Composites: Part A 41 (2010) 16281635

Contents lists available at ScienceDirect

Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Agrobre reinforced poly(lactic acid) composites: Effect of moisture

on degradation and mechanical properties
M.J.A. van den Oever a,, B. Beck b, J. Mssig b
a
b

Wageningen UR Food & Biobased Research, PO Box 17, 6700 AA Wageningen, The Netherlands
Hochschule Bremen University of Applied Sciences, Faculty 5/Biomimetics Biological Materials, Neustadtswall 30, 28199 Bremen, Germany

a r t i c l e

i n f o

Article history:
Received 1 April 2010
Received in revised form 9 July 2010
Accepted 25 July 2010

Keywords:
A. Polymermatrix composites
B. Mechanical properties
E. Injection moulding
PLA degradation

a b s t r a c t
Natural bre reinforced PLA composites are a 100% biobased material with a promising mechanical properties prole. However, natural bres are hygroscopic whereas PLA is sensitive to hydrolytic degradation
under melt processing conditions in the presence of small amounts of water. Here, we determine the
effect of water content in undried and dried natural bres on semi crystalline grade PLA degradation during processing as well as on the composites mechanical performance. The bres evaluated are ramie, ax
and cotton, containing 69 mass% moisture in the undried state and 0.20.4 mass% in the dried state.
Intrinsic viscosity and melt ow index analysis indicate that the effect of the different levels of moisture
in the bres have a similar and small effect on PLA degradation, PLA hydrolysis appears rather affected by
bre diameter. Morphology, exural strength and stiffness and Charpy impact of the composites are not
signicantly affected by the water present in the undried bres.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
The continuously increasing environmental awareness during
the past decades has resulted in the introduction of natural bre
reinforced polymer composites as common materials in e.g. automotive industry. NMT materials have been used since the 1990s
and currently agrobre based injection moulding compounds are
nding applications [1]. With the introduction of large scale production of polylactic acid (PLA), a biobased thermoplastic polymer
has become available that has properties that may provide a basis
for materials that are competitive with composites based on polyolens and other bulk polymers. At the same time, PLA promises to
be nearly CO2 neutral and reduces dependency on oil for the production of composite materials [2,3]. In fact, NEC and Unitika have
already started the marketing of kenafPLA composite mobile
phone housing [4].
Similar to other polyester polymers, PLA is sensitive to hydrolysis under melt processing conditions in the presence of small
amounts of water [5]. NatureWorks recommends that moisture
content in the PLA during melt processing is lower than
0.025 mass% [2]. This poses the question how PLA behaves during
processing into natural bre polymer composites, since natural
bres are hygroscopic and contain 610 mass% of moisture at
5070% relative humidity conditions. Several researchers of natural brePLA composites have dried the PLA as well as the bres
Corresponding author. Tel.: +31 317 480105; fax: +31 317 483011.
E-mail address: martien.vandenoever@wur.nl (M.J.A. van den Oever).
1359-835X/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2010.07.011

before processing [617], others only refer to drying of the bres

[18]. Some do not mention drying of the material prior to processing at all, without further addressing potential PLA hydrolysis
[19,20]. Nishino et al. and Petersson et al. only refer to drying of
the bres, however they produce PLA composites from solution,
thus avoiding PLA to enter the molten state [21,22]. Wong et al.
and Shanks et al. have dried their solution casted composites under
vacuum at 50 and 60 C for 2 h and 3 h, respectively, prior to consolidation at 175 C [23,24]. Due to the high bre content of
50 vol%, it may be expected that also residual water will be removed under these drying conditions.
Oksman et al. [25] show that during extrusion compounding of
axPLA, the Mw of PLA only reduced from 97,000 to 80,000 g/mol
as determined with gel permeation chromatography (GPC) and that
molecular mass distribution was unimodal. Liu et al. [8] state that
GPC indicates no PLA scission after a 4 min compression moulding
process at 180200 C after vacuum drying prior to moulding. Plackett et al. [26] have evaluated the effect of jute bre drying prior to
processing on the molar mass of PLA, however, they have not reported its effect on composite mechanical performance.
Despite no mentioning of drying of bres and/or PLA prior to
melt processing by Bodros et al. they still nd an improvement
of strength of PLA composites with increasing bre content up to
the level where bre agglomeration takes place [20]. Shibata
et al. have observed a constant strength with increasing bre
content [18]. Mathew et al. have not presented the strength
performance of their cellulose bre and wood brePLA composites [19].

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M.J.A. van den Oever et al. / Composites: Part A 41 (2010) 16281635

In order to particularly address the effect of natural bre moisture content on PLA composite properties, in this paper a worst
case scenario for natural brePLA composite production will be
studied by incorporation of undried agrobres in pre-dried PLA.
A best practice reference will consist of drying the bres as well
as possible on lab scale directly prior to compounding. The effect
of the drying of the natural bres on the composites exural and
impact properties has been discussed in short in a recent publication [27]. In the present paper a more detailed study of the effect of
water in the bres on PLA chain scission has been evaluated by
analysis of intrinsic viscosity (IV) of the PLA. IV analysis of PLA molar mass was preferred over GPC analysis because within several of
our PLA project we have been confronted with GPC results which
turned out to be misleading. The IV of various PLA grades relates
to the molar mass according to the MarkHouwink equation
[2834]. The MarkHouwink constants vary a lot between these
authors. However, together with many other researchers [3545],
we believe that the IV of PLA may provide a good indication of
PLA molar mass reduction, caused by PLA hydrolysis. From all
MarkHouwink values found in literature [2834], those determined by Dorgan et al. [34] yield the most median molar mass values, Mv,

g 0:0153  M 0:759
v

where [g] represents the IV. This relation will be used in the present
study to obtain an indication of the number of scissions in the PLA
molecular chain due to hydrolysis.
The degradation of PLA during melt processing can also be evaluated by determination of the melt ow index (MFI) values of the
polymer composites, if the contribution of the bres to the MFI
does not change at the same time. An advantage of this route is
that the MFI of a polymer composite can be easily determined.
From the only small reduction in exural strength of jutePP composites upon 30 min heating at 200 C [46] it may be concluded
that such natural bre structure retains its integrity, and as a consequence retains its structure and effect on ow. Further, from the
low shear rate in MFI analysis it is not expected that bre orientation will take place during such analysis [47].
The added value of a composite most often includes its
mechanical performance. Therefore, the effect of natural bres,
processed by both the best practice and the worst case approach,
on the exural and impact performance of PLA will be addressed.
The analysis includes PLA composites based on ramie, ax and cotton bres.

Fibres were dried at 105 C for 24 h and subsequently at 80 C

using pre-dried air for 1220 h.
Dried PLA granules were melted in a Haake Rheomix batch
kneader (Thermo Fischer Scientic, Karlsruhe, Germany) at a set
temperature of 175 C and at a rotor speed of 100 RPM during
2.5 min under a constant ow of pre-dried nitrogen. Subsequently,
pre-dried or undried bres were fed to the PLA melt and compounded up to a total time of 13 min. The temperature of the polymer melt was determined using a thermocouple. The compositions
of the produced composites and related codes are indicated in
Table 1.
The composites were granulated and dried overnight in a Gerco
granules dryer at 80 C with pre-dried air and injection moulded to
exural/impact test bars with dimensions 80  10  4 mm3 using
a Demag ERGOtech 2580 (Mannesmann Demag Kunststofftechnik, Wiehe, Germany). All composite specimens were conditioned
for at least 7 d at 23 C and 50% RH before further analysis.
2.3. PLA extraction
Injection moulded specimens of kneaded PLA (C1) and all
30 mass% brePLA compounds (C4, C6, C9, C11, C14, C16) were
put each in 160 ml of chloroform and heated under reux in a
250 ml ask until the PLA was dissolved in the boiling chloroform.
The PLAchloroform solution was ltered over a P2 lter with pore
size 40100 lm to remove bres and collected. Subsequently, the
lter was washed with boiling pure chloroform and the ltrates
were combined. The combined ltrate was heated again and ltered over a Whatman GF/A glass microbre paper with particle
retention of 1.6 lm. The obtained ltrate was dried using a Rotavap R-124 (Bchi Labortechnik, Flawil, Switzerland) to obtain the
PLA.
2.4. Intrinsic viscosity (IV)
Intrinsic viscosities [g] (ml/g), of all extracted PLA grades were
each determined from four solutions of PLA in chloroform in the
concentration range of 0.0010.01 g/ml. Efux times of xed volumes of PLA solutions were measured (via stopwatch) using a CannonFenske capillary (type 50) viscometer (Schott Gerte GmbH,
Hofheim, Germany) at 25 C according to ASTM D 2857-95. Molar
mass, Mv, was determined from [g], using Eq. (1). Virgin PLA (herewith coded C0) was included as a reference.
2.5. Melt ow index (MFI)

2. Materials and methods

2.1. Materials
PLA polymer (NatureWorks 4042D, having a Tg of 5258 C
and Tm of 150 C) was purchased from NatureWorks LLC (Minnesota, USA). Ramie, ax and cotton bre samples were used in sliver
form, which is an intermediate product from the textile spinning
process. The ramie was chemically separated, and was supplied
by Buckmann company (Bremen, Germany) in 2001. The cotton
was delivered by Trtzschler GmbH & Co. KG (Mnchengladbach,
Germany) in 2006. Flax bast bres originated from Holstein Flachs
(Mielsdorf, Germany) and were purchased in 2005.

Composite granules were dried at 80 C with pre-dried air for 4

and for 24 h. The MFI was determined at 190 C and 2.16 kg mass
under pre-dried nitrogen using Zwick MFI equipment (Zwick
GmbH, Ulm, Germany). After 240 s pre-heating, samples were collected after such time intervals that ca. 0.40 g of material was collected per time interval. The data were calculated into amounts of
own compound per 10 min.

Table 1
Codes for compound composition produced.
Fibre content

Flax
Dried

2.2. Compounding and Injection moulding

PLA was dried in a Gerco granules dryer (Gerco Apparatenbau
GmbH & Co KG, Sassenberg, Germany) at 80 C with pre-dried air
before melt compounding for at least 4 h, but no longer than 8 h.

0
10
20
30
50

C1
C2
C3
C4
C5

Ramie
Undried

C6

Dried
C7
C8
C9
C10

Cotton
Undried

C11

Dried
C12
C13
C14
C15

Undried

C16

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M.J.A. van den Oever et al. / Composites: Part A 41 (2010) 16281635

Table 2
Temperature of PLA melt at end of compounding in C.
Fibre mass%

Flax
Dried

0
10
30
50

191
197
203
211

Ramie

Cotton

Undried

Dried

Undried

Dried

Undried

202

193
205
219

205

196
201
227

204

compounds. Analysis was performed using a Jeol JSM-6300 F scanning electron microscope (Jeol Ltd., Tokyo, Japan) after covering the
fracture surfaces with a 10 nm layer of platinum using an Oxford
CT1500 sputter coater (Oxford Instruments, Abingdon, England).
2.9. Mechanical performance tests

2.6. Moisture analysis

Fibre samples of ramie, ax and cotton were conditioned at
23 C and 50% RH, weighed and dried overnight in an oven at
105 C in open glass bottles of known mass. Subsequently the bottles were sealed immediately upon removal from the oven with a
lm of known mass. The mass of the dried bres was determined
from the previously measured tare mass of bottle and seal and
the gross mass of the bottle, bres and seal. The moisture content
of the conditioned bres was determined after drying at 105 C.
The dried bre samples were heated in a Mettler Toledo Stromboli
(Mettler Toledo GmbH, Schwerzenbach, Switzerland) at 200 C and
the released gas was analysed for water content using a Mettler Toledo DL39 Karl Fisher Coulometer, thus obtaining a value for water
release at 200 C from bres that were pre-dried at 105 C. Hydranal Coulomat AG oven (Riedel No. 34739) was used as anolyte and
Hydranal Coulomat CG (Riedel No. 34840) was used as catholyte.
2.7. Fibre width analysis
The image analysis system Fibreshape (IST AG, VIlters, Switzerland) was used to determine the width distribution of the bres
and the bre bundles. The samples were prepared between two
glass slides for colour positives (Company Gepe, Zug, Switzerland,
type 69 01) after 24 h conditioning at 20 C and 65% RH of air. The
slides of the cotton and ramie bres were scanned by a CanoScan
FS 4000 US (Canon Gmbh, Krefeld, Germany) at 4000 dpi. The ax
bre bundles were scanned with a Epson Perfection V700 scanner
(Epson Deutschland GmbH, Meerbusch, Germany) at 2400 dpi. The
Software GIMP was used for the scanning operation. To measure
the width of the prepared bres and bre bundles with the system
Fibreshape (version 5.03) an adapted setup based on a standard
long bre measuring mask was used. The system was calibrated
using 8 IWTO wool standards.
2.8. Scanning electron microscopy (SEM)
SEM micrographs were made from fracture surfaces obtained
by Charpy impacting of injection moulded 30 mass% brePLA

The exural properties were measured on a Zwick 1445 (Zwick

GmbH & Co. KG, Ulm, Germany) according to ISO 178 at a support
length of 64 mm and a crosshead speed of 2 mm/min for the modulus and 10 mm/min for the strength. The exural strength and
modulus were determined from ve specimens per batch. The
Charpy unnotched impact strength was determined using a Ceast
Resil 50 pendulum impact tester (Ceast S.p.A., Pianezza, Italy)
according to ISO 179/1fU using an impact hammer of 4 J at a speed
of 2.9 m/s. The Charpy impact strength was determined from eight
specimens per composition.
3. Results and discussion
3.1. Processing
A total feeding time of 12 min has been required for the
50 mass% brePLA compounds. In order to enable all bres to
mix well with the PLA, a total kneading time of 13 min has been selected for all compositions. The long feeding time was a result of
the manual feeding of the bres into the batch compounder. For
industrial processing, bre in sliver form could be automatically
fed to an extruder [46]. The highest temperatures of the melt of
the natural brePLA compounds during processing are presented
in Table 2. Obviously, the higher the bre content, the more pronounced the melt temperature rises. No difference in odour and
colour could be observed between the dried and undried bre
composites.
3.2. Morphology
SEM micrographs of impact fracture surfaces of 30 mass% bre
PLA composites are presented in Figs. 14. The far majority of the
bres are well embedded by the polymer matrix, which is of
importance for the strength performance of the composites. For
the ax and ramie composites even several split single bres can
be observed in the close up micrographs, indicating that brematrix bonding must be stronger than the internal bre lateral
strength.
All three bre grades have a typical bre diameter in the range
of 1020 lm. Based on SEM pictures (not presented), it is concluded that the diameter of ramie and cotton bres was in this

Fig. 1. SEM of fracture surface of 30 mass% dried axPLA composite.

M.J.A. van den Oever et al. / Composites: Part A 41 (2010) 16281635

1631

Fig. 2. SEM of fracture surface of 30 mass% undried axPLA composite.

Fig. 3. SEM of fracture surface of 30 mass% dried ramiePLA composite.

Fig. 4. SEM of fracture surface of 30 mass% dried cottonPLA composite.

range already prior to compounding into PLA. The ax starting

material however contained a fraction of bre bundles, which are
known to rene during compounding [46].
3.3. PLA chain scission
In the worst case scenario, each water molecule present in the
compound causes one hydrolytic cleavage in a PLA molecule chain.

The maximum number of cleavages per PLA molecule, #cleavages, is

equal to the quotient of the moles of water molecules and the moles of PLA molecules present in the composite. The moles of water,
molH2 O , and PLA, molPLA, in the composites can be determined
from:

molH2 O mcomp  X f  X H2 O;f X m  X H2 O;m =M H2 O

molPLA mcomp  X m =MPLA

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M.J.A. van den Oever et al. / Composites: Part A 41 (2010) 16281635

Table 3
Water contents present in dried and undried bres and calculated number of maximum possible PLA chain cleaves and related average molar mass of PLA in 30 mass% agrobre
PLA composites.
Fibre

Ramie
Flax
Cotton

H2O content in bres (mass%)

Calculated maximum nr. of cleaves (molH2 O /molPLA)

Calculated worst case molar mass (D)

Dried

Undried

Dried

Undried

Dried

Undried

0.0022
0.0040
0.0029

0.067
0.090
0.066

12.7
23.1
17.1

391
525
385

19,310
10,593
14,364

627
467
636

where mcomp is the composite mass, Xf and Xm are bre and matrix
mass fractions, X H2 O;f and X H2 O;m are the mass fractions of water in
the bre and the matrix, and MPLA and M H2 O , are the molar masses
of the virgin PLA and water. Considering Xm = 1  Xf, the number of
cleavages per PLA molecule can be expressed as:

#cleavages MPLA  X f  X H2 O;f 1  X f  X H2 O;m =

M H2 O  1  X f

Considering the water contents of the bres as summarized in

Table 3, and assuming that the water content in the PLA after drying is negligible, and assuming that the PLA molar mass is
245,000 g/mol, then the maximum number of cleavages for
30 mass% brePLA composites can be calculated as summarized
in Table 3. The water present in a 30 mass% undried axPLA compound could result in a maximum average of 525 cleavages per virgin PLA chain. Even the dried bres contain a relatively large
amount of water that is being released at 200 C and the water
present in the dried ax bre bundles could still result in 23 cleavages in each virgin PLA chain. The worst case PLA molar mass values calculated from these number of cleavages per PLA molecule
are 10,593 and 467 g/mol for dried and undried ax, respectively.
Polymers with such molar mass would rather have waxy properties, not able to provide high strength and stiffness. In the next
paragraphs we will discuss the actual PLA degradation and the natural brePLA composite properties.
The kneading of pre-dried pure PLA during 13 min at 190 C results in a signicant reduction of IV (Table 4). Following Eq. (1), the
reduction of IV corresponds to a reduction of the Mv of PLA from
245,000 to 149,400 (Table 4). The reduction of Mv can be explained
by hydrolysis of the polyester backbone in the molten state in the
presence of even small amounts of water [5,47]. PLA degradation,
despite 48 h of pre-drying at 80 C as recommended by NatureWorks [2], is conrmed by an increase of the MFI of PLA after
kneading (Table 4), as previously reported [27].
The incorporation of 30 mass% of agrobres into PLA causes a
further decrease of IV and Mv of the PLA (Table 4). The effect of bre grade appears to have a larger effect on the reduction in IV and
Mv than drying/not drying the bres. The calculated Mv of PLA containing dried ax and cotton differs as much as a factor of 2.5,
whereas the calculated Mv of the dried and undried ax compounds only differs 10%, and Mv of dried and undried cotton compounds only differs 3%. The larger reduction in Mv for cotton bre
may be caused by its larger surface area compared to ramie and

Table 4
IV and Mv of pure PLA and PLA extracted from 30 mass% agrobrePLA composites
and MFI of pure PLA and 30 mass% agrobrePLA composites.
Composition

IV (ml/g)
Dried

Virgin PLA
Kneaded PLA
RamiePLA
FlaxPLA
CottonPLA

188.4
129.4
105.6
126.7
62.9

Mv (D)
Undried

Dried

117.1
61.6

245,000
149,400
114,300
145,300
57,800

MFI (g/10 min)

Undried

Dried

Undried

131,000
56,200

2.26
3.53
0.51
0.53
1.00

0.31
0.61
0.47

ax bre. Before compounding the average diameters of the ax,

ramie, and cotton samples were 62.3, 25.5 and 16.6 lm, respectively. After compounding and injection moulding the ax, ramie
and cotton bres have a diameter in the range 1520, 1015, and
1015 lm, respectively, as can be concluded from Figs. 14. Integrated over compounding time, the cotton bres have the largest
surface area in contact with PLA, followed by ramie and ax. Considering that the diffusion coefcient of water in PLA is far lower
than in natural bres, the water diffusion rate is expected to be
rather affected by brePLA contact surface than by moisture content in the bres. As a consequence, water diffusion from cotton bres to the PLA matrix is expected to be highest and leading to a
higher chance for PLA hydrolysis, followed by ramie and ax. Future research work will address natural bre chemical composition
and a more detailed analysis of bre surface area on PLA degradation during processing.
The IV analysis is considered to be based on PLA without any bre residues because the used lter had a pore size of 1.6 lm,
which is expected to lter all bres as from SEM analysis (Figs. 1
4) it can be concluded that the bres have a diameter of about
5 lm and larger.
Further, it may be noted that using the MarkHouwink constants as dened by other researchers [2833] will exhibit exactly
the same trends in PLA molar mass reduction, though being
slightly less or slightly more pronounced. These same trends are
obtained despite the MarkHouwink constants being determined
in different solvents at different temperatures for different PLA
grades.
Comparing the worst case molar mass data to the Mv of 145,300
and 131,000 g/mol as calculated from actual IV data, it is concluded
that by far not all water molecules available in the melt compounded material cause PLA cleavage. Whereas the PLA processing
guides [5] mention that even small amounts of moisture will
hydrolize PLA in the melt phase, it is concluded that relatively large
amounts of moisture present in the natural bres have a limited
additional effect on PLA degradation during 13 min of
compounding.
Similar observations have been reported by Placket et al. [26].
Only very small differences in weight-average molar mass, Mw,
as determined with size exclusion chromatography, were observed
for PLA composites based on vacuum-oven dried and undried jute
bres. Actually, the reduction in Mw of PLA in pre-dried and undried jutePLA composites was very similar to that for similarly
processed pure PLA.
MFI values of 30 mass% bre reinforced PLA are presented in Table 4, together with the values for virgin and kneaded PLA. The effect of different bre grade and of drying or not drying the bres
prior to compounding on MFI appears smaller than the effect of bre content. Apparently, the MFI values do not provide a simple
method to compare PLA degradation in different natural bre
composites.
The development of MFI of 30 mass% dried bre reinforced PLA
composites versus storage time at 190 C is presented in Fig. 5. The
composites dried at 80 C for 4 h show a sharp increase of the MFI
after about 500 s residence time at 190 C, which is a typical processing temperature for PLA and its composites. The bres are

M.J.A. van den Oever et al. / Composites: Part A 41 (2010) 16281635

signicant effect was found for ax and cotton though. The levels
of exural stiffness are signicantly larger than the maximum values of axPP presented by Bos et al. [48], being 3.8 GPa and
5.7 GPa for 30 and 50 mass% axPP composites versus 7.3 and
10.0 GPa for 30 and 50 mass% axPLA, respectively. These ax
PP compounds have been produced with the same batch kneading
equipment under fairly similar conditions. The higher stiffness for
the PLA compounds is partly due to the higher stiffness of PLA
compared to the stiffness of PP at room temperature, being 3.2
and 1.2 GPa, respectively. However, also the bre stiffness efciency, A, as dened in Eq. (5) is larger in the PLA composites [27].

MFI (g/10min)

6
5
4
3
2
1
0
0

500

1000

1500

Time (s)
Fig. 5. Melt ow index (MFI) versus storage time at 190 C of 30 mass% agrobre
PLA composites, based on pre-dried bres, after 4 h (grey symbols) and 24 h drying
(black symbols) at 80 C prior to analysis: Ramie (N), Flax (j), Cotton (). Adapted
from Recent advances in research on biodegradable polymers and sustainable
composites (Vol. 1), M.J.A. van den Oever, B. Beck, J. Mssig, Natural bre-PLA
composites: processing and mechanical properties, 8193. Copyright 2009, with
permission of Nova Science Publishers, Inc.

not expected to affect composite ow during indicated residence

times and temperatures, because they are likely to retain their
integrity and structure as may be concluded from only a small
reduction in exural strength of jutePP composites observed after
30 min heating at 200 C [46]. The sharp increase of MFI after 500 s
is therefore attributed to an onset point for accelerated degradation of PLA. These results indicate that the drying time for natural
brePLA composites prior to further processing should exceed the
4 h drying time recommended for pure PLA [2] in order to avoid
accelerated PLA degradation in case processing of the composite
takes more than 10 min. After 24 h of drying, degradation of the
PLA in the composite granules proceeds more steadily with
increasing residence time at 190 C.
3.4. Mechanical properties
The injection moulded pure NatureWorks PLA 4042D has a exural strength of 103(1) MPa, a exural modulus of 3.16(0.05) GPa
and a Charpy impact strength of 25(4) kJ/m2; between brackets
the standard deviation is provided. Fig. 6 shows the normalized effect of the incorporation of ramie, ax and cotton in PLA on these
mechanical properties. The exural stiffness increases linearly with
bre content and the increase is most pronounced for ramie bre.
Absence of bre drying before compounding had a small, yet signicant, negative effect on stiffness of the ramie composites, no
350

Normalized properties (%)

1633

300
250
200
150
100

A Ecomp  EPLA =X f

where Ecomp, EPLA, and Xf are the stiffness of the composite and the
PLA and the bre mass fraction respectively.
Further increase of the exural strength of PLA, which is high already, was marginally with increasing bre content. The slight increase however conrms the observations made by SEM that bres
and PLA matrix exhibit good interaction. Also, the increase in composite strength conrms that the bres have not fatally suffered
from the temperatures of the melt being over 200 C. The absence
of bre drying before compounding had rather a small positive effect on exural strength of ax and ramie composites. From the
SEM micrographs it has been concluded that brePLA compatibility was in between that of axPP composites and axPP composites in which MAPP coupling agent has been used. The use of
suitable coupling agents may further improve the PLA composite
strength. Nishino et al. [49] report the application of silane coupling agent on kenaf bre nonwoven before PLLA composite production by solution casting method. This increases the tensile
strength of the PLLA grade composites from 50 to 65 MPa.
When comparing to performance data presented in literature, it
must be noted that the PLA family exhibits a wide range of properties. These properties depend on the (co)polymer structure, molar
mass and crystallinity [50]. Furthermore, the mechanical properties of bre reinforced PLA composites depend on brematrix
adhesion, which may also be directly related to processing conditions. Plackett et al. [26] show that the tensile strength and modulus of jute nonwovenPLA composites increase by 38% and 17%,
respectively, when increasing the compression moulding temperature from 180 C to 210220 C. The possible explanations for the
increased performance are mentioned by Placket et al. to be improved bre wetting, differences in crystallinity and composite
porosity. The normalized increase in exural strength and modulus
obtained in this study is similar to what has been reported for
other melt blended PLA composites with good brematrix adhesion, being concluded from SEM analysis [10]. Some other authors
report a small reduction in exural strength, indicating poor bre
matrix adhesion [7,9].
The Charpy impact strength reduces with increasing bre content. The trend in reducing impact strength is similar for the three
bre sources investigated. Drying of the bres before compounding
had no signicant effect on impact strength. The reduction in impact strength of PLA by incorporation of natural bres has been reported before [7,9,10,15]. Only the incorporation of rayon bres
[15,17,18] and long kenaf bres [9] have resulted in an increase
of PLA impact strength.

50
0
0

10

20

30

40

50

Fibre content (mass %)

Fig. 6. Mechanical properties of undried (open symbols) and pre-dried (closed
symbols) bre reinforced PLA composites versus bre content: Ramie (N), Flax (j),
Cotton (), exural modulus (black symbols), exural strength (dark grey symbols),
Charpy impact strength (light grey symbols).

4. Conclusions
The analysis of the molar mass of PLA in the evaluated natural
bre composites, which have been melt compounded for 13 min,
indicates that by far not all water molecules available in the bres
cause PLA cleavage. Actually, the difference in PLA degradation is
larger between different bre grades than between drying and

1634

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not drying the bres prior to compounding; the number of chain

scissions calculated from intrinsic viscosity analysis was 0.73.2
per PLA molecule for the dried bre grades and 0.93.4 per PLA
molecule for the undried bres, while based on the water present
in the natural bres the maximum possible number of chain scissions was 12.723.1 for the dried bres and 385525 for the undried bres. The different effect of the bre grades on PLA
degradation is mainly attributed to a difference in brePLA contact surface area, which is related to bre or bre bundle diameter.
It is concluded that relatively large amounts of moisture present in
the bres did not cause fatal PLA degradation during 13 min of
compounding, whereas the PLA processing guides indicate that
even small amounts of moisture will hydrolize PLA in the melt
phase. This is good news for natural brePLA composite processors. At industrial processing scale, the required level of bre drying may signicantly inuence the economic feasibility of natural
brePLA composite production. If further processing of the composite takes more than 10 min, however, residual moisture in the
composite appears to cause accelerated PLA degradation.
Differences in morphological and mechanical properties between compounds based on dried and undried bres were marginal. SEM shows that the ax and ramie bre bundles have been
rened during compounding to a similar level of bre diameter.
All three bre grades are able to improve the polymers exural
properties to a level above that of natural brePP composites,
independent of bre pre-drying. Impact behaviour decreased with
increasing bre content as expected.
Acknowledgements
This work was performed within the Ecobinders EU project,
contract FP6-2005-NMP-011734. The European Commission is
kindly acknowledged for partly funding this project. The authors
thank mr Martin Snijder of GreenGran BV (Wageningen, The Netherlands) for kindly providing the ax sliver, Buckmann company
(Bremen, Germany) for providing the ramie sliver and Trtzschler
GmbH & Co. KG (Mnchengladbach, Germany) for providing the
cotton sliver, Mrs Jacqueline Donkers of Wageningen UR for performing the SEM analysis.
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