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Progress in Polymer Science 33 (2008) 820–852

Contents lists available at ScienceDirect

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- heat-resistant properties can be injection molded using
ization, and/or polymerization through lactide formation PLA resins of less than 1% d-isomer. Alternatively, nucle-
(Fig. 1). By and large, commercially available high molecular ating agents may be added to promote the development of
weight PLA resins are produced via the lactide ring-opening crystallinity under relatively short molding cycles. In con-
polymerization route [3,4,29]. trast, PLA resins of higher d-isomer contents (4–8%) would
Commercial PLA are copolymers of poly(l-lactic acid) be more suitable for thermoformed, extruded, and blow
(PLLA) and poly(d,l-lactic acid) (PDLLA), which are pro- molded (e.g., injection molded preform for blow molding)
duced from l-lactides and d,l-lactides, respectively [3]. The products, since they are more easily processed when the
l-isomer constitutes the main fraction of PLA derived from crystallinity is low [38].
renewable sources since the majority of lactic acid from When exposed to elevated temperatures, PLA is known
biological sources exists in this form. Depending on the to undergo thermal degradation, leading to the formation
composition of the optically active l- and d,l-enantiomers, of lactide monomers (Section 3). It has been suggested
PLA can crystallize in three forms (␣, ␤ and ␥). The ␣- that this property may be leveraged for the feedstock
structure is more stable and has a melting temperature Tm recycling of PLA [39,40]. However, the propensity for the
of 185 ◦ C compared to the ␤-structure, with a Tm of 175 ◦ C lactide monomer to undergo racemization to form meso-
[3]. The optical purity of PLA has many profound effects lactide can impact the optical purity and thus the material
on the structural, thermal, barrier and mechanical proper- properties of the resulting PLA polymer [39–43]. Recently,
ties of the polymer [30–36]. PLA polymers with l-content Tsukegi et al. reported that at temperature less than
greater than ∼90% tend to be crystalline while those with 200 ◦ C, conversion of PLLA into meso-lactide and oligomers
lower optical purity are amorphous. Moreover, Tm , glass was minimal. However, above this temperature, the for-
transition temperature Tg , and crystallinity decrease with mation of meso-lactide became quite significant (4.5 wt%
decreasing l-isomer content [30,34,37]. Tsuji et al. reported at 200 ◦ C and 38.7 wt% at 300 ◦ C for 120 min heating).
that the optical impurity of PLLA films ranging from 0–50% Oligomers were reported to form at temperatures higher
was insignificant in affecting the water vapor transmis- than 230 ◦ C [39]. These authors also reported that the
sion rate (WVTR) of the polymer; nevertheless, the WVTR oligomerization proceeded rapidly in the presence of MgO,
values decreased with increasing film crystallinity in the to reach an equilibrium between monomers and oligomers;
0–20% range [31]. Thus, judicious selection of appropriate the l,l:meso:d,d lactide composition ratio converged to
PLA resin grade is important to match the conversion pro- 1:1.22:0.99 (w/w/w) after 120 min heating at 300 ◦ C [39].
cess conditions used. Usually, PLA articles which require Fan et al. reported that the racemization at 250–300 ◦ C
L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 823

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
Fig. 2. Comparison of glass transition and melting temperatures of PLA weight can be represented by the Flory–Fox equation:
with other thermoplastics.
Tg∞ − K
Tg = (1)
can be controlled by adding calcium oxide to PLLA, which M̄n
reduces the pyrolysis temperature, and more importantly,
where Tg∞ is the Tg at the infinite molecular weight, K is a
leads to predominant l,l-lactide formation [40].
constant representing the excess free volume of the end
groups for polymer chains, and M̄n is the number aver-
3. Thermal properties 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
Similar to many thermoplastic polymers, semicrys- for PLLA and PDLLA, respectively [45].
talline PLA exhibits Tg and Tm . Above Tg (∼58 ◦ C) PLA is The glass transition behavior of PLA is also dependent
rubbery, while below Tg , it becomes a glass which is still on the thermal history of the polymer. Quenching the poly-
capable to creep until it is cooled to its ␤ transition tem- mer from the melt at a high cooling rate (>500 ◦ C/min, such
perature at approximately −45 ◦ C, below which it behaves as during injection molding) will result in a highly amor-
as a brittle polymer [44]. Fig. 2 compares PLA’s Tg and Tm phous polymer. PLA polymers with low crystallinity have a
values with other polymers. As shown, PLA has relatively tendency to undergo rapid aging in a matter of days under
high Tg and low Tm as compared to other thermoplastics. ambient conditions [46,47]. The phenomenon is an impor-
The Tg of PLA is dependent on both the molecular tant contributor to the embrittlement of PLA. This topic will
weight and the optical purity of the polymer (Fig. 3). The be discussed in greater details in Section 7.2.
Tg increases with molecular weight to maximum values The Tm of PLA is also a function of its optical purity.
at infinite molecular weight of 60.2, 56.4 and 54.6 ◦ C for The maximum practical obtainable Tm for stereochemically
PLA consisting of 100, 80, and 50% l-stereoisomer contents, pure PLA (either l or d) is around 180 ◦ C with an enthalpy
respectively. Furthermore, PLA with higher content of l- of 40–50 J/g. The presence of meso-lactide in the PLA struc-
lactide has higher Tg values than the same polymer with ture can depress the Tm by as much as 50 ◦ C, depending
the same amount of d-lactide [37]. Similar relationships on the amount of d-lactide incorporated to the polymer.
were reported by Tsuji and Ikada [34]. Table 1 shows the Fig. 4 shows the variation of the Tm as a function of % meso-
lactide introduced in the PLA based on data from Witzke

Fig. 3. Glass transition temperatures for PLAs of different l-contents as a Fig. 4. Peak melting temperature of PLA as a function of % meso-lactide.
function of molecular weight. Curves are created based on the original data () Represents values reported by Witzke [48]; (䊉) represents values
published by Dorgan et al. [37] by permission of The Society of Rheology. 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) 820–852 825

Fig. 7. DSC scans at 20 K/min for PLA with 1.5% (PLA-L), 8.1% (PLA-M), Fig. 8. Development of crystallinity in biaxially stretched PLA at 80 ◦ C
and 16.4% (PLA-H) d-isomers. All samples were cooled quickly from the using 100% s−1 strain rate. Data are adapted from Drumright et al. [38]
melt and isothermally crystallized at 145 ◦ C for 15 h. The quenched PLA-L by permission of Wiley–VCH Verlag GmbH & Co. KGaA.
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. increasing heating rate, whereas the high temperature Tm
decreased. In contrast, increasing the cooling rate reduced
isothermal kinetic analysis of PLLA. Solving Eq. (4) with the low Tm peak, while the high Tm peak increased. The
Tm = 480 K, Hf = 111.083 × 106 J/m3 ; b = 5.17 × 10−8 cm, double-melting peak behavior was explained based on
12.03 × 10−3 J/m2 , and  e = 6.089 × 10−4 J/m2 , Kg can be melt-recrystallization model, in which small and imper-
determined. This value can be used to evaluate the transi- fect crystals changed successively into more stable crystals
tion between two types of crystallization behavior in PLA. through the melting and recrystallization [60].
In the first type of crystallization, the nucleation rate is Another strategy to increase the crystallinity of PLA is
low and axialite morphology in the films is prevalent. In by incorporating nucleating agent in the polymer during
the second type, the nucleation rate is high, so multinu- extrusion. This lowers the surface free energy barrier for
cleation occurs and spherulitic morphology in the films nucleation and enables crystallization at higher tempera-
is observed [57]. For PLLA, both crystallization processes ture to take place upon cooling. Kolstad showed that talc
have been observed depending on the molecular weight can be added to PLLA to effectively modify the crystalliza-
of the samples. The infinite dissolution temperature Td0 tion rate of the polymer [56]. With 6% talc added to PLLA,
(determined by the extrapolation of dissolution tempera- the crystallization half-time of the polymer reduced from
ture Td versus crystallization temperature Tc plots to the 3 min at 110 ◦ C to approximately 25 s. At the same percent of
intersection where Td = Tc ) for PLLA in p-xylene solution talc, for 3% mesolactide copolymerized with the l-lactide,
was determined by Kalb and Pennings to be 126.5 ◦ C [58]. the half-time reduced from about 7 min to about 1 min [56].
This temperature is relevant for fiber formation processes, Li and Huneault compared the crystallization kinetics of
since fibers prepared from solution near this temperature talc and montmorillonite (MMT, Cloisite® Na+ ) for 4.5% d-
have ultra-high strength properties [58]. PLA. They reported that the lowest crystallization induction
The formation of crystallinity may or may not be favor- period and maximum crystallization speeds were observed
able depending on the end-use requirements of the PLA around 100 ◦ C. By adding 1% (w/w) of talc, the crystalliza-
articles. For instance, high crystallinity will not be opti- tion half time of PLA was decreased from a few hours to
mal for injection molded preforms which are intended 8 min. In contrast, the MMT tested was less effective as a
for further blow molding since rapid crystallization of the nucleating agent; the lowest half-time achieved was 30 min
polymer would hamper the stretching of the preform and [61].
optical clarity of the resulting bottle. In contrast, increased Unlike quiescent crystallization discussed above, strain-
crystallinity will be desirable for injection molded articles induced crystallization occurs when the polymer is
for which good thermal stability is important. Crystal- mechanically orientated. This phenomenon is prevalent
lization of PLA articles can be initiated by annealing at during the production of oriented PLA films, stretch blow
temperatures higher than Tg and below the melting point molding of bottles, thermoforming of containers, and fiber
to improve their thermal stability. For instance, Perego et spinning. As expected, the proportion of d- and l-isomers
al. showed that crystallization of injection molded PLLA has an effect on the strain-induced crystallinity during
parts by annealing at 105 ◦ C for 90 min increased tensional the mechanical orientation. As shown in Fig. 8, the per-
and flexural elasticity, Izod impact strength, and heat resis- cent crystallinity of amorphous PLA sheet increases with
tance [59]. After annealing PLA copolymers, the presence increasing draw ratio. Moreover, the crystallinity decreases
of two melting peaks in a DSC scan is quite common, as as the stereoisomeric purity of the polymer decreases [38].
previously observed by Yasuniwa et al. [60]. They reported The amount of crystallinity attained through orientation
that the low temperature Tm peak height increased with also depends on the mode of stretching (sequential ver-
826 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852

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)
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 where Wmeso and Wl-mer are the initial weight frac-
[48], and PLLA at 180 ◦ C as reported by Dorgan et al.[12]. tions for meso-lactide and l-lactide, respectively,
a1 = −13,000, a2 = −142,000, a3 = 112,000, C1 = 15.6 ± 1.6,
sus simultaneous), strain rate, temperature, and annealing and C2 = 110 ± 11 ◦ C; a1 , a2 , a3 , and C1 do not have units;
conditions [38,62,63]. More discussions on this topic will and T(C) is the testing temperature in ◦ C. Eq. (6) can
be presented in Section 7.2. be used to predict 0 of amorphous polylactides with
l-monomer composition higher than 50% between Tg
5. Rheological properties and Tg + 100 ◦ C. The equation predicts that 0 increases
with increasing l-monomer and decrease as meso-lactide
Melt rheological properties of PLA have a profound content increases [48].
effect on how the polymer flows during the conver- The rheological properties of PLA can be modified by the
sion process. Since the PLA rheological properties are introduction of branching into the polymer chain architec-
highly dependent on temperature, molecular weight and ture. Many routes, such as multifunctional polymerization
shear rate, they must be taken into consideration during initiators, hydroxycyclic ester initiators, multicyclic ester,
tooling design, process optimization, and process model- and crosslinking via free radical addition have been used
ing/simulation. Melt viscosities of high-molecular-weight to introduce branching in PLA [12,67–69]. Lehermeier
PLA are in the order of 5000–10,000 P (500–1000 Pa s) and Dorgan blended PLA with 5% d-isomer with varying
at shear rates of 10–50 s−1 . These polymer grades are proportions of branched PLA produced through peroxide
equivalent to Mw ∼100,000 Da for injection molding to initiated crosslinking of linear PLA by reactive extrusion
∼300,000 Da for film cast extrusion applications [4]. The [67]. They observed that 0 of the blends deviated con-
melts of high molecular weight PLA behave like a pseu- siderably from the log additive rule and attributed this to
doplastic, non-Newtonian fluid. In contrast, low molecular the effect of free volume. Lehermeier and Dorgan showed
weight PLA (∼40,000 Da) shows Newtonian-like behavior that tris(nonylphenyl) phosphite was effective for stabi-
at shear rates typical of film extrusion [64]. Under iden- lizing the viscosity of PLA during the thermorheological
tical processing conditions, semicrystalline PLA tends to time sweep experiment of branched PLA polymers [67]. In
possess higher shear viscosity than its amorphous counter- another study from the same research group, the stabiliz-
part. Moreover, as shear rates increase, the viscosities of the ing effect of tris(nonylphenyl) phosphate was elucidated
melt decrease considerably, i.e., the polymer melt exhibits by using the time-temperature superposition technique,
shear-thinning behavior [65]. showing that this compound greatly facilitated the ther-
Viscoelastic properties of polymer melts can be charac- morheological experiments by prevented the confounding
terized by zero-shear viscosity, 0 , and recoverable shear effect from degradation reactions [69,70].
compliance JeO . Both of these parameters can be obtained Carreau–Yasuda model (Eq. (7)) has been used to model
from dynamic experiments by determining the dynamic the viscosity and shear rate relationship of linear PLA and
moduli at the limit of low frequency [48]. The product of linear-branched PLA blends [69]:
these two values (0 × JeO ) gives the average relaxation time ˙ C3 ](C4 −1/C3 )
 = C1 [1 + (C2 ) (7)
required for final stress equilibration time in the liquid  0 .
The value of 0 is strongly affected by the molecular weight, where  is the viscosity,  is the shear rate, and C1 , C2 , C3
which is typically described empirically by the power law and C4 are material dependent parameters. The constants
equation. Cooper-White and Mackay reported that the 0 for the model are summarized in Table 3. C1 determines
of PLLA melt showed dependence on Mw to the 4.0 power 0 which decreases with increasing linear content. C2 is
instead of the theoretical value of 3.4 [64]. In comparison, the relaxation time approximately corresponded to the
Dorgan et al. reported a power index of 4.6 [66]. Fig. 9 shows reciprocal of frequency for the onset of shear thinning.
the relationship between 0 and Mw for PLLA (100:0) at 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- formulation point of view, the residual polymerizing
ered to be non-toxic and it is naturally present in many catalysts present in the resin are also known to catalyze
foods, the acetaldehyde generated during melt processing the reverse depolymerization and hydrolysis reactions
of PLA must be minimized, especially if the converted PLA [48,79]. This may partially explain the large variation of
(e.g., container, bottle, and films) are to be used for food molecular weight drop for melt processed PLA reported
packaging. The migration of acetaldehyde into the con- in the literature. For instance, Witzke, Gogolewski et al.
tained food can result in off-flavor which may impact the and Perego et al. reported molecular weight losses for
organoleptic properties and consumer acceptance of the injection molded PLA parts of 5–52%, 50–88% and 14–40%,
product [75–77]. respectively [48,59,80]. To stabilize the polymer during
From the production point of view, the formation of melt processing, the removal or deactivation of the residual
lactide due to depolymerization is undesirable. Besides catalyst is important to minimize the molecular weight
reducing PLA melt viscosity and elasticity, the volatile lac- loss which will impact the mechanical properties of the
tide formed can result in fuming and/or fouling of the PLA parts. Strategies to improve the melt stability of PLA
processing equipment such as chilled rollers, molds and can be found in patent publications [79,81,82]. Due to
tooling surfaces [78]. The latter is characterized by the the different processes and technologies used, the melt
gradual building up of a layer of lactide on the equipment stability of PLA polymer may be different from supplier to
surfaces, commonly known as plate out. To overcome this supplier. Injection molded PLA made from properly dried
problem, the temperature of the equipment is generally good quality PLA resins and optimal processes should
elevated to reduce the tendency of condensation of lactide. exhibit molecular weight loss of 10% or less [83].
Taubner and Shishoo showed that the moisture content
of resin, temperature, and residence time of PLA melt 7. Processing of PLA
during extrusion are important contributors to molecular
weight drop of the polymer during extrusion [72]. Pro- 7.1. Drying and extrusion
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 Prior to melting processing of PLA, the polymer must be
33,600 and 30,200 g/mol, when screw rotation speeds of dried sufficiently to prevent excessive hydrolysis (molec-
120 and 20 rpm were used, respectively. Using the same ular weight drop) which can compromise the physical
120 and 20 rpm screw speeds but processing at 240 ◦ C, properties of the polymer. Typically the polymer is dried to
the Mn values decreased dramatically to 25,600 and less than 100 ppm (0.01%, w/w). Natureworks LLC, one of
13,600 g/mol, respectively. In contrast, Mn for extruded the main suppliers for PLA polymers, recommended that
articles produced from wet resins (equilibrated at 20 ◦ C resins should be dried to 250 ppm (0.025%, w/w) mois-
65% RH to give 0.3%, w/w, moisture content) were 18,400 ture content or below before extrusion. Processes that
and 12,000 g/mol, respectively. These results highlighted have long residence times or high temperature approaching
the importance of minimizing the residence time and 240 ◦ C should dry resins below 50 ppm to achieve maxi-
process temperature during PLA extrusion. From a resin mum retention of molecular weight [84,85]. Drying of PLA
L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 829

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 Fig. 12. Typical closed loop dual-bed regenerative desiccant-type dryer
bridge and plug the dryer. It is noteworthy that because for drying PLA before extrusion.
PLA degrades at elevated temperatures and high relative
humidity, the resins should be protected from hot and process air is greater than the set point, the desiccant goes
humid environments. Henton et al. reported that amor- into the regeneration cycle where the desiccant is heated
phous PLA can dramatically reduce its Mw in less than a to desorb the moisture from the desiccant and vent it to the
month when exposed to 60 ◦ C and 80% RH (Fig. 11) [44]. atmosphere. Meanwhile, the process air is directed to the
To achieve an effective drying, the dew point of the stand-by desiccant which was previously dried.
drying air should be −40 ◦ C or lower. Drying of PLA is com- Extrusion is the most important technique for contin-
monly achieved using a closed loop dual-bed regenerative uously melt processing of PLA. The plasticizing extruder
desiccant-type dryer. In this type of dryer, the resin pellets can be part of the forming machine systems for injection
are contained in a hopper that is purged with dry air at molding, blow molding, film blowing and melt spinning.
elevated temperature. The dry air is generated by the des- Fig. 13 shows a schematic representation of the major com-
iccant bed. During the operation, one desiccant bed is in ponents of an extruder for an injection molding machine. A
the process air stream which removes moisture from the typical screw consists of three sections: (1) feed section –
resin, while the other stand-by bed is being regenerated acts as an auger which receives the polymer pellets and
(Fig. 12). The hot air from the process stream removes the conveys the polymer into the screw; (2) transition sec-
moisture from the resin in the hopper. The air is then circu- tion (also known as compression or melting sections) –
lated back to the dryer where it is cooled and the moisture flight depth decreases gradually, which compresses the pel-
is stripped by the desiccant. The air is reheated before it is lets to enhance the friction and contact with the barrel. In
channeled back to the hopper. When the dew point of the 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
Fig. 11. Plots of molecular weight loss of PLA versus time under different
environment conditions. Curves are based on the original data published the shear heating it provides. The recommended compres-
by Henton et al. [44]. 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 shooting pot and extruder in a single machine, have also
fed from a hopper near the end of a barrel. The screw, been deployed for injection molding of preforms for PLA
driven by an electric or hydraulic motor, rotates and trans- bottles. The two-stage system consists an in-line extruder
ports the material towards the other end of the barrel. The integrated to a shooting pot. The extruder plasticizes and
heat required for melting is provided by the heater bands feeds the melt into the shooting pot under relatively low
wrapped around the barrel. As the screw rotates, the flights injection pressure, from which the melt is injected into the
shear and push the polymer against the wall of the barrel hot runner under high pressure by a plunger in the shooting
which also provides frictional heat for melting the poly- pot. While the reciprocating machine must stop the screw
mer. The combined thermal energy from the heater and during the injection and packing phases, the screw for the
frictional heat due to friction between the plastic and the two-stage machine can rotate during the majority of the
screw and barrel, provide sufficient heat to raise the PLA cycle. The two-stage system presents some advantages over
polymer above its melting point (170–180 ◦ C) by the time its reciprocating counterpart, including shorter cycle time,
it reaches the end of the barrel. To ensure that all the crys- small screw motor drive, more consistent melt quality, and
talline phases are melted and to achieve an optimal melt more consistent shot size [87].
viscosity for processing, the heater set point is usually set A typical cycle for an injection molding machine is pre-
at 200–210 ◦ C. sented in Fig. 15. The beginning of mold close is usually
taken as the start of an injection molding cycle. Immedi-
7.2. Injection molding ately after the molds clamp up, the nozzle opens and the
screw moves forward, injecting the polymer melt into the
Injection molding is the most widely used converting mold cavity. To compensate for the material shrinkage dur-
process for thermoplastic articles, especially for those that ing cooling in the mold, the screw is maintained in the
are complex in shape and require high dimensional preci- forward position by a holding pressure. At the end of the
sion. All injection molding machines have an extruder for holding phase, the nozzle is shut off and the screw begins to
plasticizing the polymer melt. Unlike a standard extruder, recover, while the part continues to be cooled in the mold.
the extruder unit for injection molding machine is designed During the recovery phase, the screw rotates and conveys
such the screw can reciprocate within the barrel to pro- the polymer forward along the screw. At the same time,
vide enough injection pressure to deliver the polymer melt the screw is allowed to slide backward within the barrel
into the mold cavities (Fig. 14). Most injection molding against a controlled back pressure exerted on the screw
machines for PLA are based on the reciprocating screw by a hydraulic cylinder. To ensure that the part is dimen-
extruder, although two-stage systems, which integrate a sionally stable enough to withstand the opening stroke the

Fig. 14. Major components of an injection molding machine showing the extruder (reciprocal screw) and clamp units.
L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 831

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
Fig. 15. Typical cycle for an injection molding process.
injected and packed to the holding pressure (trace ab in
Fig. 16). The polymer then undergoes isobaric cooling in
molds, sufficient cooling time must be given. In the mold- the holding phase (trace bc), followed by isochoric cool-
ing cycle, heat removal takes place predominantly during ing. When the polymer cools below the freezing point, the
the fill, hold and cool phases, although mold opening phase gate freezes and the pressure in the mold cavities drops
also contributes to partial cooling since one side of the part to one atmospheric pressure (trace cd). In the last cool-
(core-contacting side) is still being cooled prior to ejection. ing phase, the article continues to cool isobarically to room
Cycle time is an important process parameter which is temperature (trace de). The change in specific volume dur-
often minimized to maximize the production throughput. ing the final isobaric cooling (trace de) dictates the extent
To reduce the cycle time, it is quite common to transfer of part shrinkage. The hold pressure and temperature play
the partially cooled injection molded article to a post-mold an important role in determining how much the molded
cooling device, to provide an extended cooling of the part article shrinks.
outside the molds, either by direct contact on a chilled sur- The PVT relationship can be modeled mathematically,
face and/or by forced air. From Fig. 15, it is also evident such as by using the modified two-domain Tait model
that minimizing the duration for non-process events, such [90–92]. This model is often used for numerical simula-
as mold opening, part ejection and mold closing is also tion of injection molding processes involving finite element
important for reducing the cycle time. Lowering mold tem- analysis for predicting the shrinkage behavior of injection

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)).
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 rapid physical aging of the polymer since ambient tem-
takes the form: perature is only about 25 ◦ C below the Tg [37,46,48]. The
  p
 aging of PLA can be evaluated by studying the Tg region of
v(T, p) = V0 (T ) 1 − C ln 1 + + Vt (T, p) (9) a DSC scan. By measuring the development of endother-
B(T )
mic enthalpy relaxation Hrel using DSC on injection
where v(T, p) is specific volume at temperature T and pres- molded samples made from PLA (96% l-lactide), Cai et al.
sure P; V0 is specific volume at zero gauge pressure and C is showed that Hrel increased with increasing aging time
a constant, 0.0894. When the temperature of the material [47] (Fig. 17). They also showed that as the aging temper-
is greater than the transition temperature, V0 (T) and B(T) ature increased towards the Tg , the rate of physical aging
are determined by b1m , b2m , b3m , b4m and b5 as follows: also became faster. However, when the aging temperature
V0 = b1m + b2m (T − b5 ) (10) went above the Tg (60 ◦ C), the excess enthalpy relaxation
was reduced, indicating that physical aging was no longer
B(T ) = b3m exp[−b4m (T − b5 )] (11) taking place when the aging temperature was above Tg [47].
In contrast, when the material temperature is lower than Celli and Scandola observed a similar aging trend for PLLA
the transition temperature, V0 (T) and B(T) are determined using DSC and a dynamic mechanical analyzer [46]. They
by b1s , b2s , b3s , b4s and b5 as follows: observed that the extent of aging increased with decreas-
ing molecular weight (i.e., Hrel increased with decreasing
V0 = b1s + b2s (T − b5 ) (12) molecular weight), which was attributed to the increased
chain terminals that possess higher motional freedom than
B(T ) = b3s exp[−b4s (T − b5 )] (13)
the internal chain segments [46]. The physical implication
Because the transition temperature, Ttrans (P), is often pres- of aging was elucidated by Witzke, who reported that injec-
sure dependent, it is often correlated with pressure and tion molded articles tested immediately after quenching
the transition temperature at zero gauge pressure (b5 ) as to very cold temperatures exhibited a much larger exten-
follows: sion to break. However, when the molded specimens were
aged at room temperature for 3–8 h, they became very
Ttrans (P) = b5 + b6 p (14)
brittle [48]. This phenomenon was attributed to the reduc-
For non-amorphous materials, an additional transition tion of free volume of the polymer due to rapid relaxation
function is required: towards the equilibrium amorphous state. Aging below Tg is
exclusively related to the amorphous phase of the polymer;
Vt (T, p) = b7 exp[b8 (T − b5 ) − b9 p] (15) accordingly, increasing the crystallinity of the polymer (e.g.,
The estimated parameter values for the modified two- by adjusting d-isomer composition or the use of nucleat-
domain Tait model are shown in the inserts in Fig. 16. ing agents) will reduce the aging effect. Furthermore, the
In general, injection molded PLA articles are relatively crystallites formed also act like physical crosslinks to retard
brittle. The brittleness of PLA has been attributed to the the polymer chain mobility. However, amorphous injection
L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 833

molded articles which are intended for further process- physical and barrier properties compared to injec-
ing (e.g., preforms for stretch blow molding), the storage tion molded amorphous PLA. The molecular orientation
conditions prior to subsequent processing may need to induced during the ISBM process decreases the effect of
be controlled. Moreover, process parameters such as mold aging by stabilizing the polymer free volume [48]. The
temperature, packing pressure, cooling rate, and post-mold crystallites produced during strain-induced crystallization
cooling treatment are expected to influence the PLA aging also reduce the aging effect since they can act as physical
behavior as well. crosslinks to stabilize the amorphous phase, thereby reduc-
ing its brittleness. Similar effects have been reported for
7.3. Stretch blow molding semicrystalline PET [93]. The ISBM process for PLA bottles
is depicted in Fig. 18. It involves first the formation of pre-
Due to the recent consumers’ heightened environmen- form (also known as parison) using an injection molding
tal awareness, there is a sustained interest from the food machine. The preform is then transferred to a blow mold-
industry to replace the existing non-biodegradable ther- ing machine where it is stretched in the axial direction and
moplastics with PLA for certain beverage products. To date, blown in the hoop direction to achieve biaxial orientation
PLA bottles are predominantly used for beverages which are of the polymer. In the blow molding machine, the preform
not sensitive to oxygen (e.g., flat water beverages, pasteur- is heated in front of several banks of infrared heater to tem-
ized milk). While barrier properties of PLA bottles may be peratures (85–110 ◦ C) suitable for blow molding (Fig. 18a).
improved by various technologies (multilayer structures, Different power settings are usually applied to the infrared
external coating, internal plasma deposition, oxygen scav- heaters to give a temperature profile optimal for stretch-
enger), their implementation is currently limited due to ing the preform into bottle with uniform wall thickness
higher production costs. distribution. Frequently, reheat additives, such as carbon
The production of PLA bottles is based on injection black dispersed in a liquid carrier, are added to the resin
stretch blow molding (ISBM) technique. This process pro- in the extruder to increase its infrared energy absorption.
duces biaxial orientated PLA bottle with much improved PLA preforms have a tendency to shrink after reheat, espe-

Fig. 18. Injection stretch blow molding (ISBM) of PLA bottle.


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 ing due to the compression load from the blow nozzle. The
residual injection molding stresses are the greatest. This blow mold temperature for PLA is typically set at around
may be moderated through proper preform design, with 35 ◦ C. Because the base of the bottle tends to be quite thick,
gradual transition regions. When the preform has attained the residual heat can cause the base to roll out after the
the optimal temperature, it is transferred to the blow mold bottle is ejected from the blow mold. This problem can be
(Fig. 18b). The blow nozzle is lowered to seal the preform overcome by incorporating radial ribs to reinforce the base
finish, while the stretch rod travels towards the preform, and/or chilling the base mold insert to a temperature lower
at a typical speed of 1–1.5 m/s, and stretches the preform than the mold halves [94].
to the base cup (Fig. 18c–e). During the preblow phase Similarly to PET, PLA exhibits strain-hardening when
(Fig. 18d and e), compressed air of 0.5–2.0 MPa is admitted stretched to high strain. This self-leveling phenomenon is
to the preform through the blow nozzle to partially inflate desirable for blow molding of preforms to achieve optimal
the preform to prevent it from touching the stretch rod dur- bottle side wall orientation and minimize wall thickness
ing the axial stretching. When the stretch rod arrives at the variation. Since strain-hardening occurs only when the PLA
base cup and pins the preform to the mold base, the air pres- is stretched beyond its natural stretch ratio, the preform
sure ramps up to 3.8–4.0 MPa to fully inflate the preform. must be designed to match the target bottle size and shape,
This forces the inflated preform to take the shape of the such that optimal stretch ratios are achieved during blow
blow mold and to imprint the surface details of the bottles molding (Fig. 20). Preforms that are under-stretched will
(Fig. 18f and g). The high blow pressure is maintained for result in bottles with excessive wall thickness variation,
several seconds to allow the bottle to cool down sufficiently weak mechanical properties and poor aesthetic appeal (e.g.,
before discharging the bottle. lens defect below the support ledge region). In contrast,
The aforementioned process is known as the two-stage overstretched bottles can also result in stress whitening
process. In contrast, the one-stage process entails the injec- due to the formation of micro-cracks on the bottle surfaces
tion and blow molding of the preform within the same that diffract light. Typical commercial grade PLA resins for
machine equipped with both injection and blow mold- bottle applications require preform axial stretch ratios of
ing units. In this process, the injection molded preform 2.8–3.2 and hoop stretch ratios of 2–3, with the desirable
is partially cooled down to 100–120 ◦ C and then stretch planar stretch ratio of 8–11 [94,95]. It is noteworthy that the
blown in the blow molding station. Fig. 19 summarizes the ultimate amount of crystallinity after stretching decreases
thermal history of PLA from resin pellets to bottle for the with the decreasing stereoisomeric purity of the polymer
two processes. As shown, PLA preform made in the one- [38]. Accordingly, the optimal stretch ratios depend on the
stage process does not go through the aging process during grade of PLA used.
which the polymer tends to embrittle. Thus, PLA preforms Preform designs are often proprietary, and therefore
intended for one- and two-stage processes may need to be there is a lack of information in the open literature. An opti-
designed and processed differently. The neck finish of the mal preform design should meet the minimum required
preform is highly amorphous and is quite brittle. Therefore, stretching which is above the natural stretch ratio, by vary-
the neck finish must be designed such that the side wall is ing the shape, diameter, length, blend radius, and transition
thick enough to prevent the neck from blowing out or crack- features, to meet the part weight requirement. Depending

Fig. 19. Thermal history of PLA polymer during one- and two-stage PLA bottle manufacturing.
L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 835

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 are usually used. Lactide monomer buildup around the
as transition shape (reverse versus standard taper), step die could be further prevented by using an exhaust sys-
changes, and pinch points on the core and cavity may also tem. Nevertheless, extreme high temperatures should be
be incorporated in the preform design. Since the stretching avoided as the web will stick to the rollers, resulting in
behavior of PLA is similar to PET but not entirely the same, poor quality sheet. To reduce the chance of trapping air
conversion of materials using existing PET preform designs and reduce film or sheet defects, one resin supplier recom-
may be feasible, although design modifications are often mended that the die be positioned as close as possible to
required to achieve an optimized bottle. the entrance nip and slightly higher than the nip to accom-
modate the slight drooping of the molten PLA web [84].
7.4. Cast film and sheet 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
PLA with l-lactide contents of 92–98% have been 15 mm [96]. Generally, hydraulic rolls stands, capable of
successfully extruded using conventional extruders. The producing pressure around 800–900 lbs/linear inch of die is
production of PLA film and sheet is practically identical; the required to prevent floating of the rolls which would result
main difference between them is their stiffness and flexi- in uneven PLA surfaces, edge instability, and neck-in [84].
bility due to the difference in their thicknesses. Typically, Good contact between the web and rolls is also important
films are ≤0.076 mm (0.003 in.) in thickness, while sheets to minimize lactide buildup. Casting of PLA film usually
are typically ≥0.25 mm (0.01 in.). In cast film extrusion, the requires edge pinning (electrostatic or low pressure air) to
molten PLA is extruded through a sheet die and quenched eliminate streaking, reduce neck-in, and improve edge sta-
on polished chrome rollers that are cooled with circulating bility [97]. Slitting and web handling of PLA is similar to
water. Due to the thermal sensitivity of PLA, the use of exter- PS. Edge trimming of PLA should be carried out with rotary
nal deckles on the die should be avoided since the degraded shear knives since razor knives may yield rough edges and
resin behind the deckles can lead to edge instability. Usually web breaks. Winding of the PLA web should be done with
the die gap is set to 10% or 25–50 ␮m (1–2 mils) greater than good tension control in order to obtain a consistent gauge.
the target sheet thickness [84]. Ljungberg et al. extruded Similar to PP, PET and PS films, the physical properties
neat PLA in a Haake Rheomex 254 extruder with a Rheo- of PLA films can be enhanced through orientation. Uniaxial
cord 90 drive unit (Karlsruhe, Germany) [96]. The 19.3 mm orientation of PLA is achieved in conventional machine-
diameter screw has a compression ratio of 2:1 and l/d ratio direction orientation (MDO) rolls. Since PLA tends to neck in
of 25. In this study, the temperatures for the feeding zone, during drawing, nipped rolls are usually required. Through
the barrel and the die were 160, 180, and 175 ◦ C, respec- mechanical drawing, it is possible to improve thermal and
tively [96]. Similar extruder temperature profiles were used impact resistance of the PLA film or sheet to a level simi-
by Gruber et al. [79]. lar as oriented polystyrene (OPS), oriented polypropylene
Sheet and film forming can be achieved on a three-roll (OPP) or polyester. An oriented PLA film can be obtained
stack. Because of the low melt strength of PLA, horizontal by stretching it to two to ten times its original length at
roll stacks configuration is preferred. To avoid the con- 60–80 ◦ C [51], which is much lower compared with OPP
densation of lactide monomers and slippage of web on and PET. Typical drawing temperatures for PLA films in the
the rollers, relatively high roller temperatures (25–50 ◦ C) machine (MD) and transverse directions (TD) are presented
836 L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852

Table 6 To overcome these shortcomings, PLA is often coextruded


Recommended drawing conditions in the machine and transverse direc-
with other polymers to form multilayer structures to
tion for PLA [97]
enhance its properties. For instance, to reduce electrostatic
Section Temperature range (◦ C) buildup, Rosenbaum et al. disclosed methods for forming
Machine direction preheat 45–65 biaxially oriented multilayer films made of one PLA-based
Slow draw 55–70 layer and two outer layers consist of PLA and glycerol fatty
Fast draw 70–75 acid esters to achieve films with antistatic surfaces [98]. The
Annealing 45–55
extruder temperatures used ranged from 170 to 200 ◦ C with
Transverse direction the take off roll set at 60 ◦ C. The biaxial orientation took
Preheat 65–70 place sequentially, first at 68 ◦ C in the machine direction
Draw 70–85 by rollers running at different speeds, followed by trans-
Annealing 125–140
verse direction stretching using a tenter frame at 88 ◦ C.
Stretch ratios were 2.0 and 5.5 for machine and transverse
in Table 6. In generally, for 98% l-lactide PLA, machine direction stretching, respectively. To impart dimensional
direction orientation of 2–3× is expected, while transverse stability to the film, heat-setting was conducted at 75 ◦ C.
stretch ratios of 2–4× may be used. At higher d-lactide Noda et al. disclosed a method of coextruding multi-
contents, the machine and transverse stretch ratio can be layer laminate film consisting of polyhydroxyalkanoate
increased. Fig. 21 shows a typical extrusion cast line for (PHA) copolymer (copolymer of 3-hydroxybutyrate with 3-
producing biaxially oriented PLA film. hydroxyhexanoate) and PLA to impart softness to the PLA,
The orientation in PLLA films depends on the draw and at the same time reduce the tackiness of the PHA. By
rate, temperature and ratio. High strain rate, low tem- preventing the web from sticking to itself or the processing
perature and high stretch ratio favor strain-induced equipment, the speed of production and product quality
crystallization during orientation. Taking the competitive can be improved [99].
crystallization and relaxation effects into consideration, PLA films tend to have higher surface energy than
Lee at al. concluded that the optimal drawing tem- untreated polyolefin films. Gruber et al. reported surface
perature to obtain highly oriented PLLA films (Mw of energy of about 44 dynes/cm for pure PLA films [79].
190,000 g/mol) is about 80 ◦ C [63]. In contrast, Gruber et al. The surface energy values for 98% l-lactide and 94% l-
used somewhat lower temperatures for biaxial orientation lactide films were reported as 42 and 34–38 dynes/cm,
of 100,000–150,000Mn PLA polymer with 10–20% meso- respectively [100]. Higher surface energy will provide more
lactide content (65–72 and 20 ◦ C for preheat and cooling satisfactory printing properties without surface treatment.
rolls, respectively, for MD stretching; 63–70 ◦ C and circu- If higher surface energy is needed for downstream process-
lated ambient air cooling for TD drawing) [79]. Ou and ing, the surface can be treated by corona discharge.
Cakmak prepared biaxially oriented PLA films by stretching
cast PLA in both MD and TD to different ratios, followed by 7.5. Extrusion blown film
annealing these films at elevated temperatures to induce
crystallinity and dimensional stability [62]. Their wide In extrusion blow film process, molten PLA is extruded
angle X-ray (WAXS) results showed that the development to form a tube using an annular die. By blowing air through
of crystalline order and orientation were dependent on the die head, the tube is inflated into a thin tubular bub-
the mode of orientation. They observed that simultaneous ble and cooled. The tube is then flattened in the nip rolls
biaxial stretching of PLA film resulted in poor crystalline and taken up by the winder (Fig. 22). The ratio of bubble
order, while sequential stretching promoted a greater crys- diameter to the die diameter is called the blow-up-ratio
talline order [62]. Hence, the properties of PLA films are (BUR). BUR ratios of 2:1–4:1 with the die temperature
expected to change depending on the stretching sequence of 190–200 ◦ C have been used for extrusion blowing of
used during the orientation process. PLA films [101,102]. By varying the BUR, screw speed, air
PLA has excellent optical properties and high modulus. pressure, and winder speed, films of different thicknesses
However, it has low elongation, tear and burst strengths. (∼10–150 ␮m) and degree of orientation can be achieved.

Fig. 21. Biaxial oriented extrusion cast film machine.


L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 837

Fig. 22. Extrusion blown film line.

PLA has a specific density of about 1.24 g/cm3 which is (e.g., oleamide, stearamide, N,N
-ethylene bisstearamide,
much higher than polyolefins (0.91–0.96 g/cm3 ). While PLA oleyl palmitamide) have also been added to reduce the
may be processed in extruders designed for polyolefins, coefficient of friction between overlapping films [102]. Typ-
if the extruder is already operating at close to maximum ically, slip additive of less than 0.5–1.0% by polymer weight
power of the screw drive, the extruder may not have enough is used, as excessive amounts will compromise the abil-
power to process PLA due to the substantial higher den- ity of print inks, stickers to adhere to the film surface. To
sity for PLA [103]. Compared to polyolefins, PLA has weaker avoid the use of copolymerization techniques, blending, or
melt strength, and therefore, the formation of a stable bub- plasticizers, Tweed et al. developed a method to obtain PLA
ble during extrusion blowing is more difficult. As a result, blown films by elevating the viscosity of PLA through suc-
extrusion blowing of PLA film often requires the use of addi- cessive steps in a polymer cooling unit or by internal cooling
tives, such as viscosity enhancers to strengthen its melt of the die mandrel using air or liquid fluid to control the
strength. These additives protect the polymer from degra- temperature of the die [102]. Mitsui Chemicals successfully
dation and/or couple polymer chains to attenuate overall developed PLA-based films by copolymerization technol-
loss of molecular weight and viscosity of the polymer melt. ogy, and it is commercializing it as one of the LACEA brand
The formulation of coupling agents is often proprietary. One resins [51].
commercially available coupling agent for PLA is made up
of copolymer of styrene, methyl methacrylate and glycidyl 7.6. Thermoforming
methacrylate [102]. Sodergard et al. disclosed a method to
stabilize PLA and enhance its melt strength by adding an Thermoforming is commonly used for forming pack-
organic peroxy compound (e.g., tert-butylperoxybenzoate, aging containers that do not have complicated features.
dibenzoylperoxide, tert-butylperoxyacetate) during melt PLA polymers have been successfully thermoformed into
processing, wherein the peroxide is added in about 0.01–3% disposable cups, single-use food trays, lids, and blister pack-
by weight of PLA [101]. aging.
Since PLA films are quite stiff and have much lower elon- Fig. 23 shows the typical steps for thermoforming of
gation than polyolefins, collapsing of bubble in the nips PLA container. In this process, PLA sheet is heated to soften
rolls tends to produce wrinkles which tend to permanently the polymer, forced either pneumatic and/or mechanically
remain in the film due to the high dead-fold properties of against the mold, allowed to cool, removed from the mold,
PLA. This problem can be overcome by incorporating fillers and then trimmed. Heating of PLA sheet for thermoform-
into PLA during extrusion. To reduce the adhesion between ing is generally achieved by infrared red (IR) radiation
films, Hiltunen et al. blended PLA with triacetin plasticizer from heater elements. Each polymer has an optimum IR
(glycerol triacetate), together with various anti-adhesion absorbance frequency in the IR region. Therefore, the heater
agents, such as talc, TiO2 and CaCO3 . They claimed that the element should be set at the temperature at which the
bursting strengths of the resulting blown films were better majority of energy is absorbed by the polymer. For PS, the
than typical polyethylene and PP films [104]. Slip additives 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) 820–852 839

mixing various proportions of PLLA and PDLA together neat PLA and PLA reinforced with two commercial organ-
with 0.5% talc (w/w) in an extruder at 200 ◦ C. An expand- ically treated MMT samples. They found that the foam of
ing agent, either dichlorodifluoromethane or butane was PLA/MMT exhibited a nicely interconnected, energetically
charged under pressure into the extruder. The mixture was stable closed-cell structure with pentagonal and hexagonal
cooled to 140 ◦ C and extruded through a slit die to give sheet faces [121]. In contrast, pure PLA foam showed a relatively
foam. An alternate method adopted by these inventors large cell size (∼230 ␮m). The size of the cells decreased as
involved mixing and heating azodicarbonamides powder the amount of MMT increased, and it leveled off at higher
(a food additive) with PLA resins using an extruder, in MMT concentrations. Di et al. concluded that it is possible
which the azodicarbonamide decomposed, thereby releas- to foam PLA with different cellular structures by controlling
ing nitrogen gas to induce the formation of bubbles [115]. the amount of organoclay content [121].
Another patent described a method for injection molding Recently, supercritical CO2 has attracted consider-
of PLA foams by adding 15–25 wt% of solvent to PLA dur- able research attention as an environmentally friendly
ing extrusion [116]. Solvents reported to be suitable here solvent for many processes because it is inexpensive, non-
were methyl formate, ethyl formate, methyl acetate, propyl flammable and can be easily removed from the products.
acetate, dioxane and methyl ethyl ketone. A liquid becomes a supercritical fluid when both pressure
Loose-fill packaging materials provide cushioning, pro- and temperature are above the critical point. In this state,
tection, and stabilization of packaged goods during the substance possesses a combined gas-like viscosity and
shipping. Over the past decade, the use of expanded PS liquid-like density, making it an excellent solvent for var-
foams for loose-fill packaging has declined due to the ious applications. For CO2 , its solubility and diffusivity in
replacement with the environmentally more benign starch- many polymers tend to increase considerably when it exists
based expanded foams. To overcome the hydrophilic nature in the critical state, thereby facilitating the plasticization
of starch, these biobased foams are often blended with of many polymers and enabling the forming process to be
petroleum polymers. Recently, PLA has been use for blend- conducted at lower temperatures [122]. Moreover, the crit-
ing with starch during foaming. Guan et al. extruded ical conditions of CO2 at 31.1 ◦ C and 7.38 MPa are readily
PLA and acetylated starches, along with 5% talc (w/w) attainable within the safety of commercial and laboratory
and various amounts of ethanol in a co-rotating conical setups [123,124]. The supercritical CO2 approach is based
twin-screw extruder (180 rpm screw speed; 160 ◦ C barrel on the larger Tg depression effect of supercritical CO2 on
and die temperatures) [117]. The blends were conditioned polymers, which keeps the polymer in the liquid state at rel-
for 24 h at 25 ◦ C before extrusion. The authors observed atively low temperatures. The sudden reduction in pressure
that ethanol functioned as an effective blowing agent to leads to the formation of CO2 nuclei which grow sponta-
expand the foams, and it acted as a solubilizing agent to neously. Meanwhile, as the pressure decreases, the Tg for
depolymerize PLA and starch to form homogenous dough. the polymer also elevates and eventually rises above the
They observed that increasing the PLA content caused an foaming temperature, at which point the cellular structure
increased foam expansion [117]. In an attempt to improve is locked in place to produce a cellular network. Fujiwara
the physical/mechanical properties, and moisture resis- et al. investigated the effect of d- and l-lactide composi-
tance of starch-based foams, Preechawong et al. prepared tions (1.0–28.5% d-lactide contents) on PLA foaming using
starch–PLLA hybrid foams by baking PLA–starch mixtures supercritical CO2 [125]. The samples were heated to 50 ◦ C in
in a hot mold at 220 ◦ C for 2 min [118]. They found that the the reactor chamber followed by adding CO2 . The pressure
addition of PLA improved the ultimate tensile strength and of the vessel was ramped to 69 and 414 bar, respectively,
elongation at break, as compared to the starch foam, with for amorphous and crystalline samples. The temperature
a concomitant increased resistance to water absorption. was increased stepwise while the pressure was kept con-
Besides adjusting the cellular morphology of PLA stant. The expansion of the polymer was monitored during
through the use of different blowing agents and pro- heating using a linear variable differential transducer. Fuji-
cess optimization (pressure and temperature adjustments), wara et al. reported that the average pore diameters for the
much recent research activity has been directed at affect- porous structures were 5.4 and 3.3 ␮m for 1 and 4.2% d-
ing the size and formation of the cellular structure by lactide polymers, respectively, suggesting that the cellular
dispersing MMT nanoclay particles in the bulk material morphology was crystallinity dependent. In contrast, under
[119]. Ray and Okamoto foamed pure PLA and PLA com- the same conditions employed, porous structures were not
posite with organically modified MMT in a batch system detected for amorphous PLA samples with 10 and 28.5% d-
below Tm . These authors found that foamed PLA reinforced lactide content. Moreover, they also reported an increased
with MMT produced homogeneous cells with closed cell linear swelling of the polymer with decreasing crystallinity
structure with a diameter of 2.6 ␮m; however, in the case and the porous supercritical CO2 treated PLA samples
of neat PLA the cells were non-uniform with average cell have higher crystallinity than the as received polymers
size of 230 ␮m [23]. They concluded that the MMT parti- [125]. Porosity of supercritical CO2 treated foams not only
cles acted as nucleating agents for the cell formation. Ema depends on the pressure and temperature, but also on the
et al. also incorporated nanoclay in PLA for batch foam- rate of its release from the polymer (Fig. 24) [123]. Mooney
ing using supercritical carbon dioxide as a foaming agent. et al. showed that the formation of PLA foams can also take
These researchers noted that cells of ∼200 nm were local- place below the critical conditions by exposing the poly-
ized along the surfaces of the dispersed nanoclay and drew mer to a pressure of 55 bar at 20–23 ◦ C for 72 h, followed by
a similar conclusion that the dispersed nanoclay acted as rapid depressurization to atmospheric pressure in 10–15 s
nucleating sites for the cell formation [120]. Di et al. foamed [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 are generally produced using the melt spinning tech-
rapid diffusion of the dissolved gas from the surfaces [126]. nique [128–136]. Here, PLA fibers are typically melt-spun
Matuana investigated the effect of microcellular structures at approximately 185–240 ◦ C through spinnerets with l/d
on the mechanical properties of foamed PLA by using a ratios of 2–10. The processing temperature is compara-
two-stage CO2 foaming process. The process first involved ble to polyolefins [137,138]. The melting temperature used
saturating PLA samples with CO2 in a pressure chamber also depends on the optical purity of the polymer used.
at 5.5 MPa and room temperatures for 2 days. The CO2 - Lower processing temperatures can be used for lower opti-
saturated samples were then removed from the chamber cal purity polymer (i.e., greater d-isomer content), which
and heated above Tg in a glycerin bath [127]. Compared with can help reduce the thermal and hydrolytic degradation.
the unfoamed PLA, Matuana reported a twofold increase in Similar to the injection molding process, fiber-grade PLA
impact resistance, up to twofold increase in strain at break, needs to be dried to less than 0.005% (w/w) moisture before
and up to fourfold increase in toughness for the foamed melting in the extruder to minimize molecular weight
samples. The increased impact strength was attributed to drop.
the presence of small bubbles which inhibited the crack In a two-stage melt spinning process, the polymer is first
propagation by blunting the crack tip and increasing the heated above its melting point and extruded through the
amount of energy needed to propagate the crack [127]. spinneret. The solidification of the extrudate is achieved
The low temperature supercritical CO2 processes reviewed by cooling in the air and the take up roller. In the second
above are expected to find their place in the manufactur- stage, the fiber undergoes hot drawing, where the filament
ing of structural foams for which mechanical properties are is pulled down by a take-up roll with a specific speed to
critical, since thermal and hydrolytic degradation encoun- achieve fiber orientation, which is important to increase the
tered in the typical thermal processes can be avoided. tenacity and stiffness of the fibers. PLA can be melt spun in a
high-speed spinning process with take-up velocity of up to
7.8. Fiber spinning 5000 m/min and a draw ratio of up to six [130]. The degree
of crystallinity of the fiber increases with spinning veloc-
High water vapor transmission rate of PLA often pre- ity due to stress-induced crystallization. By adjusting the
cludes its use in applications where moisture barrier draw ratio, a wide range of mechanical properties can be
is critical. However, this property can be leveraged for achieved for the fiber (Fig. 25). While high speed spinning
fabricating fibers used in garments (e.g., shirts, dresses, provides high fiber manufacturing throughput, manufac-
underwear, shoes, etc.) to improve their “breathability”. turing of fiber of uniform diameter is not a trivial task under
While PLA fibers are not as wettable as cotton, they exhibit high speed condition due to process instability caused by
much greater water vapor transmission than polyester or the draw resonance known as spinline neck-like deforma-
nylon fibers. tion, which is characterized by an abrupt attenuation of the
The manufacturing of PLA fiber is carried out either by spin-line cross-sectional area. The phenomenon is related
dry or melt spinning processes. Commercially PLA fibers 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 the solution during solvent evaporation caused the heli-
spinning process, which involves dissolving the polymer cal aggregates to form crystalline junctions that hampered
in a solvent (typically chloroform, toluene or a mixture of re-entangling of polymer chains, leading to crystalline
the two solvents) and extruding the polymer solution in air polymer with good draw-ability [140]. In this binary sys-
or inert gas. Evaporation of the solvent causes the extruded tem which contained a good PLA solvent (chloroform) and
filaments to solidify [136,140–143]. Although the melt spin- a poor PLA solvent (toluene), the greater tendency for chlo-
ning process is relatively straightforward, the process tends roform to evaporate during spinning causes an increased
to induce molecular weight drop of the PLA polymer due to PLA concentration with a concomitant decrease in sol-
thermal-induced hydrolytic degradation during the melt- vent power, resulting in the formation of polymer-poor
ing step in the presence of residual water. In contrast, and polymer-rich phases. The polymer-rich phase under-
the dry spinning technique is quite effective in preserv- went rapid solidification, thereby generating porous fiber
ing the molecular weight of the polymer due to the lower structures [142,143].
processing temperature used. In general, solution-spun The wet process is similar to the dry process except
fibers are superior to melt-spun fibers from the stand- that the polymer solution is spun into a bath containing
point of mechanical properties. This is attributed to the coagulating solution which causes the polymer filament
lower chain entanglement of polymer molecules in the to solidify. With this approach, PLA is normally dissolved
solution state as compared to the melt state. By transfer- in chloroform which is then extruded into a toluene or
ring this dilute entanglement network to the solid state methanol bath [136]. Tables 8 and 9 compare the pro-
in the spinning process, the as-spun fibers tend to exhibit cess parameters between the melt and solution spinning.
high draw ratios. For instance, Penning et al. reported that Compared to polyester, Lyocell, cotton, and viscose fibers,
dry spinning followed by hot drawing resulted in low crys- PLA fiber tends to be more extensible. When PLA stretches
tallinity fibers having a tensile strength of 1 GPa, whereas beyond several percent of extension, it yields, stretches
fibers prepared from melt spinning followed by hot draw- quite easily, and then ruptures at relatively high elonga-
ing have much considerably lower strengths, ranging from tion values. As shown in Fig. 26, the tenacity behavior of
0.19 for completely amorphous copolymer to 0.53 GPa for PLA is akin to wool.
PLA homopolymer [141]. The major drawback to solution One variant of dry spinning is known as electrospinning
spinning is the use of organic solvents, which can pose which utilizes an electrostatic force to draw fiber. Recently,
environmental problems. several research groups have successfully spun PLA fibers of
One important parameter that affects the fiber mor- submicron diameter using this approach. The electrospin-
phology during dry solution-spinning is the composition ning process is discussed in the next section.
of the solvent. Instead of using one solvent, several studies
have successfully manipulated the morphology and physi- 7.9. Electrospinning of ultrafine fibers
cal properties of PLA fibers by using multi or binary solvent
systems. Postema et al. showed that PLA fibers spun from Electrospinning is a technique for producing fibers
a solvent made up of 40/60 chloroform/toluene exhibited that are much smaller in diameter than those produced
the highest tensile strength of 2.3 GPa after hot draw- using the conventional techniques. Electrospun fibers typi-
ing among other chloroform/toluene proportions tested cally have diameters range from micrometer to nanometer
[142,143]. Similar observations were reported by Leenslag (Fig. 27). Similar to the conventional dry spinning process,
and Pennings [140]. They postulated that under the 40/60 electrospinning requires the solubilization of the polymer
chloroform/toluene condition, the PLA adopted an inter- in a solvent. However, unlike drying spinning which relies
rupted helical conformation. Solidification of PLA from 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) 820–852 843

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
Fig. 26. Tenacity–stretch ratio curves of PLA as compared to other com-
using collector of different configurations. For instance, by
mon textile fibers. The curves are based on the data originally published translating the collector plate in the X–Y plane, a large area
by Farrington et al. [137] and Rajkhowa et al. [187]. 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)
electrostatic force to spin the solution into fibers. Due to [150].
their small diameter, electrospun fibers possess very large PLA has been successfully electrospun into fibers,
area, making them an ideal material for applications such as primarily for tissue engineering and biomedical appli-
medical tissue scaffold, wound dressing, carrier for drugs, cations. For instance, a number of studies showed that
protective fabrics, high performance filter media, filler for scaffolds for the regeneration of cardiac, neural, bone
nanocomposite materials, etc. [144]. and blood vessel tissues can be fabricated from electro-
A typical laboratory electrospinner is made up of four spun PLA fiber through post-spinning orientation and/or
main components: (1) a high voltage DC supply; (2) a spin- using rotating target collectors [151–154]. PLA has been
neret, charged by a DC power supply; (3) an infusion or electrospun into different forms of ultrafine fiber and
peristaltic pump to deliver polymer solution to the spin- used as carriers for bioactive agents, including antibiotics
neret; and (4) a metal fiber collector which also acts as a [155], anticancer drugs [156,157], and antibacterial silver
counter electrode (Fig. 28). To increase throughput, mul- 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-
Fig. 27. Comparison of surface area and diameter for various fibers. trospinning PLA in the melt phase using a CO2 -laser [163].
Adapted from Ko [188]. 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 tic starch [165], poly(ethylene glycol) (PEG) [104,165,166],
to prolonged heat exposure, which has been observed pre- triacetin and tributyl citrate [96,104,167], and PHA [99,168].
viously for melt-electrospinning for other polymers based Lee and McCarthy modified the toughness of 4% d-PLA
on the heat conduction melting approach. Moreover, the with poly(3-hydroxyloctanoate) (PHO). In order to over-
laser technique also eliminates the use of solvent, making come the process difficulties due to the large difference
the process more environmentally benign. This technique in melt viscosity between the two polymers, they modi-
is capable of producing fibers with diameters smaller than fied the PHO with hexamethylene diisocyanate (HMDI) by
1 ␮m [163]. reacting the hydroxyl group of PHO to form urethane link-
While research on electrospinning has exploded in the ages. HMDI of 2–5.5% (w/w) was reacted with PHO using
past decade for fibers spun from various polymers, the a counter-rotating screw at 40 rpm for 2 min at 100 ◦ C.
commercial production of ultrafine PLA fibers using this The modified PHO was melt-blended with PLA at 40 rpm
technique has not been forthcoming due to the low pro- for 3 min at 175 ◦ C and then compression molded [168].
duction throughput, the requirement for the use of specific Noda et al. prepared plastic films by melt compounding
solvents, and variation in fiber diameter. Based on the various proportions of PLA, PHA copolymer (copolymer of
present state-the-art of electrospinning, this technique is 3-hydroxybutyrate with 21 mol% of 3-hydroxyhexanoate),
likely to find uses for products containing PLA-nanofibers and poly(ethylene oxide). These authors claimed that the
in pharmaceutical and biomedical applications. inherent tackiness of PHA polymer and brittleness of PLA
can be overcome by this approach [99]. Recently, based
7.10. PLA blends with other polymers on viscosity and gel permeation chromatography mea-
surements, Conrad et al. reported that PLA/PHA blends
In many film applications, such as grocery and garbage degraded more rapidly as compare to the neat PLA [169]. In
bags, bursting strength, elongation and tear strength are another patent, Randall et al. blended PLA with epoxidized
important properties. As discussed in Sections 7.4 and 7.3, natural rubber in the presence of a compatibilizing agent
these properties can be improved to a certain extent by (maleic anhydride/polybutadiene copolymer or maleic
mechanical drawing, such as biaxial orientation and stretch anhydride/polybutadiene/PS copolymer at 1–2 wt% relative
blow molding. However, for other PLA parts where the of the epoxidized rubber). They observed an increased ulti-
use of mechanical orientation is not feasible (e.g., injection mate elongation from 72.6 to 295%, and an increase of Izod
molded articles), blending of PLA with other polymers is a impact value from 2.08 to 3.8 ft lbs/in. for injection molded
useful strategy to impart flexibility and toughness. Another test bars, as compared to the non-compatibilized control
motive for blending PLA with other polymers is to reduce [164]. The blends were produced by extruding the poly-
the material cost since the cost of PLA is relatively higher mers through a twin-screw extruder (150–175 ◦ C extruder
compared to other petroleum plastics. zone temperatures; 250 rpm), cooling in a water trough,
Various polymers have been used for improving the chopping the extruded strand into pellets, drying to remove
properties of PLA, including elastomers [164], thermoplas- 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- 120–180 ◦ C. They reported that PEG can form miscible to
ing them through the extruder more than once, tended partially miscible blends with PLA, depending on the blend
to increase the impact resistance of the resulting molded concentration. Below 50% PEG, the plasticized PLA sam-
articles [164]. ples have high elongation with a concomitant reduction
Averous attempted to blend thermoplastic starch, PEG, in modulus values. However, above 50% PEG content, the
glycerol and oligomeric lactic acid by using a single-screw blend crystallinity increases, resulting in an increased mod-
extruder equipped with a conical-shaped shear element ulus and a considerable decrease in the elongation at break
[165]. Glycerol was found to be the least efficient plas- [166]. Although PEG is effective in decreasing the stiffness
ticizer, while oligomeric lactic acid and PEG provided of PLA, the use of low molecular weight plasticizer has a
substantial increases in elongation. Affinity of PLA and disadvantage in that it has a tendency to migrate in the PLA
thermoplastic starch was poor, leading to blends that matrix. For instance, Hiltunen et al. reported that although
possessed much weaker mechanical properties as com- PEG plasticized PLA can be extrusion blown to form film
pared to the individual polymers [165]. Moura reported with a reasonable tensile strength, PEG tended to migrate
that the tensile strength, elongation, and damping for out of the film after a few days or weeks [104]. Ljungberg
PLA blended with starch particles increased with aver- and Wesslen reported that the Tg of PLA can be effectively
age particle size of the starch granules, but declined depressed by blending with triacetine and tributyl citrate
when the granules were greater than 45 ␮m [170]. More- up to about 25% (w/w), above which phase separation of
over, crystallinity increased as the particle size decreased. plasticizer tended to occur. They also observed that phase
The use of methylenediphenyl diisocyanate as a coupling separation of plasticizer accelerated at elevated tempera-
agent dramatically improved the mechanical properties ture (50 ◦ C) due to the increased crystallinity of the PLA
of the composite [170]. Sheth et al. melt-blended PLA phase [167]. During storage of triacetine and tributyl cit-
and PEG using a counter-rotating twin-screw extruder at 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 increased flexural moduli for poly(butylenes succinate)
[26]. The dried cellulose fibers and PLA resin, mixed at 70 and polyestercarbonate/PLA blends as the fiber content
and 30% (w/w) ratios were compounded in the twin-screw increased. In contrast, for the PLA-abaca fiber composite, a
extruder with an l/d ratio of 30. The extruder tempera- minimal increase in flexural strength was observed which
ture was set at 183 ◦ C and the screw speed was 100 rpm. is attributed to inherent high flexural strength of neat PLA
The extrudate was palletized and dried prior to injection [25].
molding. The extruder temperature was 183–185 ◦ C. A rel-
atively long cooling time of 50 s was used to bring the 7.12. PLA nanocomposites
injection molded part to 65 ◦ C in the mold. The study
showed that both mechanical and thermo-physical prop- Inorganic or organic nanoparticles have been incor-
erties of the recycled newspaper composite compared porated to enhance the mechanical, barrier and thermal
favorably with glass fiber reinforced PLA composite, sug- properties of PLA. Unlike micro- and macro-scaled particles
gesting that these cellulose fiber reinforced composites (e.g., talc, glass fiber, carbon particles, etc.), nanopar-
have a potential to replace glass composite in applications ticles can improve material properties at much lower
where very high load bearing capabilities are not needed added quantities (2–8%, w/w). Over the past few years,
[26]. various nanomaterials have been investigated for rein-
The effects of cooling on the crystallization behavior of forcing PLA, including layered silicates, carbon nanotube,
PLLA-cellulose composites were investigated by Mathew et hydroxyapaite, layered titanate, aluminum hydroxide, etc.
al. [28]. The 25% (w/w) composites were prepared in a vac- [21–23,119,154,174–179]. Among the nanomaterials inves-
uum vented twin-screw extruder operated at 250 rpm and tigated, layered silicate clays have been studied in the
170–200 ◦ C. The resulting composites were pelletized and greatest detail by researchers from both academia and
subsequently injection molded at 200 ◦ C into a 50 ◦ C mold industry. The heightened interest for these nanofillers
at the injection speed of 60 mm/s. The Tg values for the can be attributed to their ability to dramatically improve
molded PLLA, microcrystalline cellulose, cellulose fiber and material properties of the nanocomposite structures as
wood flour composites, were 54.1, 56.6, 57.5 and 58.3 ◦ C, compared with the pure PLA, including improved mechan-
while the crystallinity values were 19, 45, 35 and 45%, ical and flexural properties, elevated heat distortion
respectively. These authors attributed the delayed polymer temperature, enhanced barrier properties and accelerated
relaxation for the composites to the restriction of polymer biodegradation [21,171,175,180]. This section will focus
chain mobility due to the increased crystallinity in the pres- mainly on reviewing the literature on the processing
ence of fillers. The presence of cellulose fillers has a similar aspects and material properties of MMT nanocomposites.
effect of inducing crystallinity in PLLA polymer during slow MMT belongs to a family of clays known as smectite
cooling (2 ◦ C/min) from the melt (absence of glass transi- with crystal structure made up of two fused silica tetra-
tion around 54–58 ◦ C regions for traces III and V in Fig. 30). hedral sheets sandwiched with an edge-shared octahedral
Shibata et al. evaluated the effect of dispersing abaca sheet of either aluminum or magnesium hydroxide. The
fiber (Manila hemp) in several biodegradable polyesters, thickness of a single layer is about 1 nm, while the lat-
including PLA. The biofiber was incorporated up to 20% eral dimension of the crystals can range from 30 nm to
(w/w) in a twin-screw compounder at 190 ◦ C for 5 min several microns or greater. The crystal layers are stacked
at a screw speed of 50 rpm. These authors observed an 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 disperse the silicate layers of the clay. By far, exfoliation
more hydrophilic than PLA. Therefore, it must be organi- of MMT in PLA can be best achieved by using a twin-
cally modified to compatibilize and facilitate its dispersion screw compounder. Dennis et al. reported that in order
in PLA. One useful characteristic of MMT is that the cations to exfoliate MMT effectively, the clay particles need to
in the galleries, typically Na+ , Li+ , Ca2+ , Fe2+ and Mg2+ can be sheared and fractured to form smaller stacks of tac-
be substituted readily through ion exchange with organic toid platelets (∼100 nm in thickness). Once platelets of
cations, by treating the clay with surfactants including shorter stack heights are formed, further delamination of
primary, secondary, tertiary or quaternary alkylammo- the platelets was primarily driven by the diffusion of the
nium or alkylphosphonium cations [119]. Another unique polymer chains into the clay galleries, which is highly
property of MMT is related to its ability to delaminate dependent on the chemical compatibility of the poly-
and disperse in a polymer to give individual imperme- mer and the organoclay surface [183]. Therefore, unless
able platelets of about 1 nm thick. By virtue of their very the compatibility of the clay and polymer is improved
high aspect ratio, large interfacial area and nano-thickness, through chemical treatment, increasing the shear inten-
the dispersed platelets lead to many characteristics that sity alone will only improve the distributive homogeneity
are important for enhancing the performance of poly- of the particles in the polymer, but not the delamina-
mers. tion of the clay particles. These authors concluded that
Pluta evaluated the effect of organoclay and compound- the residence time under low and mild shearing condi-
ing conditions on polylactide/organoclay nanocomposites tions is required to allow polymer chains to penetrate the
(4.1% d-lactide PLLA) [20]. The PLA pellets were melt- clay galleries and peel the platelets apart [183]. Unfortu-
blended at 180 ◦ C with Cloisite® 30B (3%, w/w; modified nately, under the typical extrusion conditions, increasing
with methyl-bis(2-hydroxyethyl) tallowalkyl ammonium the residence time will also cause unwanted thermal
cations) in a counter-rotating mixer at 50 rpm screw speed degradation, leading to molecular weight drop which
for 6–30 min. The study showed that compounding of diminishes the performance-enhancing effect of nanopar-
PLA/organoclay composite resulted in 14–32% molecular ticles [184].
weight drop, when the composite mix was compounded Various forms of modified MMT have been used to
for 6–30 min, even if a dry nitrogen atmosphere was enhance the material properties of PLA. Chang et al.
used during the melt processing. Similar reduction in incorporated hexadecylamine, dodecyltrimethyl ammo-
PLA molecular weight was reported by Ray and Okamoto nium bromide, and quaternary ammonium salt modified
on their study of various organically modified layered MMT clays in PLA films at 0–10% (w/w) MMT levels, based
silicates, which was attributed to the elevated shear on wet casting method, using N,N
-dimethylacetamide as
mixing of PLA in the presence of the silicate, and the a solvent [185]. These authors observed that there is an
presence of hydroxyl groups in the modified salt, both optimal loading of organoclay (∼3–4%, w/w) for achiev-
of which are capable of causing hydrolysis or transes- ing the greatest improvement in mechanical properties.
terification reactions in PLA when exposed to elevated At higher MMT contents, the nanoparticles tended to
processing temperature [182]. In this study, the nanocom- agglomerate, leading to mechanical weakening. In contrast,
posites were first prepared by dry-mixing of PLA resin within the 0–10% MMT loading levels, oxygen transmis-
with organoclay and extruding in twin-screw extruder sion rates decreased with increasing clay content which
(screw speed = 100 rpm, feed rate = 120 g/min) to form was attributed to the increased tortuous diffusion path
nanocomposite strands. The strand were pelletized and of oxygen molecules through the impermeable crystalline
dried under vacuum at 60 ◦ C for 48 h, pressed into platelets [185]. Ogata et al. used a similar film casting
0.7–2 mm sheet with 1.5 MPa at 190 ◦ C for 3 min, and then methodology to evaluate the impact of organophilic MMT
quenched and annealed at 110 ◦ C for 1.5 h before testing (0–10%, w/w) on PLA, except that chloroform was used
[182]. as a solvent. These authors reported that only microcom-
The properties of MMT nanocomposites are highly posites were resulted and intercalated structures were
dependent on how well the clay disperses in the polymer not achieved [18]. It is unknown whether the formation
matrix. In general, clay dispersion can be distinguished in of microcomposites was due to incomplete exfoliation
three modes: (1) when the clay particles are not delam- of MMT in the chloroform solution or caused by the
inated, the resulting materials tend to exhibit similar agglomeration of MMT during the film drying step. Nev-
properties as conventional microcomposites. The unsep- ertheless, these studies do highlight the importance of
arated MMT layers surrounded by the polymer are often solvent selection which can affect the exfoliation of the
referred to as tactoids; (2) when the polymer chains are layered silicates.
inserted into the galleries of the swollen silicate layers, Thellen et al. studied acetyltriethyl citrate plasticized
the clay is known as intercalated, leading to decreased MMT-PLA composite films formed using compounding and
polymer chain mobility and resulting in material reinforce- extrusion blowing processes [186]. They observed about
ment; and (3) when the clay is completely delaminated 50% improvement in oxygen and water barrier properties,
and homogeneously dispersed in the continuous polymer and 20% increase in modulus as compared to the neat
matrix, the layered silicates are termed exfoliated nanocom- PLA films. Although thermal properties were not affected
posites, giving rise to the maximal potential for physical by the addition of MMT, the thermal stability improved
properties enhancement. The exfoliation of MMT is largely marginally.
dependent on the chemical compatibility of the clay and In summary, MMT exhibits a strong potential for
polymer matrix, as well as the process conditions used to enhancing the material properties of PLA. The promising
L.-T. Lim et al. / Progress in Polymer Science 33 (2008) 820–852 849

outlook for MMT is mainly lies in its abundant sources, References


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