European Polymer Journal 63 (2015) 20–28

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European Polymer Journal

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

Biocompatible fibers from thermoplastic polyurethane

reinforced with polylactic acid microfibers
Vladislav Jašo a,⇑, Marko V. Rodić b, Zoran S. Petrović a
a
Kansas Polymer Research Center, Pittsburg State University, 1701 South Broadway, Pittsburg, KS 66762, USA
b
Department of Chemistry, Faculty of Sciences, University of Novi Sad, Trg Dositeja Obradovića 3, 21000 Novi Sad, Serbia

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

Article history: Fiber-reinforced composites were prepared by extrusion of biphasic thermoplastic

Received 12 August 2014 polyurethane/polylactic acid blends and the morphology was studied by electron
Received in revised form 23 November 2014 microscopy. Reinforcing effect of in-situ formed PLA microfibers on polyurethane matrix
Accepted 27 November 2014
was found. Polylactic acid (PLA) content was varied from 10 to 40 wt% resulting in
Available online 5 December 2014
reinforced polyurethane matrices with fibrils of 200–800 nm. Highly amorphous PLA fibrils
crystallized when heated above glass transition, resulting in storage modulus increase as
Keywords:
observed by dynamic mechanical analysis. Polyurethane (TPU) fibers reinforced with PLA
Polymer blends
In-situ fibrillation
microfibers had improved tensile strength and retained relatively high elongation, but
Fiber-modified composites elastic recovery decreased and hysteresis increased relative to the neat TPU. Orientation
Mechanical properties of fibers induced by cold drawing increased tensile strength and elastic modulus.
Morphology Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction A favorable condition for blending TPU with PLA is due

Thermoplastic polyurethane (TPU) elastomers are
excellent materials for many applications, but with
relatively low strength and limited biodegradability. Sim-
ple blends do improve some properties, but reinforcing
elastomers with in situ fibers of a glassy or semi-crystalline
polymer could be an efficient way of generating a
combination of new properties, such as high strength and
elongation; and also improved biodegradability with poly-
lactic acid (PLA). Preparing fiber–reinforced materials dur-
ing processing (extrusion or injection molding) requires
careful selection of conditions necessary to cause the fibril-
lation of the minority phase. In this work we investigated
feasibility of reinforcing elastomeric polyurethane fibers
with a semi-crystalline PLA by generating microfibrils of
PLA. Such fibers could be used for preparing biodegradable
elastomeric fabric with some unique properties.
⇑ Corresponding author. Tel.: +1 620 235 6591; fax: +1 620 235 4049.
E-mail addresses: vjaso@pittstate.edu (V. Jašo), marko.rodic@dh.uns.
ac.rs (M.V. Rodić), zpetrovic@gus.pittstate.edu (Z.S. Petrović).
to their potential compatibility as a result of their chemical
structure. TPU with polyester soft segments are generally
compatible with PLA, which is a polyester [1–3]. Also, car-
bamate from hard segments of TPU can form hydrogen
bonds with PLA [4].
Blend properties depend very much on blend morphol-
ogy, as well as on interaction between components in the
blend and their miscibility. Entirely new properties can
be achieved by inducing different morphologies such as
co-continuous, plate or fibrillar morphology. Microfiber-
reinforced composites (MFC) can be obtained by inducing
fibrillar morphology (micro or nanofibrils) of a minority
component. Composites with this morphology are created
during processing (in situ) by melt blending of two compo-
nents followed by elongational flow to induce orientation
(fibrillation). Some studies have been utilizing hot drawing
[5,6] of extrudate in the melt state with subsequent cool-
ing to preserve the fibrillar morphology while the others
have suggested cold stretching [7,8].
Formation of in-situ microfiber-reinforced composite
during processing is an elegant and economical way to

http://dx.doi.org/10.1016/j.eurpolymj.2014.11.041
0014-3057/Ó 2014 Elsevier Ltd. All rights reserved.
 V. Jašo et al. / European Polymer Journal 63 (2015) 20–28
improve the properties of the blends even further. Struc-
tural changes in blends are dependent on two factors, k
(viscosity ratio of the blend) and We (Weber or capillary
number). Viscosity ratio (k) is defined as:
k ¼ ld =lm ð1Þ
Here ld and lm are viscosities of the matrix and the dis-
persed phase. Weber number (We) can be calculated
according to:
lc_ R
We ¼ ð2Þ
a temperatures. In our study of PLA/TPU blends, mixing of
Shear rate is denoted as c, droplet diameter as R, and inter-
facial tension between the two phases as a.
During biphasic flow, hydrodynamic forces are acting to
deform and orient the minority phase, while at the same
time interfacial forces are acting in the opposite way to
restore their shape. Which of these would prevail and what
would be the equilibrium extent of droplet deformation
depends on processing conditions (droplet radius, shear
rate, temperature) and inherent properties of the system
(viscosities of components, interfacial tension). Droplet
breakup is also possible if capillary number exceeds critical
value. This value depends on the viscosity ratio of the sys-
tem [9]. Critical value of capillary number first decreases
with the increase of viscosity ratio, then reaches its mini-
mum near the viscosity ratio of 1, and then rapidly
increases again [9].
Fibrillation concept was used to reinforce thermoplastic
starch with PLA sub-micron fibers that were generated in-
situ by die extrusion and hot stretching [10]. Through this
process, tensile strength of thermoplastic starch was
increased three times. In the study of liquid crystalline
polymer fibrillation in polycarbonate matrix, it was
observed that for the fibrillation to occur, content of the
minority phase must be above the critical concentration
[11]. It was also found that in the particular system, matrix
viscosity plays a more important role than viscosity ratio,
as systems with higher matrix viscosity fibrillated better.
Utilization of die assembly with laminating-multiplying
elements has been found to induce fibrillation only by
higher shearing and elongation forces inside the die with-
out the need for post extrusion drawing [12]. Dynamic
packing injection molding technique was developed and
used to induce fibrillation by the introduction of an oscilla-
tory shear field on the melt–solid interface of the cooling
melt during the packing stage [13]. Biodegradable nano-
fibrillar composite was produced by melt spinning and
drawing of blends from PLA and poly(vinyl) alcohol (PVA)
[14]. These composites are both economic and ecological
and can be used for medical purposes.
In our previous work crystalline polypropylene (PP) has
been used to modify TPU and the fibrillation concept was
proved successful [15]. In the case of excessive compatibil-
ity, such as in polyurethane/PVC and liquid crystalline
polyesters/PET blends, fibrillation did not occur [16,17].
Reinforcement of TPU matrix was not achieved by the
incorporation of PP microfibers because both polymers
had roughly the same tensile strength. In this study, TPU
matrix reinforcement is expected since PLA with much
higher tensile strength than the matrix was used.
21
Combination of these two polymers has additional advan-
tages. As both polymers are biocompatible, the composite
fibers can potentially be used in the medical field. Since
PLA is polyester and TPU soft segments are also polyesters,
good conditions are provided for compatibility, good mix-
ing and good interfacial adhesion. In this way the use of
compatibilizer can be avoided. The miscibility, phase
morphology, mechanical properties, and toughening
mechanism of the PLA/TPU blend were first investigated
by Li and Shimizu [18]. The blend was found to be a
partially miscible system with shifted glass transition
components in a mixer resulted in a range of morphologies
varying from dispersed PLA globules in TPU matrix, to co-
continuous structures, and eventually dispersed spherical
TPU in PLA [19]. In this work we start from blends of a
known morphology, i.e., dispersed PLA globules in TPU
matrix (at PLA content 10–30 wt%) and co-continuous
phases (at 40 wt% PLA), expecting fibril formation during
biphasic flow. The products would be PLA fibril-reinforced
TPU fibers, but the concept can be extended to fiber-rein-
forced films and other extrusion or injection molded forms.
The work involved the study of morphology of TPU/PLA
blends after fiber spinning and the effect of PLA concentra-
tion on fibrillation and structure–property relationships of
composites.
2. Experimental
2.1. Materials
Elastollan C60A 10WH, a plasticized thermoplastic
polyester urethane having nominal Shore A hardness of
64 and density of 1.17 g/cm3, was kindly supplied by BASF
Polyurethanes GmbH Lemförde, Germany. PLA Polymer
6201D, a fiber spinning grade with density 1.24 g/cm3
and melt flow index of 15–30 g/10 min (at load 2.16 kg
and 210 °C), was obtained from Nature Works, Minne-
tonka, MN, USA.
2.2. Methods
Pellets of two polymers were dried for 5 h in a vacuum
oven at 80 °C. They were blended in the appropriate ratio
in a Rheomix 600 internal mixer with Rheocord System
40 (HAAKE, Paramus, NJ) at 190 °C for 15 min with a rotor
speed of 50 RPM. Blends were pelletized and dried for 5 h
in a vacuum oven at 80 °C. Fibers were extruded through
a 1 mm die of Malvern Rosand RH2000 capillary rheometer
(Malvern Instruments Inc, Westborough MA, USA) with a
piston speed of 5 mm/min (shear rate = 150 s1). Fibers
emerging from the die were hot drawn with the take-off
speed of 10 m/min by Postex TP1 (HAAKE, Karlsruhe, Ger-
many). In total, six samples were made, two from neat TPU
and PLA and four others from blends with 10, 20, 30 and
40 wt% of PLA.
Morphology of fibers was observed using Phenom
scanning electron microscope, SEM (Phenom-World BV,
Eindhoven, Netherlands). Samples were cryogenically bro-
ken and cross-section of fracture surfaces was observed.
22 V. Jašo et al. / European Polymer Journal 63 (2015) 20–28
Fig. 1. SEM micrographs of the cryogenically fractured surface of cross section of fibers from PLA/TPU blends: 10/90 (a), 20/80 (b), 30/70 (c) and 40/60 (d).
Also, fibers were stretched and fixed by adhesive tape to a
glass plate and partially dissolved by DMF to expose side
view. In both cases, they were sputter coated with gold
for SEM studies.
X-ray diffraction data were collected on a Gemini S
kappa-geometry diffractometer equipped with a Sapphire3
CCD area detector (Agilent Technologies UK Ltd, Yarnton,
UK) using graphite monochromated Mo Ka (k = 0.7107 Å)
X-radiation in all measurements. The fibers were oriented
perpendicular to the radiation beam and aligned parallel to
the vertical axis of the detector, with the sample-to-detec-
tor distance being 100 mm.
Thermal properties were measured using differential
scanning calorimeter (DSC) model Q100, from TA Instru-
ments, New Castle, DE, USA. Measurements were performed
in two cycles at a heating/cooling rate of 10 °C/min from
80 to 250 °C. Dynamic mechanical analysis (DMA) was
performed on a DMA 2980 from TA Instruments, at 10 Hz,
and at a heating rate of 3 °C/min in a temperature interval
from 80 °C to 120 °C.
Tensile strength, elongation at break and elastic
recovery of fibers were determined at room temperature
on QTest II tensile tester (MTS Systems Corp., Eden Prairie,
MN, USA) using 50 mm gauge length and extension rate of
50 mm/min. Elastic recovery and hysteresis were mea-
sured after 50%, 100% and 200% deformation. At least five
specimens were used for each test.
3. Results
3.1. Morphology of composite fibers
SEM micrographs of fractured fiber surfaces are shown
in Fig. 1. Short microfibers sticking out from the matrix
surface can be seen in samples with 10, 20 and 30 wt% of
PLA. Sample with 40 wt% of PLA exhibits co-continuous
morphology. Good bonding between the matrix and PLA
microfiber phase was observed in all samples. The fortu-
nate fact was that TPU is easily dissolved in DMF, revealing
the relatively insoluble PLA component. When fibers were
stretched and fixed by adhesive tape to a glass plate and
partially dissolved by DMF, SEM revealed microfibrils ori-
ented in the direction of the TPU fiber axis as shown in
 V. Jašo et al. / European Polymer Journal 63 (2015) 20–28
Fig. 2. SEM micrographs of partially dissolved surface of fibers (side view) from PLA/TPU blends: 10/90 (a), 20/80 (b), 30/70 (c) and 40/60 (d).
Fig. 2. Microfibers formed during extrusion and hot draw-
ing can be seen in fibers from blends with 10, 20 and
30 wt% of PLA (Fig. 2). With the increase of PLA wt%,
diameter of microfibers increased. Fig. 2a shows partially
dissolved fiber from blend with 10 wt% PLA with mostly
short and few long microfibers. Side view of partially
dissolved, stretched fiber with 40 wt% PLA shows tridimen-
sional co-continuous PLA phase oriented in the direction of
fiber axis (Fig. 2d). Diameter of TPU fibers after extrusion
and hot drawing was 325, 328, 330 and 345 lm, for sam-
ples with 10, 20, 30 and 40 wt% of PLA, respectively, which
translates to a draw ratio in a range of 8.5–9.5. Diameter of
PLA microfibers was between 200 and 300 nm in samples
with 10 and 20 wt% of PLA and around 800 nm in samples
with 30 wt% of PLA.
3.2. Orientation of PLA microfibers in composite fibers
Orientation of PLA microfibers (in fibers from blends
with 10, 20, 30 and 40 wt% PLA) was studied by X-ray
diffraction. In sufficiently oriented crystalline polymers,
diffraction rings are broken into arches. In our case, low
orientation resulted in continuous diffuse rings in all
23
un-stretched sample fibers (Fig. 3a, c, e, g). Stretching the
samples close to maximum elongation changed orientation
pattern, which now manifests as arches in diffractograms
of fibers with 20, 30 and 40 wt% of PLA (Fig. 3d, f and h).
Effect of orientation after stretching was also observed in
mechanical properties.
3.3. Thermal properties of composite fibers
Miscibility of two component polymers can be studied
by investigating their thermal properties. Results of the
DSC analysis are summarized in Tables 1 and 2. Pure TPU
had glass transition at around 45 °C and PLA at around
56 °C (Fig. 4). Pure PLA melts at 170 °C. Glass transition
and melting temperature of PLA phase are affected by the
presence of TPU. This is the evidence of interaction
between the components and their partial miscibility even
without the presence of compatibilizer. Partial miscibility
is a result of chemical structure of two polymers. This
was noticed and discussed in our previous study of PLA/
TPU blends [19]. Glass transition temperature of PLA in
fibers is higher than in blends [19] because better packing
24 V. Jašo et al. / European Polymer Journal 63 (2015) 20–28
Fig. 3. Diffractograms of fibers from PLA/TPU blends: 10/90 (a and b), 20/80 (c and d), 30/70 (e and f), 40/60 (g and h); un-oriented (on the left), oriented (on
the right).
of PLA molecules and orientation. Melting temperature and
glass transition temperature of TPU are almost the same as
those in blends. All transitions except crystallization are
shifted to lower temperatures in the second cycle. Glass
transition of PLA in fibers is lower in the second cycle than
in the first as a result of disorientation of microfibers but it
is still higher than the Tg of blends in the second cycle.
Crystallinity of PLA phase in the fibers was calculated
according to the procedure reported earlier [19]. In the first
cycle, crystallinity shows no regularity with the increase of
PLA concentration or correlation to the morphology data.
Crystallinity is lower in the second cycle as a result of fast
cooling. Crystallinity of pure PLA seems lower than in
fibers from blends, but it is due to overlapping of crystalli-
zation and melting, as reported earlier [19,20]. In the
second cycle, after thermal history is erased, increase of
crystallinity in PLA can be seen with the increase of its
content in fibers.
3.4. Dynamic mechanical properties of composite fibers
Study of dynamic mechanical behavior of fibers is a
useful tool for understanding morphology and reinforcing
effect of the PLA microfibers. With the increase of
temperature, fibers from immiscible blends exhibit two
distinctive drops of storage moduli that correspond to
glass transitions of continuous PLA and TPU phases as
shown in Fig. 5. This was not observed in blends with the
same PLA content [19], where only one large decrease of
modulus was present, as only TPU was a continuous phase.
Cold crystallization of amorphous phase of PLA is observed
at 60–80 °C as an increase of storage moduli in all samples
except neat TPU. Such behavior was not seen in
non-extruded original blends, indicating that stretched
and partially oriented molecules in PLA microfibrils
crystallize more easily.
Tan d curves of the fibers from blends (Fig. 5, Table 3)
show three transitions associated with Tg of the TPU, as
well as Tg of PLA and crystallization of PLA fibrils. Tg of
TPU increased by about 5 °C from pure TPU with the
increase of PLA content, and that of PLA decreased about
30 °C from pure PLA with increased TPU in fibers, suggest-
ing partial miscibility of components. In blends [19], there
is almost no change in Tg of TPU, whereas decrease in Tg of
PLA is around 30 °C, same as in fibers. Relatively high val-
ues of tan d (Fig. 5) peak associated with the PLA phase is
related to the high amorphous content. Glass transition
of TPU is a few degrees higher in fibers than in blends,
 V. Jašo et al. / European Polymer Journal 63 (2015) 20–28 25

Fig. 3 (continued)

Table 1
Transition temperatures of TPU and PLA, and PLA crystallinity, heats of crystallization and melting (first cycle).

Sample ID Tg (°C) TPU Tg (°C) PLA Tc (°C) PLA Tm (°C) PLA DHc (J/g) PLA DHm (J/g) PLA Crystallinity (%) PLA
TPU 45.9 – – – – – –
PLA–TPU 10-90 46.3 26.8 72.3 156.6 1.83 4.11 24.5
PLA–TPU 20-80 44.3 33.0 75.6 159.0 4.94 8.37 18.4
PLA–TPU 30-70 45.3 31.7 75.0 159.5 7.67 11.91 15.2
PLA–TPU 40-60 45.6 38.2 80.9 161.0 9.87 16.92 18.9
PLA – 56.2 134.2 169.2 15.11 28.62 14.5

Table 2
Transition temperatures of TPU and PLA, and PLA heats of crystallization and melting (second cycle).

Sample ID Tg (°C) TPU Tg (°C) PLA Tc (°C) PLA Tm (°C) PLA DHc (J/g) PLA DHm (J/g) PLA
TPU 43.5 – – – – –
PLA–TPU 10-90 42.9 27.9 – 155.6 0.29 0.73
PLA–TPU 20-80 42.0 32.5 88.0 158.3 3.95 5.46
PLA–TPU 30-70 43.0 29.6 83.5 157.9 8.13 11.39
PLA–TPU 40-60 42.5 35.3 82.9 160.5 10.78 17.27
PLA – 61.6 134.2 167.4 14.86 26.63

but Tg of PLA is lower in fibers. Tan d peaks are much higher blends, determined by DSC. Shoulder in tan d diagrams is
in fibers than in blends, which is in accordance with much due to cold crystallization occurring at higher tempera-
higher amorphous content of PLA in fibers compared to tures (above 50 °C).
26 V. Jašo et al. / European Polymer Journal 63 (2015) 20–28

Fig. 4. DSC thermograms of fibers from TPU, PLA, and their blends. (a) First cycle and (b) second cycle. Numbers designate wt% of PLA in the fiber.

Fig. 5. Storage modulus (left) and tan delta (right) of fibers from blends with different wt% of PLA. Numbers designate wt% of PLA in the particular fiber.

Table 3
Glass transition and cold crystallization (Tcc) of fibers from pure TPU, PLA
and fibers from their blends determined from peaks in Tan delta.

Sample ID Tan delta

Tg1 (°C) Tg2 (°C) Tcc (°C)
TPU 29.4 – –
PLA–TPU 10-90 34.0 40.3 65.3
PLA–TPU 20-80 31.9 44.9 74.2
PLA–TPU 30-70 35.6 45.6 76.5
PLA–TPU 40-60 34.9 52.5 78.1
PLA – 73.7 98.2

3.5. Mechanical properties of composite fibers

Thermoplastic PLA is a stronger material and therefore
useful for reinforcing TPU elastomers. It was expected that
in-situ fibrillation of the PLA phase would increase the ten-
sile properties of the elastomeric fibers. Stress–strain
curves of fibers (Fig. 6) change from elastic behavior of
TPU to a partly plastic deformation that is characterized
by a yield point (Fig. 6). Weak yield point is apparent in
fibers with 30 wt% of PLA and stronger in the fibers with
40 wt% of PLA (Table 4). Yield point was not observed in
blends of the same composition used for extrusion due to
differences in morphology. Initial elastic modulus
Fig. 6. Stress–strain curves of fibers from pure TPU and PLA and fibers
from their blends. Numbers designate wt% of PLA in the particular fiber.
increases from 6 to 340 MPa with the increase of PLA con-
tent in the fibers from 0 to 40 wt% of PLA (Table 4).
Mechanical properties of fibers could be improved by
cold drawing. When fibers were stretched to 90% of their
maximal elongation at break and kept for 10 min under
strain to induce orientation of both phases, tensile strength
increased twice or three times, and elastic modulus of
 V. Jašo et al. / European Polymer Journal 63 (2015) 20–28 27

Table 4
Tensile strength, elongation at break and elastic modulus of fibers from PLA, TPU and blends.

Sample ID Tensile strength (MPa) Yield stress (MPa) Elongation at break (%) Elastic modulus (MPa)
TPU 10.7 ± 0.7 – 699 ± 45 6±1
PLA–TPU 10-90 11.7 ± 1.2 – 595 ± 64 16 ± 4
PLA–TPU 20-80 16.7 ± 0.7 3.1 ± 0.3 508 ± 11 118 ± 20
PLA–TPU 30-70 17.1 ± 1.0 5.0 ± 0.3 473 ± 30 206 ± 15
PLA–TPU 40-60 17.3 ± 2.8 8.7 ± 0.7 478 ± 57 336 ± 98
PLA 48.0 ± 7.0 48.0 ± 7.0 7±5 1936 ± 172

fibers increased considerably (Fig. 7, Table 5). Elongation at

break decreased significantly, particularly at higher
concentrations of PLA, but was still higher than 400%.
Elastic recovery was determined for all fibers after elon-
gation of 50%, 100% and 200% in the first and second cycle
(Table 6). A decrease of elastic recovery with the increase
of PLA content in fibers is expected since PLA is semi-
crystalline and displays plastic flow at large deformations.
Elastic recovery also decreases with increasing elongation
(Table 6). Stress softening (Mullins effect) [21], which is
manifested as the lower stress at the same deformation
in the second cycle, results from the orientation of hard
domains in TPU in the first cycle of stretching. Elastic
recovery curves of fibers from blends with 10 wt% and
20 wt% of PLA are shown in Fig. 8a and b.
Fig. 7. Stress–strain curves of pre-stretched fibers.

Table 5
Tensile properties of pre-stretched fibers.

Sample ID Tensile strength (MPa) Yield stress (MPa) Elongation at break (%) Elastic modulus (MPa)
TPU 21.5 ± 2.9 – 525 ± 10 5±1
PLA–TPU 10-90 21.4 ± 3.2 – 380 ± 38 14 ± 2
PLA–TPU 20-80 29.6 ± 3.4 3.4 ± 0.5 219 ± 39 149 ± 23
PLA–TPU 30-70 51.9 ± 7.5 8.3 ± 1.1 137 ± 11 404 ± 72
PLA–TPU 40-60 70.5 ± 6.6 16.4 ± 1.5 90 ± 3 721 ± 79

Table 6
Elastic recovery of fibers at elongation of 50%, 100% and 200% in the first and second cycle.

Sample ID Elastic recovery (%)

50% 100% 200%
1st cycle 2nd cycle 1st cycle 2nd cycle 1st cycle 2nd cycle
TPU 96 97 94 96 90 94
PLA–TPU 10-90 72 77 61 75 54 75
PLA–TPU 20-80 39 59 34 55 31 56
PLA–TPU 30-70 30 56 28 50 25 52
PLA–TPU 40-60 25 49 22 45 17 39

Fig. 8. Elastic recovery curves of fibers from blends with 10 wt% of PLA (a) and 20 wt% of PLA (b) at elongation of 100%.
28 V. Jašo et al. / European Polymer Journal 63 (2015) 20–28

Table 7
Elastic hysteresis of fibers at elongation of 50%, 100% and 200% in the first and second cycle.

Sample ID Hysteresis (%)

50% 100% 200%
1st cycle 2nd cycle 1st cycle 2nd cycle 1st cycle 2nd cycle
TPU 27 12 38 15 54 26
PLA–TPU 10-90 60 47 67 50 79 56
PLA–TPU 20-80 81 61 84 64 86 68
PLA–TPU 30-70 88 67 88 71 89 71
PLA–TPU 40-60 92 73 93 77 94 79

Hysteresis, which is a measure of the inelastic compo-
nent in material deformation, increases with the increasing
elongation (Table 7) for all compositions. Increase is very
sudden between 10 and 20 wt% of PLA when it reaches
about 80% in the first cycle and 65% in the second cycle.
After that, hysteresis increases steadily but very little with
the increase of PLA content in the fibers. Elastic recovery
improves and hysteresis decreases in the second cycle,
which confirms previous observations that pre-stretching
can be used to orient both phases in the blend and modify
the elastic properties of the composite fibers.
4. Conclusions
Fibrillation of PLA minority phase in the TPU matrix
occurred in blends with 10, 20, and 30 wt% of PLA during
extrusion. PLA microfiber’s diameters varied between 200
and 800 nm and were not highly oriented. Excellent
interphase bonding was the result of partial miscibility of
components as reflected in the change of glass transition
temperatures.
Dynamic mechanical analysis revealed two drops in
storage moduli, which was not observed in blends, and
indicates presence of PLA microfibers which continue to
bear the stress at higher temperatures.
Stress–strain curves of blends with 20, 30 and 40 wt% of
PLA all exhibit yield point although PLA is minority phase
in these blends. Tensile strength of non-drawn fibers
increase from 11 to 17 MPa and modulus from 6 to
336 MPa with increasing PLA content from zero to
40 wt%, while elongation decreased from 700% to 480%.
Cold drawing of fibers with 10–40 wt% PLA increased
tensile strength from 12–17 MPa to 21–70 MPa, modulus
from 16–336 MPa to 14–720 MPa and decreased elonga-
tion from 600–480% to 380–90%.
Acknowledgements
This work was supported by a grant from the United
States Department of Agriculture (USDA-CSREES 2010-
38924-20706) and by the Ministry of Education and
Science of the Republic of Serbia (Grant No. 172014).
References
[1] Liu X, Dever M, Fair N, Benson RS. Thermal and mechanical
properties of poly(lactic acid) and poly(ethylene/butylene
succinate) blends. J Environ Polym Degrad 1997;5:225–35.
[2] Shibata M, Inouea Y, Miyoshib M. Mechanical properties,
morphology, and crystallization behavior of blends of poly(l-
lactide) with poly(butylene succinate-co-l-lactate) and
poly(butylene succinate). Polymer 2006;47:3557–64.
[3] Nijenhuis AJ, Colstee E, Grijpma DW, Pennings AJ. High molecular
weight poly(l-lactide) and poly(ethylene oxide) blends: thermal
characterization and physical properties. Polymer 1996;37:5849–57.
[4] Han JJ, Huang HX. Preparation and characterization of biodegradable
polylactide/thermoplastic polyurethane elastomer blends. J Appl
Polym Sci 2011;120:3217–23.
[5] Li Z, Yang M, Xie B, Feng J, Huang R. In-situ microfiber reinforced
composite based on PET and PE via slit die extrusion and hot
stretching: Influences of hot stretching ratio on morphology and
tensile properties at a fixed composition. Polym Eng Sci
2003;43:615–28.
[6] Monticciolo A, Cassagnau P, Michel A. Fibrillar morphology
development of PE/PBT blends: rheology and solvent permeability.
Polym Eng Sci 1998;38:1882–9.
[7] Jayanarayanan K, Thomas S, Joseph K. Morphology, static and
dynamic mechanical properties of in situ microfibrillar composites
based on polypropylene/poly (ethylene terephthalate) blends.
Composites A 2008;39:164–75.
[8] Taepaiboon P, Junkasem J, Dangtungee R, Amornsakchai T, Supaphol
P. In situ microfibrillar-reinforced composites of isotactic
polypropylene/recycled poly(ethylene terephthalate) system and
effect of compatibilizer. J Appl Polym Sci 2006;102:1173–81.
[9] Puyvelde PVV, Moldenaers P. Rheology and morphology
development in immiscible polymer blends. Rheol Rev 2005:101–45.
[10] Jiang L, Liu B, Zhang J. Novel high-strength thermoplastic starch
reinforced by in situ poly(lactic acid) fibrillation. Macromol Mater
Eng 2009;294:301–5.
[11] Tan LP, Yue CY, Tam KC, Lam YC, Hu X. Effects of shear rate, viscosity
ratio and liquid crystalline polymer content on morphological and
mechanical properties of polycarbonate and LCP blends. Polym Int
2002;51:398–405.
[12] Shen J, Wang M, Li J, Guo S. In situ fibrillation of polyamide 6 in
isotactic polypropylene occurring in the laminating-multiplying die.
Polym Adv Technol 2011;22:237–45.
[13] Su R, Jiang K, Ge Y, Hu S, Li Z, Li X, et al. Shear-induced fibrillation
and resultant mechanical properties of injection-molded polyamide
1010/isotactic polypropylene blends. Polym Int 2011;60:1655–62.
[14] Tran NHA, Brünig H, Hinüber C, Heinrich G. Melt spinning of
biodegradable nanofibrillary structures from poly(lactic acid) and
poly(vinyl alcohol) blends. Macromol Mater Eng 2014;299:219–27.
[15] Jašo V, Milić J, Divjaković V, Petrović ZS. Novel elastomeric
polyurethane fibers modified with polypropylene microfibers. Eur
Polym J 2013;49:3947–55.
[16] Petrović ZS, Farris R. Structure–property relationship in fibers spun
from poly(ethylene terephthalate) and liquid crystalline polymer
blends. I. The effect of composition and processing on fiber
morphology and properties. J Appl Polym Sci 1995;58:1077–85.
[17] Petrović ZS, Javni I, Shull J, Waddon A. Phase behavior and properties
of polyurethane–PVC blends and fibers. Rubber Chem Technol
1999;72:587–601.
[18] Li Y, Shimizu H. Toughening of polylactide by melt blending with a
biodegradable poly(ether)urethane elastomer. Macromol Biosci
2007;7:921–8.
[19] Jašo V, Cvetinov M, Rakić S, Petrović ZS. Bio-plastics and elastomers
from polylactic acid/thermoplastic polyurethane blends. J Appl
Polym Sci 2014;131:41104. http://dx.doi.org/10.1002/app.41104.
[20] Solarski S, Ferreira M, Devaux E. Characterization of the thermal
properties of PLA fibers by modulated differential scanning
calorimetry. Polymer 2005;46:11187–92.
[21] Aklonis JJ, MacKnight WJ. Introduction to polymer
viscoelasticity. New York: John Wiley and Sons; 1983.