Progress in Polymer Science 33 (2008) 820–852

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Progress in Polymer Science

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

Processing technologies for poly(lactic acid)

L.-T. Lim a,∗ , R. Auras b , M. Rubino b
a
Department of Food Science, University of Guelph, Guelph, Ontario N1G 2W1, Canada
b
School of Packaging, Michigan State University, East Lansing, MI 48824-1223, USA

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

Article history: Poly(lactic acid) (PLA) is an aliphatic polyester made up of lactic acid (2-hydroxy propionic
Received 6 June 2007 acid) building blocks. It is also a biodegradable and compostable thermoplastic derived from
Received in revised form 6 May 2008
renewable plant sources, such as starch and sugar. Historically, the uses of PLA have been
Accepted 7 May 2008
mainly limited to biomedical areas due to its bioabsorbable characteristics. Over the past
Available online 19 June 2008
decade, the discovery of new polymerization routes which allow the economical produc-
tion of high molecular weight PLA, along with the elevated environmental awareness of the
Keywords:
Polylactide general public, have resulted in an expanded use of PLA for consumer goods and packaging
Poly(lactic acid) applications. Because PLA is compostable and derived from renewable sources, it has been
PLA considered as one of the solutions to alleviate solid waste disposal problems and to lessen
Processing the dependence on petroleum-based plastics for packaging materials. Although PLA can
Converting be processed on standard converting equipment with minimal modifications, its unique
Review material properties must be taken into consideration in order to optimize the conversion of
PLA to molded parts, films, foams, and fibers. In this article, structural, thermal, crystalliza-
tion, and rheological properties of PLA are reviewed in relation to its converting processes.
Specific process technologies discussed are extrusion, injection molding, injection stretch
blow molding, casting, blown film, thermoforming, foaming, blending, fiber spinning, and
compounding.
© 2008 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 821
2. Structural composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 821
3. Thermal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 823
4. Crystallization behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
5. Rheological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
6. Thermal degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 827
7. Processing of PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 828

Abbreviations: BD, 1,4-butanedial; BDI, 1,4-butane diisocyanate; DSC, differential scanning calorimetry; BUR, blow-up-ratio; Hrel , endothermic
enthalpy relaxation; Hc , heat of crystallization; Hm , heat of fusion; HDPE, high density polyethylene; HIPS, high impact polystyrene; HMDI, hexamethy-
lene diisocyanate; ISBM, injection stretch blow molding; LDPE, low density polyethylene; MD, machine direction; MDO, machine direction orientation; MFI,
melt flow index; MMT, montmorillonite; Mn , number-average molecular weight; Mw , weight-average molecular weight; OPLA, oriented poly (lactic acid);
OPP, oriented polypropylene; OPS, oriented polystyrene; PEG, poly(ethylene glycol); PET, poly(ethylene terephthalate); PDI, polydispersity index; PDLLA,
poly(d,l-lactic acid); PHA, polyhydroxyalkanoate; PHO, poly(3-hydroxyloctanoate); PLA, poly(lactic acid); PLLA, poly(l-lactic acid); PP, polypropylene; PS,
polystyrene; PVT, pressure–volume–temperature; TD, transverse direction; TDO, transverse direction orientation; Tg , glass transition temperature; Tm ,
melting temperature; WAXS, wide angle X-ray scattering; WVTR, water vapor transmission rate; 0 , zero-shear viscosity.
∗ Corresponding author. Tel.: +1 519 824 4120x56586; fax: +1 519 824 6631.
E-mail address: llim@uoguelph.ca (L.-T. Lim).

0079-6700/$ – see front matter © 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2008.05.004
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 821

7.1. Drying and extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 828

7.2. Injection molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 830
7.3. Stretch blow molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 833
7.4. Cast film and sheet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 835
7.5. Extrusion blown film . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 836
7.6. Thermoforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837
7.7. Foaming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 838
7.8. Fiber spinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 840
7.9. Electrospinning of ultrafine fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 841
7.10. PLA blends with other polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
7.11. Compounding of PLA composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 846
7.12. PLA nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
8. Conclusion: prospects of PLA polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849

1. Introduction such as ethyl acetate and d-limonene, are comparable to

PET [11]. Mechanically, unoriented PLA is quite brittle, but
Thermoplastic polymers exhibit many properties ideal possesses good strength and stiffness. Oriented PLA pro-
for use in packaging and other consumer products, such vides better performance than oriented PS, but comparable
as light weight, low process temperature (compared to to PET [9]. Tensile and flexural moduli of PLA are higher than
metal and glass), variable barrier properties to match end- high density polyethylene (HDPE), polypropylene (PP) and
use applications, good printability, heat sealable, and ease PS, but the Izod impact strength and elongation at break val-
of conversion into different forms. Today, most plastics ues are smaller than those for these polymers [12]. Overall,
are derived from non-renewable crude oil and natural PLA possesses the required mechanical and barrier proper-
gas resources. While some plastics are being recycled and ties desirable for a number of applications to compete with
reused, the majority are disposed in landfills due to end-use existing petroleum-based thermoplastics.
contamination. In 2005, plastics were recovered at a rate Today, the main conversion methods for PLA are based
lower than 10% in the USA [1]. Over the past decade, there on melt processing. This approach involves heating the
has been a sustained research interest on compostable polymer above its melting point, shaping it to the desired
polymers derived from renewable sources as one of the forms, and cooling to stabilize its dimensions. Thus, under-
solutions to alleviate solid waste disposal problems and to standing of thermal, crystallization, and melt rheological
lessen the dependence on petroleum-based plastics. behaviors of the polymer is critical in order to optimize
Poly(lactic acid) (PLA) is a compostable polymer derived the process and part quality. Some of the examples of
from renewable sources (mainly starch and sugar). Until melt processed PLA are injection molded disposable cut-
the last decade, the main uses of PLA have been limited to lery, thermoformed containers and cups, injection stretch
medical applications such as implant devices, tissue scaf- blown bottles, extruded cast and oriented films, and melt-
folds, and internal sutures, because of its high cost, low spun fibers for nonwovens, textiles and carpets [6,13,14].
availability and limited molecular weight. Recently, new PLA also finds uses in other less conventional applications,
techniques which allow economical production of high such as for the housing for laptop computers electronics
molecular weight PLA polymer have broadened its uses [14–17]. Recently, PLA has also been processed in conjunc-
[2]. Since PLA is compostable and derived from sustain- tion with other filler materials to form composites which
able sources, it has been viewed as a promising material possess various unique properties, including those based
to reduce the societal solid waste disposal problem [3,4]. on nanoclays [18–23], biofibers [16,24,25], glass fibers [26]
Its low toxicity [5], along with its environmentally benign and cellulose [27,28]. The aim of this review is to discuss
characteristics, has made PLA an ideal material for food the key process technologies for PLA and summarize the
packaging and for other consumer products [6]. properties of PLA related to the processing techniques used.
PLA belongs to the family of aliphatic polyesters derived
from ␣-hydroxy acids. The building block of PLA, lactic 2. Structural composition
acid (2-hydroxy propionic acid), can exist in optically active
d- or l-enantiomers. Depending on the proportion of the The basic building block of PLA, lactic acid, can be pro-
enantiomers, PLA of variable material properties can be duced by carbohydrate fermentation or chemical synthesis.
derived. This allows the production of a wide spectrum of Currently, the majority of lactic acid production is based
PLA polymers to match performance requirements. PLA has on the fermentation route. Various purification technolo-
reasonably good optical, physical, mechanical, and barrier gies for lactic acid and lactide can be found in a recent
properties compared to existing petroleum-based poly- review by Datta and Henry [2]. One of the main drivers
mers [7]. For instance, the permeability coefficients of CO2 , for the recent expanded use of PLA is attributable to the
O2 , N2 , and H2 O for PLA are lower than for polystyrene (PS), economical production of high molecular weight PLA poly-
but higher than poly(ethylene terephthalate) (PET) [8–10]. mers (greater than ∼100,000 Da). These polymers can be
The barrier properties of PLA against organic permeants, produced using several techniques, including azeotropic
822 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 1. Synthesis of PLA from l- and d-lactic acids. Adapted from Auras et al. [3] by permission of Wiley–VCH Verlag GmbH & Co. KGaA.
dehydrative condensation, direct condensation polymer-
ization, and/or polymerization through lactide formation
(Fig. 1). By and large, commercially available high molecular
weight PLA resins are produced via the lactide ring-opening
polymerization route [3,4,29].
Commercial PLA are copolymers of poly(l-lactic acid)
(PLLA) and poly(d,l-lactic acid) (PDLLA), which are pro-
duced from l-lactides and d,l-lactides, respectively [3]. The
l-isomer constitutes the main fraction of PLA derived from
renewable sources since the majority of lactic acid from
biological sources exists in this form. Depending on the
composition of the optically active l- and d,l-enantiomers,
PLA can crystallize in three forms (␣, ␤ and ␥). The ␣-
structure is more stable and has a melting temperature Tm
of 185 ◦ C compared to the ␤-structure, with a Tm of 175 ◦ C
[3]. The optical purity of PLA has many profound effects
on the structural, thermal, barrier and mechanical proper-
ties of the polymer [30–36]. PLA polymers with l-content
greater than ∼90% tend to be crystalline while those with
lower optical purity are amorphous. Moreover, Tm , glass
transition temperature Tg , and crystallinity decrease with
decreasing l-isomer content [30,34,37]. Tsuji et al. reported
that the optical impurity of PLLA films ranging from 0–50%
was insignificant in affecting the water vapor transmis-
sion rate (WVTR) of the polymer; nevertheless, the WVTR
values decreased with increasing film crystallinity in the
0–20% range [31]. Thus, judicious selection of appropriate
PLA resin grade is important to match the conversion pro-
cess conditions used. Usually, PLA articles which require
heat-resistant properties can be injection molded using
PLA resins of less than 1% d-isomer. Alternatively, nucle-
ating agents may be added to promote the development of
crystallinity under relatively short molding cycles. In con-
trast, PLA resins of higher d-isomer contents (4–8%) would
be more suitable for thermoformed, extruded, and blow
molded (e.g., injection molded preform for blow molding)
products, since they are more easily processed when the
crystallinity is low [38].
When exposed to elevated temperatures, PLA is known
to undergo thermal degradation, leading to the formation
of lactide monomers (Section 3). It has been suggested
that this property may be leveraged for the feedstock
recycling of PLA [39,40]. However, the propensity for the
lactide monomer to undergo racemization to form meso-
lactide can impact the optical purity and thus the material
properties of the resulting PLA polymer [39–43]. Recently,
Tsukegi et al. reported that at temperature less than
200 ◦ C, conversion of PLLA into meso-lactide and oligomers
was minimal. However, above this temperature, the for-
mation of meso-lactide became quite significant (4.5 wt%
at 200 ◦ C and 38.7 wt% at 300 ◦ C for 120 min heating).
Oligomers were reported to form at temperatures higher
than 230 ◦ C [39]. These authors also reported that the
oligomerization proceeded rapidly in the presence of MgO,
to reach an equilibrium between monomers and oligomers;
the l,l:meso:d,d lactide composition ratio converged to
1:1.22:0.99 (w/w/w) after 120 min heating at 300 ◦ C [39].
Fan et al. reported that the racemization at 250–300 ◦ C
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 2. Comparison of glass transition and melting temperatures of PLA
with other thermoplastics.
can be controlled by adding calcium oxide to PLLA, which
reduces the pyrolysis temperature, and more importantly,
leads to predominant l,l-lactide formation [40].
3. Thermal properties
Similar to many thermoplastic polymers, semicrys-
talline PLA exhibits Tg and Tm . Above Tg (∼58 ◦ C) PLA is
rubbery, while below Tg , it becomes a glass which is still
capable to creep until it is cooled to its ␤ transition tem-
perature at approximately −45 ◦ C, below which it behaves
as a brittle polymer [44]. Fig. 2 compares PLA’s Tg and Tm
values with other polymers. As shown, PLA has relatively
high Tg and low Tm as compared to other thermoplastics.
The Tg of PLA is dependent on both the molecular
weight and the optical purity of the polymer (Fig. 3). The
Tg increases with molecular weight to maximum values
at infinite molecular weight of 60.2, 56.4 and 54.6 ◦ C for
PLA consisting of 100, 80, and 50% l-stereoisomer contents,
respectively. Furthermore, PLA with higher content of l-
lactide has higher Tg values than the same polymer with
the same amount of d-lactide [37]. Similar relationships
were reported by Tsuji and Ikada [34]. Table 1 shows the
Fig. 3. Glass transition temperatures for PLAs of different l-contents as a
function of molecular weight. Curves are created based on the original data
published by Dorgan et al. [37] by permission of The Society of Rheology.
823
Table 1
Primary transition temperatures of selected PLA copolymers
Copolymer ratio Glass transition Melting temperature (◦ C)
temperature (◦ C)
100/0 (l/d,l)-PLA 63 178
95/5 (l/d,l)-PLA 59 164
90/10 (l/d,l)-PLA 56 150
85/15 (l/d,l)-PLA 56 140
80/20 (l/d,l)-PLA 56 125
Adapted from Bigg [33].
glass transition and melting temperatures of different PLA
polymers produced with different ratios of copolymer.
In general, the relationship between Tg and molecular
weight can be represented by the Flory–Fox equation:
Tg∞ − K
Tg = (1)
M̄n
where Tg∞ is the Tg at the infinite molecular weight, K is a
constant representing the excess free volume of the end
groups for polymer chains, and M̄n is the number aver-
age molecular weight. The values of Tg∞ and K are around
57–58 ◦ C and (5.5–7.3) × 104 as reported in the literature
for PLLA and PDLLA, respectively [45].
The glass transition behavior of PLA is also dependent
on the thermal history of the polymer. Quenching the poly-
mer from the melt at a high cooling rate (>500 ◦ C/min, such
as during injection molding) will result in a highly amor-
phous polymer. PLA polymers with low crystallinity have a
tendency to undergo rapid aging in a matter of days under
ambient conditions [46,47]. The phenomenon is an impor-
tant contributor to the embrittlement of PLA. This topic will
be discussed in greater details in Section 7.2.
The Tm of PLA is also a function of its optical purity.
The maximum practical obtainable Tm for stereochemically
pure PLA (either l or d) is around 180 ◦ C with an enthalpy
of 40–50 J/g. The presence of meso-lactide in the PLA struc-
ture can depress the Tm by as much as 50 ◦ C, depending
on the amount of d-lactide incorporated to the polymer.
Fig. 4 shows the variation of the Tm as a function of % meso-
lactide introduced in the PLA based on data from Witzke
Fig. 4. Peak melting temperature of PLA as a function of % meso-lactide.
() Represents values reported by Witzke [48]; (䊉) represents values
reported by Hartmann [49]; solid line is calculated based on Eq. (2).
824 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852

[48] and Hartmann [49]. The relationship of Tm and meso-

lactide content can be approximated reasonably well by the
following expression [48]:

Tm (◦ C) ≈ 175 ◦ C − 300 Wm (2)

where Wm is the fraction of meso-lactide below 0.18 level,

and 175 ◦ C is the melting temperature of PLA made of 100%
l-lactide. Typical Tm values for PLA are in the range of
130–160 ◦ C. The Tm depression effect of meso-lactide has
several important implications as it helps expand the pro-
cess windows, reduce thermal and hydrolytic degradation,
and decrease lactide formation.
Pyda et al. determined the heat capacity of PLA in solid
and liquid states ranging from 5 to 600 K [36]. The heat
capacity (Cp-liquid , J K−1 mol−1 ) can be represented in a sim-
ple form: Cp-liquid = 120.17 + 0.076T, where T is in Kelvin (K).

4. Crystallization behavior Fig. 5. DSC thermograms of water quenched, air-annealed (cooled from
220 ◦ C to ambient temperature in 5 min), and full-annealed (cooled from
220 ◦ C to ambient temperature in 105 min) PLLA samples. DSC scans were
The physical, mechanical and barrier properties of performed at a heating rate of 10 ◦ C/min. Adapted from Sarasua et al. [32]
PLA are dependent on the solid-state morphology and by permission of John Wiley & Sons, Inc.
its crystallinity. Accordingly, the crystallization behaviors
of PLA have been studied in detail by many researchers
[4,32,50–55]. PLA can be either amorphous or semicrys-
talline depending on its stereochemistry and thermal
history. The crystallinity of PLA is most commonly deter-
mined using the differential scanning calorimetry (DSC)
technique. By measuring the heat of fusion Hm and heat
of crystallization Hc , the crystallinity can be determined
based on the following equation:
Hm − Hc
crystallinity (%) = × 100 (3)
93.1
where the constant 93.1 J/g is the Hm for 100% crystalline
PLLA or PDLA homopolymers.
On quenching the optically pure PLA polymer from the
melt phase (e.g., during injection molding process), the
resulting polymer will become quite amorphous. As shown
in Fig. 5, quenching the polymer from melt at a high cooling
rate resulted in an exothermic crystallization peak on the Fig. 6. DSC scans for 1.5% d-lactide PLA samples cooled from the melt at
DSC thermogram during the subsequent reheat, while slow 10 K/min and then reheated at different heating rates from 30 to 0.3 K/min.
Adapted from Pyda et al. [36] by permission of Elsevier B.V.
cooling produced a polymer with higher crystallinity with
much lower enthalpy of crystallization. The tendency for
PLA to crystallize upon reheat also depended on the heating related in the following form [54,57]:
rate (Fig. 6), as well as the optical purity of the PLA polymer 4be Tm
(Fig. 7). As shown in Fig. 7, PLA polymers with greater than Kg = (4)
Hf k
∼8% d-isomer level remained amorphous even after 15 h of
isothermal treatment at 145 ◦ C. In contrast, at 1.5% d-isomer where Kg is the nucleation constant, b is the layer thickness
level, although the quenched sample (“Quenched PLA-l”) of the crystal,  is the lateral surface energy,  e is the
has a minimal crystallinity, the isothermal treatment at fold surface energy, Hf is the heat of fusion per unit
145 ◦ C resulted in a large endothermic melting peak around volume, and k is the Boltzmann constant. Table 2 shows
450 K (Fig. 7). In general, the crystallization half-time of the nucleation parameters from isothermal and non-
PLA increases about 40% for every 1% (w/w) meso-lactide
Table 2
in the polymerization mixture, which is mainly driven by
Nucleation parameters from isothermal and nonisothermal kinetic anal-
the reduction of the melting point for the copolymer [56]. yses for PLLA
Nucleation parameters for PLLA crystallization under
isothermal and nonisothermal conditions were determined Parameter Isothermal Non-isothermal

by Kishore and Vasanthakumari using DSC and microscopy Nucleation parameter, Kg (×10 )5
2.44 2.69
[54]. They reported that the radius growth rate of the crys- Lateral surface energy,  (×103 J/m2 ) 12.0 13.6
 ×  e (×106 J2 /m4 ) 753 830
tals decreased as molecular weight increased, as observed
in many other polymers. The nucleation parameters are Adapted from Kishore and Vasanthakumari [54].
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 7. DSC scans at 20 K/min for PLA with 1.5% (PLA-L), 8.1% (PLA-M),
and 16.4% (PLA-H) d-isomers. All samples were cooled quickly from the
melt and isothermally crystallized at 145 ◦ C for 15 h. The quenched PLA-L
sample was cooled similarly from the melt but did not undergo the 15 h
isothermal crystallization. Thermograms are recreated based on the data
originally published by Pyda et al. [36] by permission of Elsevier B.V.
isothermal kinetic analysis of PLLA. Solving Eq. (4) with
Tm = 480 K, Hf = 111.083 × 106 J/m3 ; b = 5.17 × 10−8 cm,
12.03 × 10−3 J/m2 , and  e = 6.089 × 10−4 J/m2 , Kg can be
determined. This value can be used to evaluate the transi-
tion between two types of crystallization behavior in PLA.
In the first type of crystallization, the nucleation rate is
low and axialite morphology in the films is prevalent. In
the second type, the nucleation rate is high, so multinu-
cleation occurs and spherulitic morphology in the films
is observed [57]. For PLLA, both crystallization processes
have been observed depending on the molecular weight
of the samples. The infinite dissolution temperature Td0
(determined by the extrapolation of dissolution tempera-
ture Td versus crystallization temperature Tc plots to the
intersection where Td = Tc ) for PLLA in p-xylene solution
was determined by Kalb and Pennings to be 126.5 ◦ C [58].
This temperature is relevant for fiber formation processes,
since fibers prepared from solution near this temperature
have ultra-high strength properties [58].
The formation of crystallinity may or may not be favor-
able depending on the end-use requirements of the PLA
articles. For instance, high crystallinity will not be opti-
mal for injection molded preforms which are intended
for further blow molding since rapid crystallization of the
polymer would hamper the stretching of the preform and
optical clarity of the resulting bottle. In contrast, increased
crystallinity will be desirable for injection molded articles
for which good thermal stability is important. Crystal-
lization of PLA articles can be initiated by annealing at
temperatures higher than Tg and below the melting point
to improve their thermal stability. For instance, Perego et
al. showed that crystallization of injection molded PLLA
parts by annealing at 105 ◦ C for 90 min increased tensional
and flexural elasticity, Izod impact strength, and heat resis-
tance [59]. After annealing PLA copolymers, the presence
of two melting peaks in a DSC scan is quite common, as
previously observed by Yasuniwa et al. [60]. They reported
that the low temperature Tm peak height increased with
825
Fig. 8. Development of crystallinity in biaxially stretched PLA at 80 ◦ C
using 100% s−1 strain rate. Data are adapted from Drumright et al. [38]
by permission of Wiley–VCH Verlag GmbH & Co. KGaA.
increasing heating rate, whereas the high temperature Tm
decreased. In contrast, increasing the cooling rate reduced
the low Tm peak, while the high Tm peak increased. The
double-melting peak behavior was explained based on
melt-recrystallization model, in which small and imper-
fect crystals changed successively into more stable crystals
through the melting and recrystallization [60].
Another strategy to increase the crystallinity of PLA is
by incorporating nucleating agent in the polymer during
extrusion. This lowers the surface free energy barrier for
nucleation and enables crystallization at higher tempera-
ture to take place upon cooling. Kolstad showed that talc
can be added to PLLA to effectively modify the crystalliza-
tion rate of the polymer [56]. With 6% talc added to PLLA,
the crystallization half-time of the polymer reduced from
3 min at 110 ◦ C to approximately 25 s. At the same percent of
talc, for 3% mesolactide copolymerized with the l-lactide,
the half-time reduced from about 7 min to about 1 min [56].
Li and Huneault compared the crystallization kinetics of
talc and montmorillonite (MMT, Cloisite® Na+ ) for 4.5% d-
PLA. They reported that the lowest crystallization induction
period and maximum crystallization speeds were observed
around 100 ◦ C. By adding 1% (w/w) of talc, the crystalliza-
tion half time of PLA was decreased from a few hours to
8 min. In contrast, the MMT tested was less effective as a
nucleating agent; the lowest half-time achieved was 30 min
[61].
Unlike quiescent crystallization discussed above, strain-
induced crystallization occurs when the polymer is
mechanically orientated. This phenomenon is prevalent
during the production of oriented PLA films, stretch blow
molding of bottles, thermoforming of containers, and fiber
spinning. As expected, the proportion of d- and l-isomers
has an effect on the strain-induced crystallinity during
the mechanical orientation. As shown in Fig. 8, the per-
cent crystallinity of amorphous PLA sheet increases with
increasing draw ratio. Moreover, the crystallinity decreases
as the stereoisomeric purity of the polymer decreases [38].
The amount of crystallinity attained through orientation
also depends on the mode of stretching (sequential ver-
826 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 9. Comparison of zero-shear viscosity values versus molecular weight
for poly(85% l-co-15% d-lactide) at 85 and 100 ◦ C as reported by Witkze
[48], and PLLA at 180 ◦ C as reported by Dorgan et al.[12].
sus simultaneous), strain rate, temperature, and annealing
conditions [38,62,63]. More discussions on this topic will
be presented in Section 7.2.
5. Rheological properties
Melt rheological properties of PLA have a profound
effect on how the polymer flows during the conver-
sion process. Since the PLA rheological properties are
highly dependent on temperature, molecular weight and
shear rate, they must be taken into consideration during
tooling design, process optimization, and process model-
ing/simulation. Melt viscosities of high-molecular-weight
PLA are in the order of 5000–10,000 P (500–1000 Pa s)
at shear rates of 10–50 s−1 . These polymer grades are
equivalent to Mw ∼100,000 Da for injection molding to
∼300,000 Da for film cast extrusion applications [4]. The
melts of high molecular weight PLA behave like a pseu-
doplastic, non-Newtonian fluid. In contrast, low molecular
weight PLA (∼40,000 Da) shows Newtonian-like behavior
at shear rates typical of film extrusion [64]. Under iden-
tical processing conditions, semicrystalline PLA tends to
possess higher shear viscosity than its amorphous counter-
part. Moreover, as shear rates increase, the viscosities of the
melt decrease considerably, i.e., the polymer melt exhibits
shear-thinning behavior [65].
Viscoelastic properties of polymer melts can be charac-
terized by zero-shear viscosity, 0 , and recoverable shear
compliance JeO . Both of these parameters can be obtained
from dynamic experiments by determining the dynamic
moduli at the limit of low frequency [48]. The product of
these two values (0 × JeO ) gives the average relaxation time
required for final stress equilibration time in the liquid  0 .
The value of 0 is strongly affected by the molecular weight,
which is typically described empirically by the power law
equation. Cooper-White and Mackay reported that the 0
of PLLA melt showed dependence on Mw to the 4.0 power
instead of the theoretical value of 3.4 [64]. In comparison,
Dorgan et al. reported a power index of 4.6 [66]. Fig. 9 shows
the relationship between 0 and Mw for PLLA (100:0) at
180 ◦ C [12], and 15% d-lactide PDLA at 85 and 100 ◦ C [48].
Witkze showed that the temperature effect on 0 for 15%
d-lactide PLA can be described by [48]:
 Mw
a E  1 1

a
0 = n0,ref exp − (5)
100, 000 R T (K) 373
where a = 3.38 ± 0.13, the activation energy of flow
Ea = 190 kJ/mol, 0,ref = 89,400 ± 9300 Pa s, R is the gas
constant 8.314 J/K mol, and T is the temperature in K.
Witzke further showed that 0 can be correlated with
the isomer composition by fitting to the well-known
Williams–Landel–Ferry equation (WLF) [48]:
 Mw
3.38
0 = (a1 + a2 Wmeso + a3 Wl-mer )
100, 000
 −C (T (C) − 100) 
1
×exp (6)
C2 + (T (C) − 100)
where Wmeso and Wl-mer are the initial weight frac-
tions for meso-lactide and l-lactide, respectively,
a1 = −13,000, a2 = −142,000, a3 = 112,000, C1 = 15.6 ± 1.6,
and C2 = 110 ± 11 ◦ C; a1 , a2 , a3 , and C1 do not have units;
and T(C) is the testing temperature in ◦ C. Eq. (6) can
be used to predict 0 of amorphous polylactides with
l-monomer composition higher than 50% between Tg
and Tg + 100 ◦ C. The equation predicts that 0 increases
with increasing l-monomer and decrease as meso-lactide
content increases [48].
The rheological properties of PLA can be modified by the
introduction of branching into the polymer chain architec-
ture. Many routes, such as multifunctional polymerization
initiators, hydroxycyclic ester initiators, multicyclic ester,
and crosslinking via free radical addition have been used
to introduce branching in PLA [12,67–69]. Lehermeier
and Dorgan blended PLA with 5% d-isomer with varying
proportions of branched PLA produced through peroxide
initiated crosslinking of linear PLA by reactive extrusion
[67]. They observed that 0 of the blends deviated con-
siderably from the log additive rule and attributed this to
the effect of free volume. Lehermeier and Dorgan showed
that tris(nonylphenyl) phosphite was effective for stabi-
lizing the viscosity of PLA during the thermorheological
time sweep experiment of branched PLA polymers [67]. In
another study from the same research group, the stabiliz-
ing effect of tris(nonylphenyl) phosphate was elucidated
by using the time-temperature superposition technique,
showing that this compound greatly facilitated the ther-
morheological experiments by prevented the confounding
effect from degradation reactions [69,70].
Carreau–Yasuda model (Eq. (7)) has been used to model
the viscosity and shear rate relationship of linear PLA and
linear-branched PLA blends [69]:
˙ C3 ](C4 −1/C3 )
 = C1 [1 + (C2 ) (7)
where  is the viscosity,  is the shear rate, and C1 , C2 , C3
and C4 are material dependent parameters. The constants
for the model are summarized in Table 3. C1 determines
0 which decreases with increasing linear content. C2 is
the relaxation time approximately corresponded to the
reciprocal of frequency for the onset of shear thinning.
C3 determined the shear thinning which increased with
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 827

Table 3 weight. The Mark–Houwink equation is dependent on the

Carreau–Yasuda model parameters for Eq. (7)
type of PLA, the solvent used, and the temperature of the
Blend, % Carreau–Yasuda parameters solution. Table 4 summarizes the Mark–Houwink parame-
C1 (Pa s) C2 (s) C3 C4 ters for different compositions of PLA polymers in different
solvent solutions.
0 10,303 0.01022 0.3572 −0.0340
20 8,418 0.00664 0.3612 −0.0731
40 6,409 0.01364 0.4523 0.0523
60 5,647 0.00513 0.4356 −0.1002 6. Thermal degradation
80 4,683 0.00450 0.4754 −0.1108
100 3,824 0.01122 0.7283 0.0889 One of the drawbacks of processing PLA in the molten
Adapted from Lehermeir and Dorgan [69]. state is its tendency to undergo thermal degradation, which
is related both to the process temperature and the resi-
dence time in the extruder and hot runner [72]. By and
increasing linear content, i.e., branched PLA shear thinned
large, thermal degradation of PLA can be attributed to:
stronger than the linear material [69]. The increase of both
(a) hydrolysis by trace amounts of water, (b) zipper-like
0 and shear thinning with the addition of branching is
depolymerization, (c) oxidative, random main-chain scis-
also reported by other studies on PLA polymers with star
sion, (d) intermolecular transesterification to monomer
polymer chain architectures [12,66].
and oligomeric esters, and (e) intramolecular transesteri-
Palade et al. studied the extensional viscosities of high l-
fication resulting in formation of monomer and oligomer
content PLA (100,000–120,000Mw ). They showed that PLA
lactides of low Mw [73]. Kopinke et al. proposed that above
can be drawn to large Hencky strains without breaking. The
200 ◦ C, PLA can degrade through intra- and intermolecu-
polymer also exhibited strain-hardening behaviors during
lar ester exchange, cis-elimination, radical and concerted
the deformation [70], which is an important characteris-
non-radical reactions [41], resulting in the formation of CO,
tic for processing operations, such as fiber spinning, film
CO2 , acetaldehyde and methylketene. In contrast, McNeill
casting, and film blowing. Yamane et al. reported that the
and Leiper proposed that thermal degradation of PLA is a
addition of PDLA to PLLA enhanced the strain hardening
non-radical, “backbiting” ester interchange reaction involv-
properties of the resulting blends even at very low PDLA
ing the -OH chain ends [74]. Depending on the point in
contents (<5 wt%). They also reported that low Mw PDLA
the backbone at which the reaction occurs, the product
affected the shear rheology of the blends much more sig-
can be a lactide molecule, an oligomeric ring, or acetalde-
nificantly than high Mw PDLA [71]. This may provide an
hyde plus carbon monoxide (Fig. 10). Similar degradation
effective avenue for modifying the spinning behavior of the
mechanisms were reported by Kopinke et al. [41]. At tem-
PLA.
peratures in excess of 270 ◦ C, homolysis of the polymer
Although solution viscosity of PLA in solvent does not
backbone can occur. The formation of acetaldehyde is
provide direct relevance to the processing of molten PLA
expected to increase with increasing process temperature
polymer, this property is frequently evaluated to deter-
due to the increased rate of the degradation reactions. In
mine the molecular weight of resins and processed parts
the 230–440 ◦ C temperature range explored by McNeill and
to ensure that they are within the required specifications.
Leiper [74], acetaldehyde is formed in highest proportion at
The relationship between viscosity and molecular weight
230 ◦ C and a marked decrease is observed at 440 ◦ C, which
of PLA dissolved in dilute solution is commonly modeled
is believed to be caused by the thermal degradation of
using the Mark–Houwink equation:
acetaldehyde, involving a complex chain reaction to form
[] = K × Mva (8) methane and carbon monoxide at the elevated tempera-
ture. McNeill and Leiper also proposed that the formation
where [] is the intrinsic viscosity, K and a are constants, of butane-2,3-dione, another byproduct detected, is likely
and Mv is the experimental viscosity average molecular caused by the radical combination of acetyl radicals from

Table 4
Mark–Houwink constants PLA in selected solvents

Polymer types Equations Conditions

(1) PLLA [] = 5.45 × 10−4 Mv0.73 25 ◦ C in chloroform [59,189]

(2) PDLLA [] = 1.29 × 10−5 Mv0.82 25 ◦ C in chloroform [190]
(3) PDLLA [] = 2.21 × 10−4 Mv0.77 25 ◦ C in chlofoform [59,189]
(4) Linear PLLA [] = 4.41 × 10−4 Mv0.72 25 ◦ C in chloroform [190]
(5) “Star” PLLA (six arms) [] = 2.04 × 10−4 Mv0.77 25 ◦ C in chloroform [190]
(6) PDLLA []¦ = 2.59 × 10−4 Mv0.689 35 ◦ C in THFa [191]
(7) PDLLA [] = 5.50 × 10−4 Mv0.639 31.15 ◦ C in THF [191]
(8) PLLA (amorphous) [] = 6.40 × 10−4 Mv0.68 30 ◦ C in THF [192]
(9) PLLA (amorphous/semi-crystalline) []¦ = 8.50 × 10−4 Mv0.66 30 ◦ C in THF [192]
(10) PLLA (semi-crystalline) [] = 1.00 × 10−3 Mv0.65 30 ◦ C in THF [192]
(11) PDLLA [] = 2.27 × 10−4 Mv0.75 (one point method) 30 ◦ C in benzene [193], Tuan–Fuoss viscometer
(12) PDLLA [] = 1.58 × 10−4 Mv0.78 25 ◦ C in ethyl acetate [194]

Adapted from Garlotta [4].

a
THF: tetrahydrofuran.
828 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 10. Thermal degradation of PLA. Adapted from McNeill and Leiper [74] by permission of Elsevier B.V.
the chain reaction [74]. Although acetaldehyde is consid-
ered to be non-toxic and it is naturally present in many
foods, the acetaldehyde generated during melt processing
of PLA must be minimized, especially if the converted PLA
(e.g., container, bottle, and films) are to be used for food
packaging. The migration of acetaldehyde into the con-
tained food can result in off-flavor which may impact the
organoleptic properties and consumer acceptance of the
product [75–77].
From the production point of view, the formation of
lactide due to depolymerization is undesirable. Besides
reducing PLA melt viscosity and elasticity, the volatile lac-
tide formed can result in fuming and/or fouling of the
processing equipment such as chilled rollers, molds and
tooling surfaces [78]. The latter is characterized by the
gradual building up of a layer of lactide on the equipment
surfaces, commonly known as plate out. To overcome this
problem, the temperature of the equipment is generally
elevated to reduce the tendency of condensation of lactide.
Taubner and Shishoo showed that the moisture content
of resin, temperature, and residence time of PLA melt
during extrusion are important contributors to molecular
weight drop of the polymer during extrusion [72]. Pro-
cessing of dried PLLA with initial Mn of 40,000 g/mol in
a twin-screw extruder at 210 ◦ C caused the Mn to drop to
33,600 and 30,200 g/mol, when screw rotation speeds of
120 and 20 rpm were used, respectively. Using the same
120 and 20 rpm screw speeds but processing at 240 ◦ C,
the Mn values decreased dramatically to 25,600 and
13,600 g/mol, respectively. In contrast, Mn for extruded
articles produced from wet resins (equilibrated at 20 ◦ C
65% RH to give 0.3%, w/w, moisture content) were 18,400
and 12,000 g/mol, respectively. These results highlighted
the importance of minimizing the residence time and
process temperature during PLA extrusion. From a resin
formulation point of view, the residual polymerizing
catalysts present in the resin are also known to catalyze
the reverse depolymerization and hydrolysis reactions
[48,79]. This may partially explain the large variation of
molecular weight drop for melt processed PLA reported
in the literature. For instance, Witzke, Gogolewski et al.
and Perego et al. reported molecular weight losses for
injection molded PLA parts of 5–52%, 50–88% and 14–40%,
respectively [48,59,80]. To stabilize the polymer during
melt processing, the removal or deactivation of the residual
catalyst is important to minimize the molecular weight
loss which will impact the mechanical properties of the
PLA parts. Strategies to improve the melt stability of PLA
can be found in patent publications [79,81,82]. Due to
the different processes and technologies used, the melt
stability of PLA polymer may be different from supplier to
supplier. Injection molded PLA made from properly dried
good quality PLA resins and optimal processes should
exhibit molecular weight loss of 10% or less [83].
7. Processing of PLA
7.1. Drying and extrusion
Prior to melting processing of PLA, the polymer must be
dried sufficiently to prevent excessive hydrolysis (molec-
ular weight drop) which can compromise the physical
properties of the polymer. Typically the polymer is dried to
less than 100 ppm (0.01%, w/w). Natureworks LLC, one of
the main suppliers for PLA polymers, recommended that
resins should be dried to 250 ppm (0.025%, w/w) mois-
ture content or below before extrusion. Processes that
have long residence times or high temperature approaching
240 ◦ C should dry resins below 50 ppm to achieve maxi-
mum retention of molecular weight [84,85]. Drying of PLA
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Table 5
Drying half times for PLA pellets under −40 ◦ C dew point and air flow rate
of 0.016 m3 /(min kg) [108]
Drying temperature (◦ C) Drying half time (h)
Amorphous pellets
40 4.0
Crystalline pellets
40 4.3
50 3.9
60 3.3
70 2.1
80 1.3
100 0.6
takes place in the temperature range of 80–100 ◦ C. The
required drying time is dependent on the drying temper-
ature (Table 5). Commercial grade PLA resin pellets are
usually crystallized, which permits drying at higher tem-
peratures to reduce the required drying time. In contrast,
amorphous pellets must be dried below the Tg (∼60 ◦ C) to
prevent the resin pellets from sticking together, which can
bridge and plug the dryer. It is noteworthy that because
PLA degrades at elevated temperatures and high relative
humidity, the resins should be protected from hot and
humid environments. Henton et al. reported that amor-
phous PLA can dramatically reduce its Mw in less than a
month when exposed to 60 ◦ C and 80% RH (Fig. 11) [44].
To achieve an effective drying, the dew point of the
drying air should be −40 ◦ C or lower. Drying of PLA is com-
monly achieved using a closed loop dual-bed regenerative
desiccant-type dryer. In this type of dryer, the resin pellets
are contained in a hopper that is purged with dry air at
elevated temperature. The dry air is generated by the des-
iccant bed. During the operation, one desiccant bed is in
the process air stream which removes moisture from the
resin, while the other stand-by bed is being regenerated
(Fig. 12). The hot air from the process stream removes the
moisture from the resin in the hopper. The air is then circu-
lated back to the dryer where it is cooled and the moisture
is stripped by the desiccant. The air is reheated before it is
channeled back to the hopper. When the dew point of the
Fig. 11. Plots of molecular weight loss of PLA versus time under different
environment conditions. Curves are based on the original data published
by Henton et al. [44].
829
Fig. 12. Typical closed loop dual-bed regenerative desiccant-type dryer
for drying PLA before extrusion.
process air is greater than the set point, the desiccant goes
into the regeneration cycle where the desiccant is heated
to desorb the moisture from the desiccant and vent it to the
atmosphere. Meanwhile, the process air is directed to the
stand-by desiccant which was previously dried.
Extrusion is the most important technique for contin-
uously melt processing of PLA. The plasticizing extruder
can be part of the forming machine systems for injection
molding, blow molding, film blowing and melt spinning.
Fig. 13 shows a schematic representation of the major com-
ponents of an extruder for an injection molding machine. A
typical screw consists of three sections: (1) feed section –
acts as an auger which receives the polymer pellets and
conveys the polymer into the screw; (2) transition sec-
tion (also known as compression or melting sections) –
flight depth decreases gradually, which compresses the pel-
lets to enhance the friction and contact with the barrel. In
order to segregate the molten polymer pool from the pellet
unmelted pellets, various barrier flight designs have been
adopted; (3) metering section – characterized by a constant
and shallow flight depth, which acts as a pump to meter
accurately the required quantity of molten polymer. The
l/d ratio, which is the ratio of flight length of the screw
to its outer diameter, determines the shear and residence
time of the melt. Screws with large l/d ratio provide greater
shear heating, better mixing, and longer melt residence
time in the extruder. Commercial grade PLA resins can typ-
ically be processed using a conventional extruder equipped
with a general purpose screw of l/d ratio of 24–30. Extruder
screws for processing PET, which are typically low-shear for
gentle mixing to minimize resin degradation and acetalde-
hyde generation, are also suitable for processing PLA resin
[14]. Another important screw parameter is the compres-
sion ratio, which is the ratio of the flight depth in the feed
section to the flight depth in the metering section. The
greater the compression ratio a screw possesses, the greater
the shear heating it provides. The recommended compres-
sion ratio for PLA processing is in the range of 2–3 [86].
830 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 13. Typical geometries of a screw for single-screw extruder.
During the plasticizing process, PLA resin pellets are
fed from a hopper near the end of a barrel. The screw,
driven by an electric or hydraulic motor, rotates and trans-
ports the material towards the other end of the barrel. The
heat required for melting is provided by the heater bands
wrapped around the barrel. As the screw rotates, the flights
shear and push the polymer against the wall of the barrel
which also provides frictional heat for melting the poly-
mer. The combined thermal energy from the heater and
frictional heat due to friction between the plastic and the
screw and barrel, provide sufficient heat to raise the PLA
polymer above its melting point (170–180 ◦ C) by the time
it reaches the end of the barrel. To ensure that all the crys-
talline phases are melted and to achieve an optimal melt
viscosity for processing, the heater set point is usually set
at 200–210 ◦ C.
7.2. Injection molding
Injection molding is the most widely used converting
process for thermoplastic articles, especially for those that
are complex in shape and require high dimensional preci-
sion. All injection molding machines have an extruder for
plasticizing the polymer melt. Unlike a standard extruder,
the extruder unit for injection molding machine is designed
such the screw can reciprocate within the barrel to pro-
vide enough injection pressure to deliver the polymer melt
into the mold cavities (Fig. 14). Most injection molding
machines for PLA are based on the reciprocating screw
extruder, although two-stage systems, which integrate a
Fig. 14. Major components of an injection molding machine showing the extruder (reciprocal screw) and clamp units.
shooting pot and extruder in a single machine, have also
been deployed for injection molding of preforms for PLA
bottles. The two-stage system consists an in-line extruder
integrated to a shooting pot. The extruder plasticizes and
feeds the melt into the shooting pot under relatively low
injection pressure, from which the melt is injected into the
hot runner under high pressure by a plunger in the shooting
pot. While the reciprocating machine must stop the screw
during the injection and packing phases, the screw for the
two-stage machine can rotate during the majority of the
cycle. The two-stage system presents some advantages over
its reciprocating counterpart, including shorter cycle time,
small screw motor drive, more consistent melt quality, and
more consistent shot size [87].
A typical cycle for an injection molding machine is pre-
sented in Fig. 15. The beginning of mold close is usually
taken as the start of an injection molding cycle. Immedi-
ately after the molds clamp up, the nozzle opens and the
screw moves forward, injecting the polymer melt into the
mold cavity. To compensate for the material shrinkage dur-
ing cooling in the mold, the screw is maintained in the
forward position by a holding pressure. At the end of the
holding phase, the nozzle is shut off and the screw begins to
recover, while the part continues to be cooled in the mold.
During the recovery phase, the screw rotates and conveys
the polymer forward along the screw. At the same time,
the screw is allowed to slide backward within the barrel
against a controlled back pressure exerted on the screw
by a hydraulic cylinder. To ensure that the part is dimen-
sionally stable enough to withstand the opening stroke the
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 15. Typical cycle for an injection molding process.
molds, sufficient cooling time must be given. In the mold-
ing cycle, heat removal takes place predominantly during
the fill, hold and cool phases, although mold opening phase
also contributes to partial cooling since one side of the part
(core-contacting side) is still being cooled prior to ejection.
Cycle time is an important process parameter which is
often minimized to maximize the production throughput.
To reduce the cycle time, it is quite common to transfer
the partially cooled injection molded article to a post-mold
cooling device, to provide an extended cooling of the part
outside the molds, either by direct contact on a chilled sur-
face and/or by forced air. From Fig. 15, it is also evident
that minimizing the duration for non-process events, such
as mold opening, part ejection and mold closing is also
important for reducing the cycle time. Lowering mold tem-
Fig. 16. PVT plots for PLA based on the data from Sato et al. and Natureworks LLC [88,89]. The continuous lines represent the fitted results based on the
two-domain modified Tait model (Eq. (8)).
831
perature can also increase the heat extraction rate from
the polymer. Nevertheless, the propensity of lactide con-
densation on the cold tooling surfaces, which can affect
the surface finish and weight of the molded articles, limits
the minimal temperature that can be used during injec-
tion molding of PLA to 25–30 ◦ C. The use of molds with
polished surfaces, in conjunction with an increased injec-
tion speed during fill, can also reduce the deposition of the
lactide layers.
The fill, hold and cool events that take place during
injection molding have an important implication on the
shrinkage of the injection molded articles. This effect can
be best elucidated using a pressure–volume–temperature
(PVT) diagram. Fig. 16 shows PVT diagrams for PLA from two
references [88,89]. The different profiles shown here are
likely due to the different grades of PLA used. During injec-
tion molding, the polymer is first subjected to isothermal
injection of the polymer melt into the mold cavity, dur-
ing which the pressure increases as the polymer is being
injected and packed to the holding pressure (trace ab in
Fig. 16). The polymer then undergoes isobaric cooling in
the holding phase (trace bc), followed by isochoric cool-
ing. When the polymer cools below the freezing point, the
gate freezes and the pressure in the mold cavities drops
to one atmospheric pressure (trace cd). In the last cool-
ing phase, the article continues to cool isobarically to room
temperature (trace de). The change in specific volume dur-
ing the final isobaric cooling (trace de) dictates the extent
of part shrinkage. The hold pressure and temperature play
an important role in determining how much the molded
article shrinks.
The PVT relationship can be modeled mathematically,
such as by using the modified two-domain Tait model
[90–92]. This model is often used for numerical simula-
tion of injection molding processes involving finite element
analysis for predicting the shrinkage behavior of injection
832 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 17. Effects of temperature and time on the aging of injection molded 4% d-lactide PDLA specimens. (A) DSC curves of PLA aged at room temperature
for various aging times. (B) DSC curves of PLA annealed for 24 h at different temperatures. Plots are created based on the data from Cai et al. [47].
molded articles. The modified two-domain Tait PVT model
takes the form:
  p

v(T, p) = V0 (T ) 1 − C ln 1 + + Vt (T, p)
B(T )
where v(T, p) is specific volume at temperature T and pres-
sure P; V0 is specific volume at zero gauge pressure and C is
a constant, 0.0894. When the temperature of the material
is greater than the transition temperature, V0 (T) and B(T)
are determined by b1m , b2m , b3m , b4m and b5 as follows:
V0 = b1m + b2m (T − b5 )
B(T ) = b3m exp[−b4m (T − b5 )]
In contrast, when the material temperature is lower than
the transition temperature, V0 (T) and B(T) are determined
by b1s , b2s , b3s , b4s and b5 as follows:
V0 = b1s + b2s (T − b5 )
B(T ) = b3s exp[−b4s (T − b5 )]
Because the transition temperature, Ttrans (P), is often pres-
sure dependent, it is often correlated with pressure and
the transition temperature at zero gauge pressure (b5 ) as
follows:
Ttrans (P) = b5 + b6 p
For non-amorphous materials, an additional transition
function is required:
Vt (T, p) = b7 exp[b8 (T − b5 ) − b9 p]
The estimated parameter values for the modified two-
domain Tait model are shown in the inserts in Fig. 16.
In general, injection molded PLA articles are relatively
brittle. The brittleness of PLA has been attributed to the
rapid physical aging of the polymer since ambient tem-
perature is only about 25 ◦ C below the Tg [37,46,48]. The
aging of PLA can be evaluated by studying the Tg region of
(9) a DSC scan. By measuring the development of endother-
mic enthalpy relaxation Hrel using DSC on injection
molded samples made from PLA (96% l-lactide), Cai et al.
showed that Hrel increased with increasing aging time
[47] (Fig. 17). They also showed that as the aging temper-
ature increased towards the Tg , the rate of physical aging
also became faster. However, when the aging temperature
(10) went above the Tg (60 ◦ C), the excess enthalpy relaxation
was reduced, indicating that physical aging was no longer
(11) taking place when the aging temperature was above Tg [47].
Celli and Scandola observed a similar aging trend for PLLA
using DSC and a dynamic mechanical analyzer [46]. They
observed that the extent of aging increased with decreas-
ing molecular weight (i.e., Hrel increased with decreasing
(12) molecular weight), which was attributed to the increased
chain terminals that possess higher motional freedom than
(13)
the internal chain segments [46]. The physical implication
of aging was elucidated by Witzke, who reported that injec-
tion molded articles tested immediately after quenching
to very cold temperatures exhibited a much larger exten-
sion to break. However, when the molded specimens were
aged at room temperature for 3–8 h, they became very
(14)
brittle [48]. This phenomenon was attributed to the reduc-
tion of free volume of the polymer due to rapid relaxation
towards the equilibrium amorphous state. Aging below Tg is
exclusively related to the amorphous phase of the polymer;
(15) accordingly, increasing the crystallinity of the polymer (e.g.,
by adjusting d-isomer composition or the use of nucleat-
ing agents) will reduce the aging effect. Furthermore, the
crystallites formed also act like physical crosslinks to retard
the polymer chain mobility. However, amorphous injection
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
molded articles which are intended for further process-
ing (e.g., preforms for stretch blow molding), the storage
conditions prior to subsequent processing may need to
be controlled. Moreover, process parameters such as mold
temperature, packing pressure, cooling rate, and post-mold
cooling treatment are expected to influence the PLA aging
behavior as well.
7.3. Stretch blow molding
Due to the recent consumers’ heightened environmen-
tal awareness, there is a sustained interest from the food
industry to replace the existing non-biodegradable ther-
moplastics with PLA for certain beverage products. To date,
PLA bottles are predominantly used for beverages which are
not sensitive to oxygen (e.g., flat water beverages, pasteur-
ized milk). While barrier properties of PLA bottles may be
improved by various technologies (multilayer structures,
external coating, internal plasma deposition, oxygen scav-
enger), their implementation is currently limited due to
higher production costs.
The production of PLA bottles is based on injection
stretch blow molding (ISBM) technique. This process pro-
duces biaxial orientated PLA bottle with much improved
Fig. 18. Injection stretch blow molding (ISBM) of PLA bottle.
833
physical and barrier properties compared to injec-
tion molded amorphous PLA. The molecular orientation
induced during the ISBM process decreases the effect of
aging by stabilizing the polymer free volume [48]. The
crystallites produced during strain-induced crystallization
also reduce the aging effect since they can act as physical
crosslinks to stabilize the amorphous phase, thereby reduc-
ing its brittleness. Similar effects have been reported for
semicrystalline PET [93]. The ISBM process for PLA bottles
is depicted in Fig. 18. It involves first the formation of pre-
form (also known as parison) using an injection molding
machine. The preform is then transferred to a blow mold-
ing machine where it is stretched in the axial direction and
blown in the hoop direction to achieve biaxial orientation
of the polymer. In the blow molding machine, the preform
is heated in front of several banks of infrared heater to tem-
peratures (85–110 ◦ C) suitable for blow molding (Fig. 18a).
Different power settings are usually applied to the infrared
heaters to give a temperature profile optimal for stretch-
ing the preform into bottle with uniform wall thickness
distribution. Frequently, reheat additives, such as carbon
black dispersed in a liquid carrier, are added to the resin
in the extruder to increase its infrared energy absorption.
PLA preforms have a tendency to shrink after reheat, espe-
834 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
cially regions near the neck and the end cap where the
residual injection molding stresses are the greatest. This
may be moderated through proper preform design, with
gradual transition regions. When the preform has attained
the optimal temperature, it is transferred to the blow mold
(Fig. 18b). The blow nozzle is lowered to seal the preform
finish, while the stretch rod travels towards the preform,
at a typical speed of 1–1.5 m/s, and stretches the preform
to the base cup (Fig. 18c–e). During the preblow phase
(Fig. 18d and e), compressed air of 0.5–2.0 MPa is admitted
to the preform through the blow nozzle to partially inflate
the preform to prevent it from touching the stretch rod dur-
ing the axial stretching. When the stretch rod arrives at the
base cup and pins the preform to the mold base, the air pres-
sure ramps up to 3.8–4.0 MPa to fully inflate the preform.
This forces the inflated preform to take the shape of the
blow mold and to imprint the surface details of the bottles
(Fig. 18f and g). The high blow pressure is maintained for
several seconds to allow the bottle to cool down sufficiently
before discharging the bottle.
The aforementioned process is known as the two-stage
process. In contrast, the one-stage process entails the injec-
tion and blow molding of the preform within the same
machine equipped with both injection and blow mold-
ing units. In this process, the injection molded preform
is partially cooled down to 100–120 ◦ C and then stretch
blown in the blow molding station. Fig. 19 summarizes the
thermal history of PLA from resin pellets to bottle for the
two processes. As shown, PLA preform made in the one-
stage process does not go through the aging process during
which the polymer tends to embrittle. Thus, PLA preforms
intended for one- and two-stage processes may need to be
designed and processed differently. The neck finish of the
preform is highly amorphous and is quite brittle. Therefore,
the neck finish must be designed such that the side wall is
thick enough to prevent the neck from blowing out or crack-
Fig. 19. Thermal history of PLA polymer during one- and two-stage PLA bottle manufacturing.
ing due to the compression load from the blow nozzle. The
blow mold temperature for PLA is typically set at around
35 ◦ C. Because the base of the bottle tends to be quite thick,
the residual heat can cause the base to roll out after the
bottle is ejected from the blow mold. This problem can be
overcome by incorporating radial ribs to reinforce the base
and/or chilling the base mold insert to a temperature lower
than the mold halves [94].
Similarly to PET, PLA exhibits strain-hardening when
stretched to high strain. This self-leveling phenomenon is
desirable for blow molding of preforms to achieve optimal
bottle side wall orientation and minimize wall thickness
variation. Since strain-hardening occurs only when the PLA
is stretched beyond its natural stretch ratio, the preform
must be designed to match the target bottle size and shape,
such that optimal stretch ratios are achieved during blow
molding (Fig. 20). Preforms that are under-stretched will
result in bottles with excessive wall thickness variation,
weak mechanical properties and poor aesthetic appeal (e.g.,
lens defect below the support ledge region). In contrast,
overstretched bottles can also result in stress whitening
due to the formation of micro-cracks on the bottle surfaces
that diffract light. Typical commercial grade PLA resins for
bottle applications require preform axial stretch ratios of
2.8–3.2 and hoop stretch ratios of 2–3, with the desirable
planar stretch ratio of 8–11 [94,95]. It is noteworthy that the
ultimate amount of crystallinity after stretching decreases
with the decreasing stereoisomeric purity of the polymer
[38]. Accordingly, the optimal stretch ratios depend on the
grade of PLA used.
Preform designs are often proprietary, and therefore
there is a lack of information in the open literature. An opti-
mal preform design should meet the minimum required
stretching which is above the natural stretch ratio, by vary-
ing the shape, diameter, length, blend radius, and transition
features, to meet the part weight requirement. Depending
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 20. Schematic representation of PLA preform (left) and bottle (right), showing their key features and main stretch ratios used for preform design.
on the shape of the bottle, subtle but critical features such
as transition shape (reverse versus standard taper), step
changes, and pinch points on the core and cavity may also
be incorporated in the preform design. Since the stretching
behavior of PLA is similar to PET but not entirely the same,
conversion of materials using existing PET preform designs
may be feasible, although design modifications are often
required to achieve an optimized bottle.
7.4. Cast film and sheet
PLA with l-lactide contents of 92–98% have been
successfully extruded using conventional extruders. The
production of PLA film and sheet is practically identical; the
main difference between them is their stiffness and flexi-
bility due to the difference in their thicknesses. Typically,
films are ≤0.076 mm (0.003 in.) in thickness, while sheets
are typically ≥0.25 mm (0.01 in.). In cast film extrusion, the
molten PLA is extruded through a sheet die and quenched
on polished chrome rollers that are cooled with circulating
water. Due to the thermal sensitivity of PLA, the use of exter-
nal deckles on the die should be avoided since the degraded
resin behind the deckles can lead to edge instability. Usually
the die gap is set to 10% or 25–50 ␮m (1–2 mils) greater than
the target sheet thickness [84]. Ljungberg et al. extruded
neat PLA in a Haake Rheomex 254 extruder with a Rheo-
cord 90 drive unit (Karlsruhe, Germany) [96]. The 19.3 mm
diameter screw has a compression ratio of 2:1 and l/d ratio
of 25. In this study, the temperatures for the feeding zone,
the barrel and the die were 160, 180, and 175 ◦ C, respec-
tively [96]. Similar extruder temperature profiles were used
by Gruber et al. [79].
Sheet and film forming can be achieved on a three-roll
stack. Because of the low melt strength of PLA, horizontal
roll stacks configuration is preferred. To avoid the con-
densation of lactide monomers and slippage of web on
the rollers, relatively high roller temperatures (25–50 ◦ C)
835
are usually used. Lactide monomer buildup around the
die could be further prevented by using an exhaust sys-
tem. Nevertheless, extreme high temperatures should be
avoided as the web will stick to the rollers, resulting in
poor quality sheet. To reduce the chance of trapping air
and reduce film or sheet defects, one resin supplier recom-
mended that the die be positioned as close as possible to
the entrance nip and slightly higher than the nip to accom-
modate the slight drooping of the molten PLA web [84].
To cast PLA film, Ljungberg et al. used a 200-mm fishtail
die with a 300–400 ␮m split gap and a casting air gap of
15 mm [96]. Generally, hydraulic rolls stands, capable of
producing pressure around 800–900 lbs/linear inch of die is
required to prevent floating of the rolls which would result
in uneven PLA surfaces, edge instability, and neck-in [84].
Good contact between the web and rolls is also important
to minimize lactide buildup. Casting of PLA film usually
requires edge pinning (electrostatic or low pressure air) to
eliminate streaking, reduce neck-in, and improve edge sta-
bility [97]. Slitting and web handling of PLA is similar to
PS. Edge trimming of PLA should be carried out with rotary
shear knives since razor knives may yield rough edges and
web breaks. Winding of the PLA web should be done with
good tension control in order to obtain a consistent gauge.
Similar to PP, PET and PS films, the physical properties
of PLA films can be enhanced through orientation. Uniaxial
orientation of PLA is achieved in conventional machine-
direction orientation (MDO) rolls. Since PLA tends to neck in
during drawing, nipped rolls are usually required. Through
mechanical drawing, it is possible to improve thermal and
impact resistance of the PLA film or sheet to a level simi-
lar as oriented polystyrene (OPS), oriented polypropylene
(OPP) or polyester. An oriented PLA film can be obtained
by stretching it to two to ten times its original length at
60–80 ◦ C [51], which is much lower compared with OPP
and PET. Typical drawing temperatures for PLA films in the
machine (MD) and transverse directions (TD) are presented
836 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Table 6
Recommended drawing conditions in the machine and transverse direc-
tion for PLA [97]
Section Temperature range (◦ C)
Machine direction preheat 45–65
Slow draw 55–70
Fast draw 70–75
Annealing 45–55
Transverse direction
Preheat 65–70
Draw 70–85
Annealing 125–140
in Table 6. In generally, for 98% l-lactide PLA, machine
direction orientation of 2–3× is expected, while transverse
stretch ratios of 2–4× may be used. At higher d-lactide
contents, the machine and transverse stretch ratio can be
increased. Fig. 21 shows a typical extrusion cast line for
producing biaxially oriented PLA film.
The orientation in PLLA films depends on the draw
rate, temperature and ratio. High strain rate, low tem-
perature and high stretch ratio favor strain-induced
crystallization during orientation. Taking the competitive
crystallization and relaxation effects into consideration,
Lee at al. concluded that the optimal drawing tem-
perature to obtain highly oriented PLLA films (Mw of
190,000 g/mol) is about 80 ◦ C [63]. In contrast, Gruber et al.
used somewhat lower temperatures for biaxial orientation
of 100,000–150,000Mn PLA polymer with 10–20% meso-
lactide content (65–72 and 20 ◦ C for preheat and cooling
rolls, respectively, for MD stretching; 63–70 ◦ C and circu-
lated ambient air cooling for TD drawing) [79]. Ou and
Cakmak prepared biaxially oriented PLA films by stretching
cast PLA in both MD and TD to different ratios, followed by
annealing these films at elevated temperatures to induce
crystallinity and dimensional stability [62]. Their wide
angle X-ray (WAXS) results showed that the development
of crystalline order and orientation were dependent on
the mode of orientation. They observed that simultaneous
biaxial stretching of PLA film resulted in poor crystalline
order, while sequential stretching promoted a greater crys-
talline order [62]. Hence, the properties of PLA films are
expected to change depending on the stretching sequence
used during the orientation process.
PLA has excellent optical properties and high modulus.
However, it has low elongation, tear and burst strengths.
Fig. 21. Biaxial oriented extrusion cast film machine.
To overcome these shortcomings, PLA is often coextruded
with other polymers to form multilayer structures to
enhance its properties. For instance, to reduce electrostatic
buildup, Rosenbaum et al. disclosed methods for forming
biaxially oriented multilayer films made of one PLA-based
layer and two outer layers consist of PLA and glycerol fatty
acid esters to achieve films with antistatic surfaces [98]. The
extruder temperatures used ranged from 170 to 200 ◦ C with
the take off roll set at 60 ◦ C. The biaxial orientation took
place sequentially, first at 68 ◦ C in the machine direction
by rollers running at different speeds, followed by trans-
verse direction stretching using a tenter frame at 88 ◦ C.
Stretch ratios were 2.0 and 5.5 for machine and transverse
direction stretching, respectively. To impart dimensional
stability to the film, heat-setting was conducted at 75 ◦ C.
Noda et al. disclosed a method of coextruding multi-
layer laminate film consisting of polyhydroxyalkanoate
(PHA) copolymer (copolymer of 3-hydroxybutyrate with 3-
hydroxyhexanoate) and PLA to impart softness to the PLA,
and at the same time reduce the tackiness of the PHA. By
preventing the web from sticking to itself or the processing
equipment, the speed of production and product quality
can be improved [99].
PLA films tend to have higher surface energy than
untreated polyolefin films. Gruber et al. reported surface
energy of about 44 dynes/cm for pure PLA films [79].
The surface energy values for 98% l-lactide and 94% l-
lactide films were reported as 42 and 34–38 dynes/cm,
respectively [100]. Higher surface energy will provide more
satisfactory printing properties without surface treatment.
If higher surface energy is needed for downstream process-
ing, the surface can be treated by corona discharge.
7.5. Extrusion blown film
In extrusion blow film process, molten PLA is extruded
to form a tube using an annular die. By blowing air through
the die head, the tube is inflated into a thin tubular bub-
ble and cooled. The tube is then flattened in the nip rolls
and taken up by the winder (Fig. 22). The ratio of bubble
diameter to the die diameter is called the blow-up-ratio
(BUR). BUR ratios of 2:1–4:1 with the die temperature
of 190–200 ◦ C have been used for extrusion blowing of
PLA films [101,102]. By varying the BUR, screw speed, air
pressure, and winder speed, films of different thicknesses
(∼10–150 ␮m) and degree of orientation can be achieved.
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 22. Extrusion blown film line.
PLA has a specific density of about 1.24 g/cm3 which is
-ethylene bisstearamide,
much higher than polyolefins (0.91–0.96 g/cm3 ). While PLA
may be processed in extruders designed for polyolefins,
if the extruder is already operating at close to maximum
power of the screw drive, the extruder may not have enough
power to process PLA due to the substantial higher den-
sity for PLA [103]. Compared to polyolefins, PLA has weaker
melt strength, and therefore, the formation of a stable bub-
ble during extrusion blowing is more difficult. As a result,
extrusion blowing of PLA film often requires the use of addi-
tives, such as viscosity enhancers to strengthen its melt
strength. These additives protect the polymer from degra-
dation and/or couple polymer chains to attenuate overall
loss of molecular weight and viscosity of the polymer melt.
The formulation of coupling agents is often proprietary. One
commercially available coupling agent for PLA is made up
of copolymer of styrene, methyl methacrylate and glycidyl
methacrylate [102]. Sodergard et al. disclosed a method to
stabilize PLA and enhance its melt strength by adding an
organic peroxy compound (e.g., tert-butylperoxybenzoate,
dibenzoylperoxide, tert-butylperoxyacetate) during melt
processing, wherein the peroxide is added in about 0.01–3%
by weight of PLA [101].
Since PLA films are quite stiff and have much lower elon-
gation than polyolefins, collapsing of bubble in the nips
rolls tends to produce wrinkles which tend to permanently
remain in the film due to the high dead-fold properties of
PLA. This problem can be overcome by incorporating fillers
into PLA during extrusion. To reduce the adhesion between
films, Hiltunen et al. blended PLA with triacetin plasticizer
(glycerol triacetate), together with various anti-adhesion
agents, such as talc, TiO2 and CaCO3 . They claimed that the
bursting strengths of the resulting blown films were better
than typical polyethylene and PP films [104]. Slip additives
837
(e.g., oleamide, stearamide, N,N
oleyl palmitamide) have also been added to reduce the
coefficient of friction between overlapping films [102]. Typ-
ically, slip additive of less than 0.5–1.0% by polymer weight
is used, as excessive amounts will compromise the abil-
ity of print inks, stickers to adhere to the film surface. To
avoid the use of copolymerization techniques, blending, or
plasticizers, Tweed et al. developed a method to obtain PLA
blown films by elevating the viscosity of PLA through suc-
cessive steps in a polymer cooling unit or by internal cooling
of the die mandrel using air or liquid fluid to control the
temperature of the die [102]. Mitsui Chemicals successfully
developed PLA-based films by copolymerization technol-
ogy, and it is commercializing it as one of the LACEA brand
resins [51].
7.6. Thermoforming
Thermoforming is commonly used for forming pack-
aging containers that do not have complicated features.
PLA polymers have been successfully thermoformed into
disposable cups, single-use food trays, lids, and blister pack-
aging.
Fig. 23 shows the typical steps for thermoforming of
PLA container. In this process, PLA sheet is heated to soften
the polymer, forced either pneumatic and/or mechanically
against the mold, allowed to cool, removed from the mold,
and then trimmed. Heating of PLA sheet for thermoform-
ing is generally achieved by infrared red (IR) radiation
from heater elements. Each polymer has an optimum IR
absorbance frequency in the IR region. Therefore, the heater
element should be set at the temperature at which the
majority of energy is absorbed by the polymer. For PS, the
ideal wavelength is 3.2–3.7 ␮m [105]. Values for PLA have
838 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852

Fig. 23. Main steps for thermoforming process.

not been reported in the literature. In general, the thermo- son of the mechanical, physical and barrier properties of
forming temperatures for PLA are much lower than other thermoformed PLA, PS, and PET containers showed that
conventional thermoformed plastics (e.g., PET, PS, and PP) PLA containers outperform PET and PS at lower temper-
in the range of 80–110 ◦ C when the sheet enters the mold atures [109]. Moreover, the use of 40–50% PLA regrind did
[106,107]. not significantly change in the container performance [9].
Typically, aluminum molds are used for thermoform-
ing PLA containers. Molds, trim tools and ovens designed
7.7. Foaming
for thermoforming of PET, high impact polystyrene (HIPS)
and OPS can be used for forming PLA containers. However,
Due to their biocompatibility and large surface area,
molds for thermoforming of PP may not be used inter-
PLA foams have a niche in tissue engineering and medical
changeably for PLA, since PP shrinks more considerably
implant applications [110–112]. Foaming of PLA is generally
than PLA during cooling. For a given part thickness, cool-
carried out by dissolving a blowing agent in the PLA matrix.
ing times required for PLA containers in the mold tend to be
The solubility of the blowing agent is then reduced rapidly
higher than PET and PS containers due to the lower thermal
by producing thermodynamic instability in the structure
conductivity and Tg for PLA polymers. Table 7 compares the
(e.g., temperature increase or pressure decrease), to induce
thermal properties of PLA, PS and PET.
nucleation of the bubbles. To stabilize the bubbles, the foam
Orientation increases toughness of PLA containers.
cells are vitrified when the temperature is reduced below
Regions of PLA articles that are highly drawn are less brit-
the Tg of the polymer [113,114].
tle as compared to flanges and lips that received minimal
Various foaming strategies have been adopted to reduce
orientation. Extruded sheet prior to thermoforming is rela-
PLA density and improve foam mechanical properties. Di
tively brittle at room temperature. To ensure smooth travel
et al. used 1,4-butanediol (BD) and 1,4-butane diisocyanate
of the web and to prevent web breakage, a tight radius
(BDI) as chain extenders to increase the molecular weight of
should be avoided in the unwind stations and skeleton
PLA so that its viscoelastic properties are more optimal for
rewind stations. A minimum rewind radius of 25 cm is
foaming. They produced modified PLA samples by sequen-
recommended [108]. If PLA sheet needs to be trimmed
tially adding different ratios of BD and BDI in a Haake melt
before thermoforming, it should be heated to tempera-
mixer operating at 170 ◦ C and mixer speed of 60 rpm under
tures near 90 ◦ C to prevent cracking. Storage conditions
a nitrogen atmosphere. Tin(II) 2-ethylhexanoate was added
for the sheet stock need to be controlled as well. As a
as a catalyst at 0.05 wt% of PLA. They found that the chain-
guide, PLA should not be exposed to temperature above
extender modified PLA produced foams with reduced cell
40 ◦ C or to RH above 50% as the sheet will block and resist
size, increased cell density and lowered bulk foam density
unwinding due to its low heat deflection temperature. After
as compared to the neat PLA foam control [113]. Mikos et
thermoforming, precaution should be taken to store PLA
al. prepared PLLA membranes with and without sodium
below 40 ◦ C since Mw breakdown can accelerate when it
chloride, sodium tartrate, and sodium citrate by solvent-
is exposed to elevated temperature (Fig. 11). A compari-
casting techniques [114]. The PLLA and PLLA/salt composite
membranes were foamed by heating them at 195 ◦ C (15 ◦ C
Table 7
higher than Tm ) for 90 min and then quenched in liquid
Thermal properties of PLA, PS, and PET [106]
nitrogen for 15 min. They were able to produce membranes
PLA PS PET with porosity as high as 93% with a desired surface/volume
Thermal conductivity (×10−4 cal. cm−1 s−1 ◦ C−1 ) 2.9 4.3 5.7 ratio depending on the salt used. Ajioka et al. disclosed in
Heat capacity (cal. g−1 ◦ C−1 ) 0.39 0.54 0.44 a patent the method of manufacturing PLA foams suitable
Glass transition temperature (◦ C) 55 105 75 for use as disposable food trays, cups, thermal insulators,
Thermal expansion coefficient (×10−6 ◦ C−1 ) 70 70 70
and cushioning materials [115]. Their approach involves
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
mixing various proportions of PLLA and PDLA together
with 0.5% talc (w/w) in an extruder at 200 ◦ C. An expand-
ing agent, either dichlorodifluoromethane or butane was
charged under pressure into the extruder. The mixture was
cooled to 140 ◦ C and extruded through a slit die to give sheet
foam. An alternate method adopted by these inventors
involved mixing and heating azodicarbonamides powder
(a food additive) with PLA resins using an extruder, in
which the azodicarbonamide decomposed, thereby releas-
ing nitrogen gas to induce the formation of bubbles [115].
Another patent described a method for injection molding
of PLA foams by adding 15–25 wt% of solvent to PLA dur-
ing extrusion [116]. Solvents reported to be suitable here
were methyl formate, ethyl formate, methyl acetate, propyl
acetate, dioxane and methyl ethyl ketone.
Loose-fill packaging materials provide cushioning, pro-
tection, and stabilization of packaged goods during
shipping. Over the past decade, the use of expanded PS
foams for loose-fill packaging has declined due to the
replacement with the environmentally more benign starch-
based expanded foams. To overcome the hydrophilic nature
of starch, these biobased foams are often blended with
petroleum polymers. Recently, PLA has been use for blend-
ing with starch during foaming. Guan et al. extruded
PLA and acetylated starches, along with 5% talc (w/w)
and various amounts of ethanol in a co-rotating conical
twin-screw extruder (180 rpm screw speed; 160 ◦ C barrel
and die temperatures) [117]. The blends were conditioned
for 24 h at 25 ◦ C before extrusion. The authors observed
that ethanol functioned as an effective blowing agent to
expand the foams, and it acted as a solubilizing agent to
depolymerize PLA and starch to form homogenous dough.
They observed that increasing the PLA content caused an
increased foam expansion [117]. In an attempt to improve
the physical/mechanical properties, and moisture resis-
tance of starch-based foams, Preechawong et al. prepared
starch–PLLA hybrid foams by baking PLA–starch mixtures
in a hot mold at 220 ◦ C for 2 min [118]. They found that the
addition of PLA improved the ultimate tensile strength and
elongation at break, as compared to the starch foam, with
a concomitant increased resistance to water absorption.
Besides adjusting the cellular morphology of PLA
through the use of different blowing agents and pro-
cess optimization (pressure and temperature adjustments),
much recent research activity has been directed at affect-
ing the size and formation of the cellular structure by
dispersing MMT nanoclay particles in the bulk material
[119]. Ray and Okamoto foamed pure PLA and PLA com-
posite with organically modified MMT in a batch system
below Tm . These authors found that foamed PLA reinforced
with MMT produced homogeneous cells with closed cell
structure with a diameter of 2.6 ␮m; however, in the case
of neat PLA the cells were non-uniform with average cell
size of 230 ␮m [23]. They concluded that the MMT parti-
cles acted as nucleating agents for the cell formation. Ema
et al. also incorporated nanoclay in PLA for batch foam-
ing using supercritical carbon dioxide as a foaming agent.
These researchers noted that cells of ∼200 nm were local-
ized along the surfaces of the dispersed nanoclay and drew
a similar conclusion that the dispersed nanoclay acted as
nucleating sites for the cell formation [120]. Di et al. foamed
839
neat PLA and PLA reinforced with two commercial organ-
ically treated MMT samples. They found that the foam of
PLA/MMT exhibited a nicely interconnected, energetically
stable closed-cell structure with pentagonal and hexagonal
faces [121]. In contrast, pure PLA foam showed a relatively
large cell size (∼230 ␮m). The size of the cells decreased as
the amount of MMT increased, and it leveled off at higher
MMT concentrations. Di et al. concluded that it is possible
to foam PLA with different cellular structures by controlling
the amount of organoclay content [121].
Recently, supercritical CO2 has attracted consider-
able research attention as an environmentally friendly
solvent for many processes because it is inexpensive, non-
flammable and can be easily removed from the products.
A liquid becomes a supercritical fluid when both pressure
and temperature are above the critical point. In this state,
the substance possesses a combined gas-like viscosity and
liquid-like density, making it an excellent solvent for var-
ious applications. For CO2 , its solubility and diffusivity in
many polymers tend to increase considerably when it exists
in the critical state, thereby facilitating the plasticization
of many polymers and enabling the forming process to be
conducted at lower temperatures [122]. Moreover, the crit-
ical conditions of CO2 at 31.1 ◦ C and 7.38 MPa are readily
attainable within the safety of commercial and laboratory
setups [123,124]. The supercritical CO2 approach is based
on the larger Tg depression effect of supercritical CO2 on
polymers, which keeps the polymer in the liquid state at rel-
atively low temperatures. The sudden reduction in pressure
leads to the formation of CO2 nuclei which grow sponta-
neously. Meanwhile, as the pressure decreases, the Tg for
the polymer also elevates and eventually rises above the
foaming temperature, at which point the cellular structure
is locked in place to produce a cellular network. Fujiwara
et al. investigated the effect of d- and l-lactide composi-
tions (1.0–28.5% d-lactide contents) on PLA foaming using
supercritical CO2 [125]. The samples were heated to 50 ◦ C in
the reactor chamber followed by adding CO2 . The pressure
of the vessel was ramped to 69 and 414 bar, respectively,
for amorphous and crystalline samples. The temperature
was increased stepwise while the pressure was kept con-
stant. The expansion of the polymer was monitored during
heating using a linear variable differential transducer. Fuji-
wara et al. reported that the average pore diameters for the
porous structures were 5.4 and 3.3 ␮m for 1 and 4.2% d-
lactide polymers, respectively, suggesting that the cellular
morphology was crystallinity dependent. In contrast, under
the same conditions employed, porous structures were not
detected for amorphous PLA samples with 10 and 28.5% d-
lactide content. Moreover, they also reported an increased
linear swelling of the polymer with decreasing crystallinity
and the porous supercritical CO2 treated PLA samples
have higher crystallinity than the as received polymers
[125]. Porosity of supercritical CO2 treated foams not only
depends on the pressure and temperature, but also on the
rate of its release from the polymer (Fig. 24) [123]. Mooney
et al. showed that the formation of PLA foams can also take
place below the critical conditions by exposing the poly-
mer to a pressure of 55 bar at 20–23 ◦ C for 72 h, followed by
rapid depressurization to atmospheric pressure in 10–15 s
[126]. Pores of 10–100 ␮m were observed, although solid
840 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 24. SEM micrographs of PDLLA polymer after processing in supercritical CO2 at 240 bar, 35 ◦ C with (a and b) 12 min venting and (c and d) 60 min venting
[123]. Reproduced from Quirk et al. by permission from Elsevier B.V.
skin layers were present on the sample surface due to the
rapid diffusion of the dissolved gas from the surfaces [126].
Matuana investigated the effect of microcellular structures
on the mechanical properties of foamed PLA by using a
two-stage CO2 foaming process. The process first involved
saturating PLA samples with CO2 in a pressure chamber
at 5.5 MPa and room temperatures for 2 days. The CO2 -
saturated samples were then removed from the chamber
and heated above Tg in a glycerin bath [127]. Compared with
the unfoamed PLA, Matuana reported a twofold increase in
impact resistance, up to twofold increase in strain at break,
and up to fourfold increase in toughness for the foamed
samples. The increased impact strength was attributed to
the presence of small bubbles which inhibited the crack
propagation by blunting the crack tip and increasing the
amount of energy needed to propagate the crack [127].
The low temperature supercritical CO2 processes reviewed
above are expected to find their place in the manufactur-
ing of structural foams for which mechanical properties are
critical, since thermal and hydrolytic degradation encoun-
tered in the typical thermal processes can be avoided.
7.8. Fiber spinning
High water vapor transmission rate of PLA often pre-
cludes its use in applications where moisture barrier
is critical. However, this property can be leveraged for
fabricating fibers used in garments (e.g., shirts, dresses,
underwear, shoes, etc.) to improve their “breathability”.
While PLA fibers are not as wettable as cotton, they exhibit
much greater water vapor transmission than polyester or
nylon fibers.
The manufacturing of PLA fiber is carried out either by
dry or melt spinning processes. Commercially PLA fibers
are generally produced using the melt spinning tech-
nique [128–136]. Here, PLA fibers are typically melt-spun
at approximately 185–240 ◦ C through spinnerets with l/d
ratios of 2–10. The processing temperature is compara-
ble to polyolefins [137,138]. The melting temperature used
also depends on the optical purity of the polymer used.
Lower processing temperatures can be used for lower opti-
cal purity polymer (i.e., greater d-isomer content), which
can help reduce the thermal and hydrolytic degradation.
Similar to the injection molding process, fiber-grade PLA
needs to be dried to less than 0.005% (w/w) moisture before
melting in the extruder to minimize molecular weight
drop.
In a two-stage melt spinning process, the polymer is first
heated above its melting point and extruded through the
spinneret. The solidification of the extrudate is achieved
by cooling in the air and the take up roller. In the second
stage, the fiber undergoes hot drawing, where the filament
is pulled down by a take-up roll with a specific speed to
achieve fiber orientation, which is important to increase the
tenacity and stiffness of the fibers. PLA can be melt spun in a
high-speed spinning process with take-up velocity of up to
5000 m/min and a draw ratio of up to six [130]. The degree
of crystallinity of the fiber increases with spinning veloc-
ity due to stress-induced crystallization. By adjusting the
draw ratio, a wide range of mechanical properties can be
achieved for the fiber (Fig. 25). While high speed spinning
provides high fiber manufacturing throughput, manufac-
turing of fiber of uniform diameter is not a trivial task under
high speed condition due to process instability caused by
the draw resonance known as spinline neck-like deforma-
tion, which is characterized by an abrupt attenuation of the
spin-line cross-sectional area. The phenomenon is related
to the spinline flow-induced crystallization [131,139].
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 841

Fig. 25. Stress–strain curves for high-speed spun PLA fiber (l-PLA with 8% d-isomer), subjected to various (a) drawing speed and (b) draw ratios. The
extruder used in both processes was 18 mm screw at 185 ◦ C. The diameter of spinneret hole was 0.3 mm with a length of 0.6 mm. For the process in (b), the
filaments were taken up at 200 m/min by the first godet and drawn by the second godet spun at 800 and 1200 m/min. The first and second godets were set
at 65 and 110 ◦ C, respectively. Curves are reproduced based on the data published by Schmack et al. [130] by permission of John Wiley & Sons, Inc.

Another approach to form PLA fiber is based on the dry
spinning process, which involves dissolving the polymer
in a solvent (typically chloroform, toluene or a mixture of
the two solvents) and extruding the polymer solution in air
or inert gas. Evaporation of the solvent causes the extruded
filaments to solidify [136,140–143]. Although the melt spin-
ning process is relatively straightforward, the process tends
to induce molecular weight drop of the PLA polymer due to
thermal-induced hydrolytic degradation during the melt-
ing step in the presence of residual water. In contrast,
the dry spinning technique is quite effective in preserv-
ing the molecular weight of the polymer due to the lower
processing temperature used. In general, solution-spun
fibers are superior to melt-spun fibers from the stand-
point of mechanical properties. This is attributed to the
lower chain entanglement of polymer molecules in the
solution state as compared to the melt state. By transfer-
ring this dilute entanglement network to the solid state
in the spinning process, the as-spun fibers tend to exhibit
high draw ratios. For instance, Penning et al. reported that
dry spinning followed by hot drawing resulted in low crys-
tallinity fibers having a tensile strength of 1 GPa, whereas
fibers prepared from melt spinning followed by hot draw-
ing have much considerably lower strengths, ranging from
0.19 for completely amorphous copolymer to 0.53 GPa for
PLA homopolymer [141]. The major drawback to solution
spinning is the use of organic solvents, which can pose
environmental problems.
One important parameter that affects the fiber mor-
phology during dry solution-spinning is the composition
of the solvent. Instead of using one solvent, several studies
have successfully manipulated the morphology and physi-
cal properties of PLA fibers by using multi or binary solvent
systems. Postema et al. showed that PLA fibers spun from
a solvent made up of 40/60 chloroform/toluene exhibited
the highest tensile strength of 2.3 GPa after hot draw-
ing among other chloroform/toluene proportions tested
[142,143]. Similar observations were reported by Leenslag
and Pennings [140]. They postulated that under the 40/60
chloroform/toluene condition, the PLA adopted an inter-
rupted helical conformation. Solidification of PLA from
the solution during solvent evaporation caused the heli-
cal aggregates to form crystalline junctions that hampered
re-entangling of polymer chains, leading to crystalline
polymer with good draw-ability [140]. In this binary sys-
tem which contained a good PLA solvent (chloroform) and
a poor PLA solvent (toluene), the greater tendency for chlo-
roform to evaporate during spinning causes an increased
PLA concentration with a concomitant decrease in sol-
vent power, resulting in the formation of polymer-poor
and polymer-rich phases. The polymer-rich phase under-
went rapid solidification, thereby generating porous fiber
structures [142,143].
The wet process is similar to the dry process except
that the polymer solution is spun into a bath containing
coagulating solution which causes the polymer filament
to solidify. With this approach, PLA is normally dissolved
in chloroform which is then extruded into a toluene or
methanol bath [136]. Tables 8 and 9 compare the pro-
cess parameters between the melt and solution spinning.
Compared to polyester, Lyocell, cotton, and viscose fibers,
PLA fiber tends to be more extensible. When PLA stretches
beyond several percent of extension, it yields, stretches
quite easily, and then ruptures at relatively high elonga-
tion values. As shown in Fig. 26, the tenacity behavior of
PLA is akin to wool.
One variant of dry spinning is known as electrospinning
which utilizes an electrostatic force to draw fiber. Recently,
several research groups have successfully spun PLA fibers of
submicron diameter using this approach. The electrospin-
ning process is discussed in the next section.
7.9. Electrospinning of ultrafine fibers
Electrospinning is a technique for producing fibers
that are much smaller in diameter than those produced
using the conventional techniques. Electrospun fibers typi-
cally have diameters range from micrometer to nanometer
(Fig. 27). Similar to the conventional dry spinning process,
electrospinning requires the solubilization of the polymer
in a solvent. However, unlike drying spinning which relies
on mechanical extrusion, the electrospinning process uses
 842
Table 8
Properties and conditions for melt-spun PLA fibers

References d-Content Initial MW Final MW Collection speed Spinneret d/l Die temperature Draw ratio Draw temperature Crystallinity Tensile strenth Modulus Fiber diameter
(%) (×103 ) (×103 ) (m/min) (mm) (◦ C) (◦ C) (%) (MPa) (GPa) (␮m)

Penning [141] 0–15 280–600 – 1 0.25/– 150–210 7–9 60–100 – 185–530 0.5–0.93 –
Cicero [129] 4 111–131 67–79 – – – 4–8 – <35 60–400 0.5–3.1
Fambri [128] 0 330 110 1.8–10 1.0/– 240 7–21 160 30–38 870 9.2 48–106
Eling [136] 0 180–260 – 0.25–0.35 1/10 185 8–25 110 – 480–500 6–7 –
Schmak et al. [130] 4 207 180 800–5000 0.3/0.6 185 4–6 65–110 0–24 198–450 3.1–6.3 <500
Cicero [132] 2 99–109 62–71 – 2.16 – 1–8 – 43–50 100–350 1–3 300

L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852

Mezghani [135] 0.7 212 163 1000 0.76/4 233 – – <43 90–380 3.6–6.0 12–73
Yuan [134] 0 263–495 105–217 3.2 1.0/– 210–240 4.7–5.9 120 17–23 42–103 1.2–5.4 110–360

Table 9
Properties of solution-spun PLA fibers

References d-Content Initial MW Solvent Collection speed Spinneret d/l Solution Draw ratio Draw Crystallinity Tensile strength Modulus Fiber diameter
(%) (×103 ) (m/min) (mm) temperature (◦ C) temperature (◦ C) (%) (MPa) (GPa) (␮m)
Postema [142] 0 910 4%, w/v, chloroform/toluene (40/60) 10–182 0.25/23 60 10–18 190 – 900–1400 – –
Postema [143] 0 910 4%, w/v, chloroform/toluene (40/60) 3 0.25/23 9–60 12–14 190 – 1100–2200 – 17–28
Penning [141] 5 – 5–6%, w/v, chloroform/toluene 3 0.25/– 60 – 110 – 950 9.2 –
Eling [136] 0 300–500 6–12%, w/w, toluene 0.025–0.035 1/– 110 4–26 180–201 – 280–1000 7–10 –
Leenslag [140] 0 900 4%, w/v, 40/60, v/v, chloroform/toluene 0.012–0.017 0.25/23 60 20 204 53 2100 9–16 6.6
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 26. Tenacity–stretch ratio curves of PLA as compared to other com-
mon textile fibers. The curves are based on the data originally published
by Farrington et al. [137] and Rajkhowa et al. [187].
electrostatic force to spin the solution into fibers. Due to
their small diameter, electrospun fibers possess very large
area, making them an ideal material for applications such as
medical tissue scaffold, wound dressing, carrier for drugs,
protective fabrics, high performance filter media, filler for
nanocomposite materials, etc. [144].
A typical laboratory electrospinner is made up of four
main components: (1) a high voltage DC supply; (2) a spin-
neret, charged by a DC power supply; (3) an infusion or
peristaltic pump to deliver polymer solution to the spin-
neret; and (4) a metal fiber collector which also acts as a
counter electrode (Fig. 28). To increase throughput, mul-
Fig. 27. Comparison of surface area and diameter for various fibers.
Adapted from Ko [188].
843
tiple spinnerets have been used in conjunction with a
conveyor belt to achieve a continuous process [145–147].
Most of the setups reported in the literature involve apply-
ing a positive electrode to the spinneret and grounding the
counter electrode, although it is also possible to spin fiber
by reversing the polarity. The basis of electrospinning is
to charge the polymer solution in the spinneret tip with
a high voltage such that the induced charges cause the
polymer solution to eject and travel towards the ground
(or oppositely charged) collector. When the polymer solu-
tion is charged, the induced electrostatic repulsion works
against the surface tension of the solution, causing the poly-
mer solution to elongate and form a characteristic feature
known as a Taylor cone (Fig. 28). When the voltage reaches
a critical level (typically in the order of 10–20 kV), the elec-
trostatic repulsion overcomes the surface tension of the
solution, causing the polymer to eject towards the collector.
As the polymer jet takes flight in the air, the solvent vapor-
izes rapidly, producing a continuous fiber which deposits
on the collector [144,148,149]. By allowing the fiber to spin
for some time, a nonwoven fibrous mat is formed on the
collector. The morphology of the fiber can be affected by
using collector of different configurations. For instance, by
translating the collector plate in the X–Y plane, a large area
of fibrous mat consists of randomly laid fiber can be formed.
To achieve a fibrous membrane with oriented fibers, a rotat-
ing drum, disc, or parallel electrodes may be used (Fig. 28)
[150].
PLA has been successfully electrospun into fibers,
primarily for tissue engineering and biomedical appli-
cations. For instance, a number of studies showed that
scaffolds for the regeneration of cardiac, neural, bone
and blood vessel tissues can be fabricated from electro-
spun PLA fiber through post-spinning orientation and/or
using rotating target collectors [151–154]. PLA has been
electrospun into different forms of ultrafine fiber and
used as carriers for bioactive agents, including antibiotics
[155], anticancer drugs [156,157], and antibacterial silver
nanoparticles [158]. Other composite PLA fibers contain-
ing nano-components such as nanoclay (montmorillonite,
MMT) and TiO2 nanoparticles have also been successfully
produced using the electrospinning technique [157,159].
By and large, PLA solutions with lower polymer con-
centrations favor the formation of small diameter fibers.
But these fibers are less consistent in morphology and
tend coexhibit beads along their length (Fig. 29A and B).
These defects can be overcome by incorporating an organic
or inorganic salt, such as pyridinium formiate, Kh2 PO4 ,
NaH2 PO4 , or NaCl, in the fiber-forming solution to enhance
its electrical conductivity [160,161] (Fig. 29C and D). The
solvent used will also affect the surface morphology of the
fiber. Using dichloromethane as a solvent and a PLLA poly-
mer solution of 5%, Bognitzki et al. observed that the surface
of the PLLA fibers exhibited regular pore structures, which
were attributed to rapid phase separation of the solvent
[162]. Typical solvents used for PLA, along with the pro-
cess conditions used for electrospinning, are summarized
in Table 10.
Recently, an innovative technique was reported for elec-
trospinning PLA in the melt phase using a CO2 -laser [163].
This technique relies on using a laser beam to melt the PLA
844 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
Fig. 28. Typical setup for electrospinning, showing the main components. Selected collector configurations are shown here: stationary plate, rotating
drum/disc, and parallel electrodes.
polymer locally, thus minimizing thermal degradation due
to prolonged heat exposure, which has been observed pre-
viously for melt-electrospinning for other polymers based
on the heat conduction melting approach. Moreover, the
laser technique also eliminates the use of solvent, making
the process more environmentally benign. This technique
is capable of producing fibers with diameters smaller than
1 ␮m [163].
While research on electrospinning has exploded in the
past decade for fibers spun from various polymers, the
commercial production of ultrafine PLA fibers using this
technique has not been forthcoming due to the low pro-
duction throughput, the requirement for the use of specific
solvents, and variation in fiber diameter. Based on the
present state-the-art of electrospinning, this technique is
likely to find uses for products containing PLA-nanofibers
in pharmaceutical and biomedical applications.
7.10. PLA blends with other polymers
In many film applications, such as grocery and garbage
bags, bursting strength, elongation and tear strength are
important properties. As discussed in Sections 7.4 and 7.3,
these properties can be improved to a certain extent by
mechanical drawing, such as biaxial orientation and stretch
blow molding. However, for other PLA parts where the
use of mechanical orientation is not feasible (e.g., injection
molded articles), blending of PLA with other polymers is a
useful strategy to impart flexibility and toughness. Another
motive for blending PLA with other polymers is to reduce
the material cost since the cost of PLA is relatively higher
compared to other petroleum plastics.
Various polymers have been used for improving the
properties of PLA, including elastomers [164], thermoplas-
tic starch [165], poly(ethylene glycol) (PEG) [104,165,166],
triacetin and tributyl citrate [96,104,167], and PHA [99,168].
Lee and McCarthy modified the toughness of 4% d-PLA
with poly(3-hydroxyloctanoate) (PHO). In order to over-
come the process difficulties due to the large difference
in melt viscosity between the two polymers, they modi-
fied the PHO with hexamethylene diisocyanate (HMDI) by
reacting the hydroxyl group of PHO to form urethane link-
ages. HMDI of 2–5.5% (w/w) was reacted with PHO using
a counter-rotating screw at 40 rpm for 2 min at 100 ◦ C.
The modified PHO was melt-blended with PLA at 40 rpm
for 3 min at 175 ◦ C and then compression molded [168].
Noda et al. prepared plastic films by melt compounding
various proportions of PLA, PHA copolymer (copolymer of
3-hydroxybutyrate with 21 mol% of 3-hydroxyhexanoate),
and poly(ethylene oxide). These authors claimed that the
inherent tackiness of PHA polymer and brittleness of PLA
can be overcome by this approach [99]. Recently, based
on viscosity and gel permeation chromatography mea-
surements, Conrad et al. reported that PLA/PHA blends
degraded more rapidly as compare to the neat PLA [169]. In
another patent, Randall et al. blended PLA with epoxidized
natural rubber in the presence of a compatibilizing agent
(maleic anhydride/polybutadiene copolymer or maleic
anhydride/polybutadiene/PS copolymer at 1–2 wt% relative
of the epoxidized rubber). They observed an increased ulti-
mate elongation from 72.6 to 295%, and an increase of Izod
impact value from 2.08 to 3.8 ft lbs/in. for injection molded
test bars, as compared to the non-compatibilized control
[164]. The blends were produced by extruding the poly-
mers through a twin-screw extruder (150–175 ◦ C extruder
zone temperatures; 250 rpm), cooling in a water trough,
chopping the extruded strand into pellets, drying to remove
water, and then injection molding into test bars. Randell et
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 845

Fig. 29. Scanning electron micrographs of electrospun PLA fibers prepared from dichloromethane with and without pyridinium formiate (PF), a salt that
increases the conductivity of the polymer solution: (A) 5% (w/w) PLA without additive; (B) 1% (w/w) PLA without additive; (C) 5% (w/w) PLA with 0.8%
(w/w) PF; (D) 0.1% (w/w) PLA with 0.8% (w/w) PF. Micrographs are adapted from [160] with permission from e-Polymers Foundation.

al. noted that reprocessing the polymer blends, i.e., pass-
ing them through the extruder more than once, tended
to increase the impact resistance of the resulting molded
articles [164].
Averous attempted to blend thermoplastic starch, PEG,
glycerol and oligomeric lactic acid by using a single-screw
extruder equipped with a conical-shaped shear element
[165]. Glycerol was found to be the least efficient plas-
ticizer, while oligomeric lactic acid and PEG provided
substantial increases in elongation. Affinity of PLA and
thermoplastic starch was poor, leading to blends that
possessed much weaker mechanical properties as com-
pared to the individual polymers [165]. Moura reported
that the tensile strength, elongation, and damping for
PLA blended with starch particles increased with aver-
age particle size of the starch granules, but declined
when the granules were greater than 45 ␮m [170]. More-
over, crystallinity increased as the particle size decreased.
The use of methylenediphenyl diisocyanate as a coupling
agent dramatically improved the mechanical properties
of the composite [170]. Sheth et al. melt-blended PLA
and PEG using a counter-rotating twin-screw extruder at
120–180 ◦ C. They reported that PEG can form miscible to
partially miscible blends with PLA, depending on the blend
concentration. Below 50% PEG, the plasticized PLA sam-
ples have high elongation with a concomitant reduction
in modulus values. However, above 50% PEG content, the
blend crystallinity increases, resulting in an increased mod-
ulus and a considerable decrease in the elongation at break
[166]. Although PEG is effective in decreasing the stiffness
of PLA, the use of low molecular weight plasticizer has a
disadvantage in that it has a tendency to migrate in the PLA
matrix. For instance, Hiltunen et al. reported that although
PEG plasticized PLA can be extrusion blown to form film
with a reasonable tensile strength, PEG tended to migrate
out of the film after a few days or weeks [104]. Ljungberg
and Wesslen reported that the Tg of PLA can be effectively
depressed by blending with triacetine and tributyl citrate
up to about 25% (w/w), above which phase separation of
plasticizer tended to occur. They also observed that phase
separation of plasticizer accelerated at elevated tempera-
ture (50 ◦ C) due to the increased crystallinity of the PLA
phase [167]. During storage of triacetine and tributyl cit-
rate plasticized PLA film, the migration of the plasticizer
846 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852

to the film surfaces and the concomitant increased crys-

tallinity of the bulk material have been reported to cause
Fiber diameter
difficulty in subsequent heat welding [96].

0.3–2.4
0.3–1

0.7–2
0.9–1

0.2–1
0.8–3

0.1–3
(␮m)

7.11. Compounding of PLA composites

1–2

3–6

∼1
While PLA has modulus and tensile strength compara-

Stainless steel sheet on

plate and rotating disc
ble to petroleum-based polymers, PLA is brittle and has

Stationary aluminum
relatively much lower thermal and impact resistance prop-
Rotating mandrel
Rotating mandrel

Stationary plate

Rotating drum

erties. Moreover, the cost of PLA is higher than that for

rotating drum
Collector type

Rotating disk
conventional thermoplastics. To overcome these limita-

Stationary

Stationary
Stationary
tions, other polymers, minerals and biobased materials
have been incorporated in PLA to produce composites
with enhanced properties [171,172]. In particular, bio-fillers
derived from renewable resources (e.g., natural fibers,
Solution feed rate

starches, proteins) have attracted a great deal of interest

for the reinforcement of PLA due to their sustainable supply
and environmentally benign production.
3.0–4.2
(mL/h)

The extent of reinforcement in PLA composites is largely

18–21
0.1

1.3
1.5

1.2

1.0

dependent on how well the filler material disperses in

6

–
–

the PLA matrix, and the nature of interfacial interaction

Voltage (kV)

between the filler and the PLA phase. Typically, a conven-

45–50.4

tional single screw extruder does not provide sufficient

35–45
16–41
20-30

dispersive mixing to break up the additive agglomerates.

25

30

40
12
13

15

Typically, a twin-screw compounder is needed to achieve

a better dispersion of filler particles. Ouchi et al. disclosed
a method of forming PLA nanocomposites which provides
Spinneret-target

a rapid crystallization rate to improve heat resistance,

distance (cm)

moldability and mold release properties. The approach

involves dispersing organically modified layered clay min-
1–5

eral, along with a low molecular weight compound that

30
20

20
15

15

15

10

14
18

has one or more amide groups. One of the examples given

Spinneret diameter

involves compounding 3 wt% MMT and 1 wt% ethylene-bis-

12-hydroxystearic acid amide with PLA in a twin-screw
compounder at 220 ◦ C at 300 rpm [173]. Mathew et al.
investigated the mechanical properties of PLA compos-
0.7–1.2
(mm)

ites containing microcrystalline cellulose, wood flour and

0.4
0.7

0.5

wood pulp. A twin-screw compounder was used to disperse

–

–
–

the biomaterials in PLA at up to 25 wt% cellulose load-

ing [27]. The compounding conditions used were: screw
1–5% (w/w) dichloromethane
5% (w/w) in dichloromethane
20–35% (w/w) in 1.5:1 (w/w)
14% (w/v) in 15:3 mixture of

5.5–6% (w/w) in chloroform

speed 250 rpm; heater temperature 170–200 ◦ C; and vac-

CHCl3 :dimethylformamide

dimethylformamide blend
Typical process conditions and solvent used for electrospinning of PLA

Melt-electrospinning—no
20% (w/v) in chloroform

14% (w/v) in chloroform

10% (w/w) in 1,1,1,3,3,3-
hexafluoro-2-propanol

uum vented extruder. The injection molding was conducted

dichloromethane/N,N-
1–5% (w/w) in 70:30
methylene chloride:

at 200 ◦ C at an injection rate of 60 mm/s, with a pack pres-

dimethylformamide
Polymer solution

sure of 400 bars. The mold temperature used was 50 ◦ C,

solvent used

and the cooling time was 15 s. The studies showed that the
microcrystalline cellulose, which exists as aggregates did
blend

not separate into nano-whiskers during the compounding

process. While good dispersion of cellulose reinforcements
in the PLA matrix was observed, these authors attributed
1.4–1.8% d-lactide

the reduced tensile strength and elongation at break to

the poor interfacial adhesion between the phases [27].
5% d-lactide

5% d-lactide
PLA grade

Using the same compounding technique, Oksman et al.

compared the compression of molded PLA and PP compos-
PLLA

PLLA

PLLA
PLLA
PLLA
PLA
PLA

ites containing flax fibers at 30 and 40 wt% loading. These

authors reported that the tensile strength for PLA-flax
Bognitzki et al. [162]

fiber composites is about 50% better than PP-flax com-

Kenawy et al. [155]

Ogata et al. [163]

Zong et al. [161]
Zong et al. [151]

Yang et al. [152]

posites, which are used today in many automotive panels

Kim et al. [154]
Vaz et al. [153]

Jun et al. [160]

Xu et al. [156]

[24].
References

Huda et al. evaluated the mechanical and thermo-

Table 10

physical properties of PLA composites containing chopped

glass fiber or recycled newspaper cellulose fiber producing
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 847

by a twin-screw extruder and an injection molding system
[26]. The dried cellulose fibers and PLA resin, mixed at 70
and 30% (w/w) ratios were compounded in the twin-screw
extruder with an l/d ratio of 30. The extruder tempera-
ture was set at 183 ◦ C and the screw speed was 100 rpm.
The extrudate was palletized and dried prior to injection
molding. The extruder temperature was 183–185 ◦ C. A rel-
atively long cooling time of 50 s was used to bring the
injection molded part to 65 ◦ C in the mold. The study
showed that both mechanical and thermo-physical prop-
erties of the recycled newspaper composite compared
favorably with glass fiber reinforced PLA composite, sug-
gesting that these cellulose fiber reinforced composites
have a potential to replace glass composite in applications
where very high load bearing capabilities are not needed
[26].
The effects of cooling on the crystallization behavior of
PLLA-cellulose composites were investigated by Mathew et
al. [28]. The 25% (w/w) composites were prepared in a vac-
uum vented twin-screw extruder operated at 250 rpm and
170–200 ◦ C. The resulting composites were pelletized and
subsequently injection molded at 200 ◦ C into a 50 ◦ C mold
at the injection speed of 60 mm/s. The Tg values for the
molded PLLA, microcrystalline cellulose, cellulose fiber and
wood flour composites, were 54.1, 56.6, 57.5 and 58.3 ◦ C,
while the crystallinity values were 19, 45, 35 and 45%,
respectively. These authors attributed the delayed polymer
relaxation for the composites to the restriction of polymer
chain mobility due to the increased crystallinity in the pres-
ence of fillers. The presence of cellulose fillers has a similar
effect of inducing crystallinity in PLLA polymer during slow
cooling (2 ◦ C/min) from the melt (absence of glass transi-
tion around 54–58 ◦ C regions for traces III and V in Fig. 30).
Shibata et al. evaluated the effect of dispersing abaca
fiber (Manila hemp) in several biodegradable polyesters,
including PLA. The biofiber was incorporated up to 20%
(w/w) in a twin-screw compounder at 190 ◦ C for 5 min
at a screw speed of 50 rpm. These authors observed an
increased flexural moduli for poly(butylenes succinate)
and polyestercarbonate/PLA blends as the fiber content
increased. In contrast, for the PLA-abaca fiber composite, a
minimal increase in flexural strength was observed which
is attributed to inherent high flexural strength of neat PLA
[25].
7.12. PLA nanocomposites
Inorganic or organic nanoparticles have been incor-
porated to enhance the mechanical, barrier and thermal
properties of PLA. Unlike micro- and macro-scaled particles
(e.g., talc, glass fiber, carbon particles, etc.), nanopar-
ticles can improve material properties at much lower
added quantities (2–8%, w/w). Over the past few years,
various nanomaterials have been investigated for rein-
forcing PLA, including layered silicates, carbon nanotube,
hydroxyapaite, layered titanate, aluminum hydroxide, etc.
[21–23,119,154,174–179]. Among the nanomaterials inves-
tigated, layered silicate clays have been studied in the
greatest detail by researchers from both academia and
industry. The heightened interest for these nanofillers
can be attributed to their ability to dramatically improve
material properties of the nanocomposite structures as
compared with the pure PLA, including improved mechan-
ical and flexural properties, elevated heat distortion
temperature, enhanced barrier properties and accelerated
biodegradation [21,171,175,180]. This section will focus
mainly on reviewing the literature on the processing
aspects and material properties of MMT nanocomposites.
MMT belongs to a family of clays known as smectite
with crystal structure made up of two fused silica tetra-
hedral sheets sandwiched with an edge-shared octahedral
sheet of either aluminum or magnesium hydroxide. The
thickness of a single layer is about 1 nm, while the lat-
eral dimension of the crystals can range from 30 nm to
several microns or greater. The crystal layers are stacked
regularly to provide Van der Waals gaps, known as gal-

Fig. 30. DSC curves of PLA composite materials obtained from different heating-cooling cycles: (a) neat PLA, (b) microcrystalline cellulose, (c) cellulose
fibers, and (d) wood flour. (I) Heating from 30 to 200 ◦ C at 10 ◦ C/min; (II) cooling from melt at 20 ◦ C/min (fast cooling); (III) heating from 30 to 200 ◦ C at
10 ◦ C/min, after fast cooling; (IV) cooling from melt at 2 ◦ C/min (slow cooling); (V) heating from 30 to 200 ◦ C at 10 ◦ C/min, after slow cooling. The curves are
based on the original data published by Mathew et al. [28] by permission from Elsevier B.V.
848 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
leries [119,181]. The silicate surface of MMT is relatively
more hydrophilic than PLA. Therefore, it must be organi-
cally modified to compatibilize and facilitate its dispersion
in PLA. One useful characteristic of MMT is that the cations
in the galleries, typically Na+ , Li+ , Ca2+ , Fe2+ and Mg2+ can
be substituted readily through ion exchange with organic
cations, by treating the clay with surfactants including
primary, secondary, tertiary or quaternary alkylammo-
nium or alkylphosphonium cations [119]. Another unique
property of MMT is related to its ability to delaminate
and disperse in a polymer to give individual imperme-
able platelets of about 1 nm thick. By virtue of their very
high aspect ratio, large interfacial area and nano-thickness,
the dispersed platelets lead to many characteristics that
are important for enhancing the performance of poly-
mers.
Pluta evaluated the effect of organoclay and compound-
ing conditions on polylactide/organoclay nanocomposites
(4.1% d-lactide PLLA) [20]. The PLA pellets were melt-
blended at 180 ◦ C with Cloisite® 30B (3%, w/w; modified
with methyl-bis(2-hydroxyethyl) tallowalkyl ammonium
cations) in a counter-rotating mixer at 50 rpm screw speed
for 6–30 min. The study showed that compounding of
PLA/organoclay composite resulted in 14–32% molecular
weight drop, when the composite mix was compounded
for 6–30 min, even if a dry nitrogen atmosphere was
used during the melt processing. Similar reduction in
PLA molecular weight was reported by Ray and Okamoto
on their study of various organically modified layered
silicates, which was attributed to the elevated shear
-dimethylacetamide as
mixing of PLA in the presence of the silicate, and the
presence of hydroxyl groups in the modified salt, both
of which are capable of causing hydrolysis or transes-
terification reactions in PLA when exposed to elevated
processing temperature [182]. In this study, the nanocom-
posites were first prepared by dry-mixing of PLA resin
with organoclay and extruding in twin-screw extruder
(screw speed = 100 rpm, feed rate = 120 g/min) to form
nanocomposite strands. The strand were pelletized and
dried under vacuum at 60 ◦ C for 48 h, pressed into
0.7–2 mm sheet with 1.5 MPa at 190 ◦ C for 3 min, and then
quenched and annealed at 110 ◦ C for 1.5 h before testing
[182].
The properties of MMT nanocomposites are highly
dependent on how well the clay disperses in the polymer
matrix. In general, clay dispersion can be distinguished in
three modes: (1) when the clay particles are not delam-
inated, the resulting materials tend to exhibit similar
properties as conventional microcomposites. The unsep-
arated MMT layers surrounded by the polymer are often
referred to as tactoids; (2) when the polymer chains are
inserted into the galleries of the swollen silicate layers,
the clay is known as intercalated, leading to decreased
polymer chain mobility and resulting in material reinforce-
ment; and (3) when the clay is completely delaminated
and homogeneously dispersed in the continuous polymer
matrix, the layered silicates are termed exfoliated nanocom-
posites, giving rise to the maximal potential for physical
properties enhancement. The exfoliation of MMT is largely
dependent on the chemical compatibility of the clay and
polymer matrix, as well as the process conditions used to
disperse the silicate layers of the clay. By far, exfoliation
of MMT in PLA can be best achieved by using a twin-
screw compounder. Dennis et al. reported that in order
to exfoliate MMT effectively, the clay particles need to
be sheared and fractured to form smaller stacks of tac-
toid platelets (∼100 nm in thickness). Once platelets of
shorter stack heights are formed, further delamination of
the platelets was primarily driven by the diffusion of the
polymer chains into the clay galleries, which is highly
dependent on the chemical compatibility of the poly-
mer and the organoclay surface [183]. Therefore, unless
the compatibility of the clay and polymer is improved
through chemical treatment, increasing the shear inten-
sity alone will only improve the distributive homogeneity
of the particles in the polymer, but not the delamina-
tion of the clay particles. These authors concluded that
the residence time under low and mild shearing condi-
tions is required to allow polymer chains to penetrate the
clay galleries and peel the platelets apart [183]. Unfortu-
nately, under the typical extrusion conditions, increasing
the residence time will also cause unwanted thermal
degradation, leading to molecular weight drop which
diminishes the performance-enhancing effect of nanopar-
ticles [184].
Various forms of modified MMT have been used to
enhance the material properties of PLA. Chang et al.
incorporated hexadecylamine, dodecyltrimethyl ammo-
nium bromide, and quaternary ammonium salt modified
MMT clays in PLA films at 0–10% (w/w) MMT levels, based
on wet casting method, using N,N
a solvent [185]. These authors observed that there is an
optimal loading of organoclay (∼3–4%, w/w) for achiev-
ing the greatest improvement in mechanical properties.
At higher MMT contents, the nanoparticles tended to
agglomerate, leading to mechanical weakening. In contrast,
within the 0–10% MMT loading levels, oxygen transmis-
sion rates decreased with increasing clay content which
was attributed to the increased tortuous diffusion path
of oxygen molecules through the impermeable crystalline
platelets [185]. Ogata et al. used a similar film casting
methodology to evaluate the impact of organophilic MMT
(0–10%, w/w) on PLA, except that chloroform was used
as a solvent. These authors reported that only microcom-
posites were resulted and intercalated structures were
not achieved [18]. It is unknown whether the formation
of microcomposites was due to incomplete exfoliation
of MMT in the chloroform solution or caused by the
agglomeration of MMT during the film drying step. Nev-
ertheless, these studies do highlight the importance of
solvent selection which can affect the exfoliation of the
layered silicates.
Thellen et al. studied acetyltriethyl citrate plasticized
MMT-PLA composite films formed using compounding and
extrusion blowing processes [186]. They observed about
50% improvement in oxygen and water barrier properties,
and 20% increase in modulus as compared to the neat
PLA films. Although thermal properties were not affected
by the addition of MMT, the thermal stability improved
marginally.
In summary, MMT exhibits a strong potential for
enhancing the material properties of PLA. The promising
 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852
outlook for MMT is mainly lies in its abundant sources,
benign characteristics to the environment, and low cost.
8. Conclusion: prospects of PLA polymers
PLA is a highly versatile biodegradable polymer which
can be tailor-made into different resin grades for process-
ing into a wide spectrum of products. More importantly,
the polymer can be processed using the conventional
production infrastructure with minimal equipment mod-
ification. New technologies for processing PLA, such as
using supercritical processes for foaming and electrospin-
ning for producing nanofibers, will further expand the
use of this polymer. From the environmental viewpoint,
the compostable characteristics of PLA are well suited
for many applications where recycling, reuse and recov-
ery of products are not feasible. Since the raw materials
for PLA is based on agricultural feedstock, the increased
demand for PLA resins will create a positive impact on
the global agricultural economy. Nevertheless, there are a
number of areas which still need to be improved, espe-
cially in applications where PLA is intended to be used
as a substitution for existing thermoplastics. For instance,
in food products where high barrier protection is impor-
tant, replacement of PET by PLA packaging may not be
feasible, since the barrier properties of PLA are not in
par with PET. The brittleness of PLA may also prevent its
use in applications where toughness and impact resis-
tance are critical. The fact that PLA is biodegradable may
in some cases result in unpredicted performance if the
polymer is exposed to uncontrollable abusive temperature
and humidity conditions. Aging studies which take a wider
perspective covering different environmental exposure and
process conditions will be useful. Some of these challenges
are expected to overcome through blending PLA with other
polymers, formation of micro- and nanocomposites, coat-
ing with high barrier materials, and polymer modification.
Research and development in these areas may open up
new opportunities for PLA for use as high performance
biodegradable materials.
To date, PLA is relatively more expensive than most
of the petroleum based polymers. Nonetheless, increas-
ing oil prices and the implementation of environmental
policies from the government, such as “green taxes” in
countries like Germany or Japan, and mandatory use of
compostable polymers for packaging by some large corpo-
rations, will create a push to expand the use of PLA. As the
uses for PLA continue to increase, the demand for the agri-
cultural feedstock for PLA production (mainly corn today),
will increase as well. To overcome the potential competi-
tive issues of raw materials with human and livestock food
supply chains, innovations involving the use of alternative
starch and sugar sources, including biomass and other low
value byproduct wastes, are expected to take place.
Acknowledgements
The authors are grateful to Susan E. Selke for value com-
ments and suggestions, and Ana Cristina Vega Lugo for her
assistance in preparing the manuscript.
849
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