulated according to knitting was done on a single jersey knitting
requirements, with fewer batch-to-batch variations machine. By hot compaction molding the two
than are typical with natural materials [83]. structures were formed into a composite at 110 1C
Poly(lactic acid), alone or in combination with 8 MPa pressure. By selecting optimum processing
other biodegradable polymers, provides good sup- conditions a loose attachment between the compo-
port for cell growth. A fibrous scaffold has nents was achieved, keeping the mesh on the
significant advantages over polymer films in the surface. It was reported that bone has been
high level of porosity needed to accommodate large favorably grown along porous surfaces. It was
number of cells. This is where the pore diameter observed that mesh gives extra support for the
(interstitial space) becomes important for cell structure and extends the strength retention time
growth, vascularization, and diffusion of nutrients. during the degradation period.
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Yang et al. [87] attempted to develop a porous

polymeric nano-fibrous scaffold from PLLA for in
vitro culture of nerve stem cells. The nano-fibrous
scaffold was fabricated by liquid–liquid phase
separation in which a PLLA solution prepared in
tetrahydrofuran and was cast into a Petri dish,
followed by cooling to 30 1C. The resultant gel
was immersed in cold water (4 1C), which is a
nonsolvent for the polymer. The sample was
subsequently freeze-dried to obtain a porous scaf-
fold. The properties of the nano-fibrous scaffold
were strongly influenced by the concentration of
PLLA in the original solution. The average fiber
diameter of the scaffolds increased and the porosity
and surface area-to-volume ratio decreased with
increasing PLLA concentration. The optimum
Fig. 21. Collagen-immobilized PLA knitting [95].
concentration was 2–7% for the best fibrous
structure. Better cell adhesion and differentiation
was observed when nerve stem cells were seeded on obtain a structural resemblance to human decellur-
the scaffold. ized matrix (Fig. 21). These protein-immobilized
The studies with PLA have been very limited. The knittings are used for seeding urothelial and smooth
use of PLA in the other forms (composite, porous muscle cells.
membrane, sponge) have been reported as scaffold-
ing devices for tissue engineering [88–93]. However,
more often investigations are carried out on References
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[6] Bastiol C. Biodegradable materials. In: Brody AL, Marsh
A successful scaffold design must include: fiber KS, editors. Wiley encyclopedia of packaging technology.
bonding that provides the required porosity, the 2nd ed. New York: Wiley; 1997. p. 77.
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Poly(lactic acid) ﬁber: An overview

Article in Progress in Polymer Science · April 2007

Bhuvanesh Gupta Nilesh Revagade

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Prog. Polym. Sci. 32 (2007) 455–482

Poly(lactic acid) ﬁber: An overview

Keywords: Poly(lactic acid); Fiber; Spinning; Applications

3.3. Wet spinning of PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472

1. Introduction surface chemistry are all crucial in medical applica-

processibility and biological properties, such as Poly(ureas) Synthetic

is accelerated by in-situ formation of carboxyl end

2. Chemistry of lactic acid and poly(lactic acid)

Fig. 3. Synthesis of polylactic acid [14].

Property Units Condition Value

Degree of crystallinity Xc % L-PLA 0–37

Year Workers Type of spinning Process highlight

1966 Kulkarni et al. [96] Wet spinning Not available

Raw materials Powder materials As-spun ﬁbers Hot-drawn ﬁbers

495 398 19.5 216 45.7 197 9.1 220

30 60 90 120 150 180 210

Fig. 5. Crystallinity versus draw ratio for linear and branched

DR Tg (1C) Tm (1C) Crystallinity Cold-draw

Fig. 6. Supramorphological model for two-step, melt-spun PLA [31].

Samples Die temperature (1C) As-spun ﬁbers Hot drawn ﬁbers

Tg (1C) Tm (1C) Crystallinity (%) Tm (1C) Crystallinity (%) Draw ratio

PLLAb 210 65.7 176.8 20.4 172.3 63.6 5.50

Heat Flow [ W/g]

60 80 100 120 140 160 180

Fig. 7. DSC scans of high-speed spun ﬁbers [2].

2.0 creases. The ‘‘D’’ content in the ﬁber has the

300 MPa and modulus of 6.8 GPa were achieved.

1.0 3.1.2. Morphology

Mechanical properties of ﬁbers obtained with different collection

Fig. 10. Modulus as a function of draw ratio [18].

elongation at break of 20%. The maximum tensile Table 9

Concentration of Nonsolvent Boiling point of Volume ratio Tensile strength (Gpa)

0.133 Pure CHCl3 0.41

average mechanical strength of 0.7 GPa and porous Table 11

Table 13 The spinning rate also has a crucial impact on

Chloroform (f) Toluene (f)

1.6 may be related to the fact that in good solvent the

First Coagulation Bath

Fig. 16. Wet spinning apparatus [46].

Bore injection liquid reservoir Spinneret (enlarged)

First coagulation bath Second coagulation bath

Fig. 17. Scheme of dry-wet spinning process [47].

Fig. 18. Effect of draw ratio on mechanical properties [49].

Syringe Needle The diversiﬁcation of these applications is such that a

An enormous literature is available on the 50

Yang et al. [87] attempted to develop a porous

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