ISSN 0965-545X, Polymer Science, Series A, 2021, Vol. 63, Suppl. 1, pp. S46–S57. © Pleiades Publishing, Ltd., 2021.

ISSN 0965-545X, Polymer Science, Series A, 2022. © Pleiades Publishing, Ltd., 2022.

POLYMER
BLENDS

Effect of Compatibilization of Thermoplastic Polyurethane

with Poly(lactic acid) for the Preparation of Sustainable Blends
K. A. Rajesha,*, Arun. M. Panickera, and T. O. Varghesea
aCentral Institute of Plastics Engineering and Technology (CIPET), Eloor, Udyogamandal P.O., Kochi, Kerala, 683501 India
*e-mail: [email protected]
Received December 25, 2021; revised January 18, 2022; accepted January 21, 2022

Abstract⎯Poly(lactic acid) (PLA) is a prominent biopolymer highly recommended for resolving environ-
mental concerns due to its biodegradability. To overcome its limitations of brittleness, blending with other
polymers is common technique but results in phase separation. In this work, impact modification of poly(lac-
tic acid) (PLA) has been carried out by melt blending with maleic anhydride grafted thermoplastic polyure-
thane (PLMTPU) and with acrylonitrile grafted thermoplastic polyurethane (PLATPU). The blends were
prepared using twin screw extruder by melt mixing of PLA with grafted TPUs in ratios of 97.5/2.5, 95/5,
92.5/7.5, and 90/10 by weight percentage. The interfacial adhesion imparted through compatibilization
shown pronounced improvement in the impact strength of PLATPU and PLMTPU by 88 and 28% respec-
tively compared to the virgin PLA. Also, improvement in the elongation at break from 1.2% (PLA) to 4.4%
(PLATPU) and 4.9% (PLMTPU) was observed. The mechanical studies were also compared with the theo-
retical models. Interestingly, incorporated flexibility to the PLA with ATPU and MTPU and the impeded
effective stress transfer mechanism was evident on probing the morphology of the blends. The novel compat-
ibilized blend of PLA with grafted TPU is potential candidate for packaging, biomedical applications and as
a feed stock material in 3D printing technologies.

DOI: 10.1134/S0965545X22030087

INTRODUCTION blends of PLA has been studied with elastomeric poly-

In recent times, quite an interest is flourishing in mers such as low density polyethylene [9], polypropyl-
the development of bio-based polymer systems in dis- ene [10], polyethylene glycol [11], and natural rubber
parate level of applications like structural, biomedical, [12] and which are showed a plasticizing effect on
pharmaceutical etc. The short in the resources, inse- PLA. Fully compatible low molecular weight sub-
cure pricing level, contribution in climate change, and stances, as well as miscible or immiscible polymer
problem related to waste disposal fueled the develop- blends of PLA with flexible polymers, results in the
ment of polymers from renewable resources than the molecules of the heterogenous phase to act as flexibile
polymers from the fossil fuel. Industrialization of bio- moieties within the molecular framework of PLA and
polymers is still evolving and expected to be in a hence effectively lowering glass transition temperature
remarkable level in the coming years. Tg and in turn resulting in improved impact properties.
Poly(lactic acid) (PLA) is an important biopoly- PLA blending offers a cost-effective option in com-
mer, ubiquitous in every field of research owing to its parison to other impact modification methodologies.
peculiar features like biodegradability, high stiffness, Copolymerization is also employed in tailoring the
strength, high workability and transparency etc. [1]. In tensile and impact properties of PLA to desired out-
order to overcome the impairments of unmodified comes through polycondensation of lactic acid (LA)
PLA like brittleness, low impact strength and elonga- with other monomers (or oligomers) or ring-opening
tion at break, blending can be adopted [2]. Enhance- copolymerization (ROC) of LA with other cyclic
ment in the toughness and stress elongation of PLA monomers (or oligomers), wherein ROC synthesis
has been observed in the studies, where, addition of method is extensively employed for the high molecular
rigid fillers, blending with polymers, flexible fillers or weight copolymers. Consequently, plasticization of
elastomers, co-polymerization, and plasticization has PLA with plasticizers/modifiers, viz. oligomeric
been executed. As reported, coir fibre [3], sugarcane malonate ester amides [13], bifunctional cyclic esters
bagasse fibre [4], flax fibre [5], sisal and hemp fibre, [14], citrate esters [15], 4,4'-methylene diphenyl diiso-
cotton fibre [6], banana/sisal fibre [7], Surface treated cyanate [16], polymerized soybean oil [17], polyeth-
cellulose fibre reinforced PLA composite materials ylene glycol and acetyl triethyl citrate etc. [18] have
exhibits an improved elongation at break [8]. Various been found to impart good processability, flexibility

S46
 EFFECT OF COMPATIBILIZATION OF THERMOPLASTIC POLYURETHANE S47

and ductility to the glassy PLA matrix. However, the compromising the biodegradability of PLA. The study
high cost of copolymerization and the migration of was successfully imparted impact modification on
low molecular weight plasticizers from PLA matrix PLA with maleic anhydride grafted thermoplastic
during modification by plasticization make these pro- polyurethane (PLMTPU) and with acrylonitrile
cesses unsuitable for wider implementation. From grafted thermoplastic polyurethane (PLATPU). The
these approaches blending can be said to be the most melt blending processes were carried out in a twin
effective and the simplest process. screw extruder with PLA and grafted TPUs in ratios of
In polymer blending a new material having differ- 97.5/2.5, 95/5, 92.5/7.5, and 90/10 by weight percent-
ent physical properties is created from at least two age. The interfacial compatibility and strong bonding
polymers. In which compatible polymer blends are among the blend components resulted in blends with
immiscible blends with macroscopically uniform desirable properties. The resulted novel PLA blends
physical properties and it is achieved from the strong ensures minimal carbon foot print and promises the
interactions among the component polymers. Twin extent of applicability of PLA.
screw extruders are often used for the blending of
polymers in an industrial scale. The physical blending
of PLA is challenging due to its intrinsic immiscibility, EXPERIMENTAL
inferior compatibility, and destitute interfacial bond-
ing between the blend components [19]. Materials
In several studies toughening of PLA was investi-
gated with flexible, biocompatible TPU elastomers. Poly(lactic acid) injection moulding grade, Ingeo
TPU is a block copolymer having alternate hard seg- 3052D (M.W: 116000 g/mol, Specific gravity:
ments (diisocyanates) and soft segments (polyester or 1.24 g/cm3, and MFI (210°C and 2.16 kg load):
polyether based polyol) [20]. Owing to the fact that 14 g/10 min) was procured from Nature Works LLC,
TPU bears lower glass transition temperature and high USA. Thermoplastic polyurethane (TPU) used in this
thermal stability, blending with PLA is more easier work is Desmopan 385 E Ester type injection mould-
[21]. It has been reported that, the brittle nature of ing grade was bought from Bayer Material science AG,
PLA became ductile after blending with TPU [22]. In USA. Acrylonitrile (AN) monomer with purity ≥99%,
several studies, elongation at break and impact Sodium hydroxide (≥97%), and dicumyl peroxide
strength were found to enhance during blending with (≥97.5%) were purchased from Zigma Aldrich. Maleic
TPU [23, 24]. anhydride with ≥ 99% was obtained from Loba Che-
However, the compatibility between TPU and PLA mie. Acetone with ≥99% (M.W: 58.08 g/mol) pro-
is poor and needs to improve for achieving in-depth cured from Merck. All allied chemicals used in this
properties and extent the applicability of the blend. study were analytical grade.
Kahraman et al., reported that PLA/TPU blend sys-
tem with enhanced phase compatibility, impact
strength and ductility with the advent of multifunc- Sample Preparation
tional epoxy Joncryl ADR 4468 chain extender (CE)
[25]. In one of the studies by Kilic et al., PLA/TPU Grafting. Preparation of ATPU and MTPU were
has been compatibilized using triglycidylisobutyl poly- carried out in a co-rotating twin-screw extruder
hedral oligomeric silsesquioxane and reported a con- (model-ZV20, Specific Engineering). Dicumyl perox-
siderable decrease in the tensile strength and increase ide (DCP) was used as the free radical initiator. For
in the impact strength over blending process [26]. In the preparation of ATPU, Acrylonitrile monomer was
another study a ternary blend system of, thermoplastic washed with 3% NaOH and 3% Orthophosphoric acid
polyurethane/poly (D-lactic) acid/poly (L-lactic) to render inhibitor free for three times and checked for
acid (TPU/PDLA/PLLA) was reported with the max- neutral pH. Further acrylonitrile (AN) monomer was
imum value of tensile strength, elongation at break, washed with distilled water and dried using molecular
and fracture work of ternary blends are 61.9 MPa, sieves 4 Å × 1.5 mm. 20 g dried DC reprecipitated
23.5%, and 1038.9 kJ/m3, respectively [27]. However, from methanol (2% of total weight) was mixed well
the use of chain extenders inversely affects the biode- with 900 g TPU. 100 mL AN was taken in a flow rate
gradability owing to the increased hard segment con- estimated burette. TPU was added through the hopper
tent [28]. Majority of the blend system of PLA with while AN was added directly into the extruder barrel
TPU reported in the literature are of higher blend ratio using a burette. The screw speed was set at 60 rpm and
by reducing more PLA content. the temperature profile was maintained at 165, 175,
Previously reported studies were done with higher 185, 195, 200, and 205°C at melt pressure of 5–15 bar.
percentages of TPU content in the PLA blend and The resulting AN grafted TPU (ATPU) was pelletized,
these effected in poor miscibility, processability, and washed repeatedly with demineralized water and dried
biodegradability. In this work, we focused on an over- in hot air oven overnight at 100 ± 5°C to constant
all magnification of the properties of PLA without weight.

POLYMER SCIENCE, SERIES A Vol. 63 Suppl. 1 2021

S48 RAJESH et al.

Table 1. Compositions of PLATPU and PLMTPU blends and melting and crystallization parameters of PLA, PLATPU,
and PLMTPU
Volume
PLA, wt % TPU, wt % Sample code Tg, °C Tcc, °C ΔHcc, J/g Tm, °C ΔHm, J/g X c, %
fraction Φd
100 0 0 PLA 61 115 34 150 37 40
97.5 2.5 0.03 2.5PLATPU 64 134 10 149 11 12
95.0 5.0 0.05 5PLATPU 64 132 13 148 15 17
92.5 7.5 0.08 7.5PLATPU 64 133 14 148 16 18
90.0 10.0 0.10 10PLATPU 64 133 13 148 15 18
97.5 2.5 0.03 2.5PLMTPU 62 131 18 147 20 22
95.0 5.0 0.05 5PLMTPU 61 130 25 147 23 10
92.5 7.5 0.08 7.5PLMTPU 59 129 23 146 24 28
90.0 10.0 0.10 10PLMTPU 58 123 27 144 30 4

Further grafting of MA on TPU was carried using 15 bar. The extruded MA grafted TPU (MTPU) was
the same technique. In this case DCP was reprecipi- pelletized, washed, and drying was carried out at 100 ±
tated from acetone. Then, MA was mixed with TPU 5°C overnight in a hot air oven and stored in airtight
and fed into the extruder hopper at 0.3 and 10% com- polybags.
positions respectively. The extruder was set in a tem- In both cases percentage yield of graft was esti-
perature profile of 165–205°C and at pressure of 10– mated by the Eq. (1) [29]:

Dry weight of grafted TPU − Dry weight of TPU

% Graft yield = × 100. (1)
Dry weight of TPU

Preparation of blends. Binary blends of PLA with Experimental Techniques

Acrylonitrile grafted Thermoplastic Polyurethane Fourier transform infrared spectroscopy. Grafting
(ATPU) and Maleic Anhydride grafted Thermoplastic of AN and MA were confirmed by FTIR and the study
Polyurethane (MTPU) were prepared by melt blend- was conducted with Avatar 370 FTIR, Thermo Nico-
ing process using co-rotating twin-screw extruder let (Thermofisher Scientific, MA, USA) spectropho-
(model-ZV20). Resulting blends were characterized in tometer. Scanning were done on dried powdered sam-
correlation to their dispersed phase volume fractions ples over a range of 400–4000 cm–1 at a resolution of
Φd and calculated according to the Eq. (2): 4 cm–1.
Thermal characterizations. Thermal characteristics
Wd  of prepared blends were obtained by means of DSC at
ρ  a heating range of 20 to 200°C and 20 K/min heating
Φd =  d , (2) rate using TA Instruments-Q20 (New Castle, DE) dif-
Wd  Wc 
+
 ρ   ρ 
ferential scanning calorimeter. Specimens for the test
 d   c  were prepared by injection moulding technique. The
thermal stability of the blends was analyzed by TGA
where W is the weight fractions and ρ is the density of using TGA-Q50 thermogravimetric analyzer (TA
the constituents wherein subscripts d and c denote dis- Instruments Inc., New Castle, USA). The test was
persed phase and continuous phases respectively. carried out over a temperature range of 30 to 600°C at
Table 1 enlists the details of blend formulations and a scan rate of 10 K/min. For this 5–10 mg of sample
their corresponding Φd values. was taken from the injection moulded specimen.
Mechanical study. Tensile and flexural tests were
Preparation of test specimens. Test specimens were performed on universal testing machine (UTM) Tin-
prepared by injection moulding technique using auto- ius Olsen H50KL (Tinius Olsen) at 23 ± 2°C and 50 ±
matic injection moulding machine (Model-OMEGA 5% RH by following ASTM D 638 and ASTM D 790
80 WIDE, Ferromatik Milacron). A temperature pro- respectively. For the tensile test, cross-head speed of
file of 180 to 200°C was maintained while the injection 50 mm/min was used. Flexural tests were conducted at
pressure and mould temperature was 60 bar and 30°C a cross-head bending speed of 2.5 mm/min and span
respectively. distance of 96 mm. Notched Izod impact strength was

POLYMER SCIENCE, SERIES A Vol. 63 Suppl. 1 2021

 EFFECT OF COMPATIBILIZATION OF THERMOPLASTIC POLYURETHANE S49

Table 2. Mechanical properties of PLA, PLATPU, and PLMTPU blends

Tensile Increase Tensile Increase Increase of Impact Increase
Elongation
Sample code modulus, of tensile strength, of tensile elongation strength, of impact
at break, %
MPa modulus, % MPa strength, % at break, % kJ/m2 strength, %
PLA 3280 ± 150 – 38.27 ± 7.00 – 1.20 ± 0.50 – 1.64 ± 0.50 –
2.5PLATPU 3040 ± 300 –7.22 45.10 ± 0.50 17.86 3.88 ± 1.00 224.14 2.07 ± 0.50 25.83
5PLATPU 3035 ± 20 –7.38 43.30 ± 1.00 13.15 4.38 ± 1.00 266.19 2.63 ± 0.50 60.14
7.5PLATPU 2980 ± 100 –9.05 39.73 ± 2.00 3.83 3.94 ± 1.00 228.88 3.10 ± 0.50 88.80
10PLATPU 2590 ± 100 –20.96 35.57 ± 6.00 –7.06 3.55 ± 1.00 196.85 2.80 ± 0.50 70.63
2.5PLMTPU 2977 ± 70 –9.16 51.77 ± 1 35.28 4.93 ± 1 311.86 1.68 ± 0.50 2.60
5PLMTPU 3085 ± 80 –5.85 43.00 ± 1 12.37 3.56 ± 1.22 197.41 1.81 ± 0.50 10.34
7.5PLMTPU 2860 ± 150 –12.72 42.23 ± 1 10.37 2.89 ± 0.94 141.72 2.10 ± 0.50 27.86
10PLMTPU 2920 ± 300 –10.78 38.67 ± 2 1.05 2.43 ± 0.83 103.01 1.71 ± 0.50 4.26

measured on Tinius Olsen Model Impact 104 machine 1700 cm–1 reveals good degree of cyclic maleic anhy-
following ASTM D 256 specifications. A minimum of dride grafting with the shift in peak of carbonyl group
five specimens were tested and reported the average of TPU to higher energy wavelength. Grafting of AN
values. over TPU was confirmed by the presence of C≡N
Morphological analysis. Evaluation of the mor- stretching at 2232 cm–1. The signs of maleation were
phology of the PLA blends was studied by SEM using evident from the spectra and these includes a small
JEOL Model, JSM-6390 L V under an accelerating shoulder in the 1725 cm–1 can be due to C=O, peak at
voltage of 10 kV. Impact fractured specimens with gold 1875 cm–1 corresponds to the COOH, and peaks pres-
sputtering were used for the test. ent in the region from 1699 to 1076 cm–1 attributes to
C=C in the MA [33, 34].
RESULTS AND DISCUSSION DSC heating scans of the samples are depicted in
Figure 1 shows the FTIR spectra of pure TPU, the Fig. 2 and the corresponding parameters are
ATPU, and MTPU. On analyzing the FTIR spectra of enlisted in Table 1. The Tg value of PLA was observed
TPU, ATPU, and MTPU, peaks present in the region at 61°C and it is in accordance with the literature [35].
of 3300–3340 cm–1 corresponds to the stretching On analyzing the thermal characteristics of blends
vibration of OH groups. On analyzing TPU spectra there observed a slight increment in the Tg value on the
NH stretching and deformation were present at 3338 addition of ATPU. This can be due to the dipole inter-
and 1530 cm–1 respectively. We may observe symmet- action between the –CN groups in the ATPU with the
ric and asymmetric CH vibrations at 2955 and chains of PLA. Mobility of the polymer chain get
2922 cm–1 [30, 31]. In the case of TPU, NH bending restricted with the increase in the dipole interaction
peak can be observed at 1533 cm–1 [32]. The carbonyl [36, 37]. While the MTPU addition caused decrement
index calculated for MTPU was 1.24. The peak at in the Tg value and it can be accredited to the increased
compatibility between the polymers [38]. The
decrease in the Tg value also has the significance in
Table 3. Adhesion parameter k, Eq. (4), Stress concentra- interface adhesion and it can be defined in terms of
tion factor α, Eq. (5), and parameter representing load
bearing capacity of disperse phase B, Eq. (6) in PLATPU strong bonding among the polymers [39]. The com-
and PLMTPU blends patibilization effect of ATPU and MTPU on blending
with PLA is evident from the DSC scans which shows
PLATPU PLMTPU
Φd a single melting peak corresponding to PLA (at
k α B k α B ca. 145°C).
0.03 –2.04 –6.37 9.80 –4.04 –11.71 15.14 The melting peaks in PLATPU and PLMTPU
0.05 –0.95 –2.40 5.77 –0.89 –2.26 5.64 blends can be accredited to the crystallization of
0.08 –0.21 –0.49 3.81 –0.57 –1.28 4.60 PLA. The percentage of crystallinity of PLATPU
and PLMTPU decreased compared to PLA and it
0.10 0.32 0.71 2.57 –0.05 –0.10 3.38
can be accredited to the soft segments present in the
Mean TPU. This is because of the decrease in the inter and
–0.72 –2.13 5.49 –1.39 –3.84 7.19
value intramolecular forces and caused f lexibility to the

POLYMER SCIENCE, SERIES A Vol. 63 Suppl. 1 2021

S50 RAJESH et al.

Transmittance, %
3

4000 3000 2000 1000

Wavenumber, cm−1

Fig. 1. FTIR spectra of (1) TPU, (2) ATPU, and (3) MTPU.

Heat flow, a.u. (a) Heat flow, a.u. (b)

0.4 0.4

0 0

−0.4 −0.4

−0.8 −0.8

−1.2 −1.2 1
2
1 3
2 4
−1.6 3 −1.6 5
4
5
−2.0 −2.0
80 120 160 200 80 120 160 200
Temperature, °C Temperature, °C

Fig. 2. DSC thermograms of (1) PLA, (a) (2) 2.5PLATPU, (3) 5PLATPU, (4) 7.5PLATPU, (5) 10PLATPU,
(b) (2) 2.5PLMTPU, (3) 5PLMTPU, (4) 7.5PLMTPU, (5) 10PLMTPU.

PLA chains and this leads to the decrease in crystallin- range of 320 to 380°C. The increase in thermal stabil-
ity [40]. ity of PLATPU and PLMTPU blends compared to
PLA may be attributed to the blend component TPU
The results of thermal stability studies of virgin absorbing more energy and consequent delay in the
PLA and PLATPU, PLMTPU blends are summarized degradation onset of PLA [41]. The presence of MA
in Table 4. Onset temperature of degradation of PLA and AN units also contributes to the thermal stability
was 316.8°C and the major degradation process was of the blend system [42].
completed by 340.4°C (Fig. 3). It was noted that all the
blend compositions had higher onset, maximum deg- Typically, PLA suffers from strain localization
radation temperature and peak degradation values induced by strong strain softening and insufficient
compared to virgin PLA. The major degradation stage strain hardening at break, leading to tri-axial stress
of PLA/TPU blends took place in the temperature concentration [43]. Consequently, the local tri-axial

POLYMER SCIENCE, SERIES A Vol. 63 Suppl. 1 2021

 EFFECT OF COMPATIBILIZATION OF THERMOPLASTIC POLYURETHANE S51

Table 4. Thermal properties of PLA, PLATPU and PLMTPU

Onset degradation Peak degradation Maximum degradation Maximum weight loss
Sample
temperature Tonset, °C temperature Tpeak, °C temperature Tmax, °C rate W, %/°C
PLA 316.8 336.9 340.4 –3.2
2.5PLATPU 332.1 369.1 376.0 –3.4
5PLATPU 336.8 365.2 372.9 –2.6
7.5PLATPU 333.8 363.8 375.9 –2.4
10PLATPU 340.2 364.6 374.7 –2.5
2.5PLMTPU 325.6 366.0 376.1 –2.7
5PLMTPU 334.2 364.5 373.7 –2.5
7.5PLMTPU 330.4 365.6 377.3 –2.1
10PLMTPU 321.8 363.4 371.7 –1.9

stresses induce void nucleation and craze leading to concentrated triaxial stresses of PLA and conse-
the brittle failure mechanism of PLA. However, the quently the lowering of yield stress and broadening of
incorporation of ATPU and MTPU flexible grafted yield peak. The blend samples exhibited a ductile
polymer moieties resulted in the delocalization of the mechanism of failure characterized by strain softening

Weight, % Weight, %
(a) 1 (b) 1
100 100 2
2
3 3
80 4 80 4
5 5
60 60

40 40

20 20

0 0
100 200 300 400 500 600 100 200 300 400 500 600
Temperature, °C Temperature, °C
Deriv. weight change, %/°C Deriv. weight change, %/°C
0 (c) 0 (d)

1 1

2 2 1
1
2 2
3 3
3 4 3 4
5 5

100 200 300 400 500 600 100 200 300 400 500 600
Temperature, °C Temperature, °C

Fig. 3. (a, b) TGA and (c, d) DTG curves of (1) PLA, (a, c) (2) 2.5PLATPU, (3) 5PLATPU, (4) 7.5PLATPU, (5) 10PLATPU,
(b, d) (2) 2.5PLMTPU, (3) 5PLMTPU, (4) 7.5PLMTPU, (5) 10PLMTPU.

POLYMER SCIENCE, SERIES A Vol. 63 Suppl. 1 2021

S52 RAJESH et al.

followed by necking and strain broadening as sug- tions and thereby a greater decrease in tensile strength
gested by the tensile characteristics of blends enlisted is witnessed [44]. The model assumes dispersed phase
in Table 2. as non-interacting pores or voids in the continuous
The blends exhibited a primary increase in tensile phase.
strength and elongation at break compared to pure
σb (−αΦd )
PLA and consequent decrease with increasing percent = e . (5)
composition of compatibilized TPU. This may be σm
attributed to the stress concentration effects of the The non-interacting discrete phase, as per the
TPU and the interactions of Acrylonitrile and Maleic assumptions of porosity model, acts as areas of stress
anhydride on PLA. concentration for lack of adhesion at phase boundar-
The variation of relative tensile strength and nor- ies. However, in the Béla Pukánszky model, (Eq. (6)),
malized tensile strength with respect to the corre- tensile strength of the blend is determined by tensile
sponding volume fractions of the respective blends strength of the continuous phase, effective load-bear-
revealed that all blends had relative tensile strength ing cross-section and interaction between the two
value in the range of unity, suggesting that the strain phases, B [45]. The parameter B signifies the load
softening effect of the less hard TPU blend component bearing capacity of the dispersed phase and is further
did not drastically affect the strength property of the dependent on the interface, contact area and proper-
matrix material. It was further noted that all blends ties, as in aggregation decreasing the physical interfa-
had normalized tensile strength values greater than cial contact area between the two polymeric blends,
unity, volume fraction 0.03Φd being four folds for consequently decreasing the value of B.
PLATPU and two folds for PLMTPU blends. This
may be attributed to the softening effect of TPU being σ b  (1 − Φ d )  ( BΦd )
= ×e . (6)
countered effectively by compatibilization and the σ m (1 + 2.5Φ d )
consequent crystallinity values. Tensile strength of
PLA/TPU blends was found to initially increase and The variations of experimental and theoretical val-
then decrease in correlation to percent crystallinity ues tensile strength of the blends against Φd values are
values. This may be the result of a positive interference plotted in the Fig. 4, wherein, NN Model and Porosity
and the enhanced nucleation and PLA crystal growth model assumes discrete and continuous phases to be
supported by the presence of a flexible substituent in non-interacting for being non-adherent type and
TPU, as evident from the DSC studies. However, the whereby the ultimate tensile strength is a function of
tensile strength values were greater than that of pure either area fraction or volume fraction of the dispersed
PLA, suggesting a positive interaction mechanism phase. The characteristic parameters of the models, k,
between the substituent groups and PLA as evident α and B for NN Model, Porosity model and Béla
from Table 2. Pukánszky model respectively, were calculated and are
Experimental values of tensile strengths of blends listed in Table 3. The negative average values of k were
were compared to theoretical predictions of model- indicative of a good degree of adhesion between the
ling, viz, rule of mixture (Eq. (3)): constituents of both PLATPU and PLMTPU blends
and subsequently denoted smaller extent of weakness
σb σb  in the blend structure [46]. Values of Porosity model α
=  − 1 × Φ d + 1, (3)
constant denotes further a lesser extent of stress con-
σ m σ m 
centration and positive values of B constant depicting
where σ is the tensile strength and subscripts b, m, and the load bearing capacity of the constituents of the
d signify the blend, continuous phase and discrete blends suggest negligible amount of aggregation and
phase respectively. excellent interactions at polymer–polymer interface.
Nicolais-Narki’s model (NN Model) (Eq. (4)) is
significant in that it defines the interface interaction Tensile Modulus values of both PLATPU and
constant k as a function of blend structure. For spher- PLMTPU blends were observed to decrease with
ical inclusions, k = 1.21 represents the extreme case of decrease in percent crystallinity of the blends. The
poor adhesion and interface adhesion increases decreasing trend in moduli values was attributed to the
through values of k < 1.21 to k = 0, considered for suf- dispersed phase acting as a flexibilizing agent facilitat-
ficient adhesion so that no decrease in polymer matrix ing nonspecific phase interaction with the continuous
strength is witnessed [44]. phase PLA. The relative modulus, E b /Em of the
blends were plotted against Φd values (Fig. 5). The
σb plots showed a decrease in relative moduli values with
= 1 − k Φd .
2/3
(4)
σm increasing Φd values, implying flexibility of the con-
In employing porosity model, (Eq. (5)), for theo- stituent TPU and decrease in crystallinity lead to sig-
retical predictions, stress concentration is described by nificant softening of the continuous phase, PLA.
the stress concentration parameter α, such that a high Variations of tensile modulus of the blends were
value of α signifies a higher extent of stress concentra- further, compared with various theoretical prediction

POLYMER SCIENCE, SERIES A Vol. 63 Suppl. 1 2021

 EFFECT OF COMPATIBILIZATION OF THERMOPLASTIC POLYURETHANE S53

Tensile strength, MPa Tensile strength, MPa

60
48 1
2
(a) 1 (b)
2
3 3
4 4
5 55 5
44
50

40 45

40
36
35
0.02 0.04 0.06 0.08 0.10 0.02 0.04 0.06 0.08 0.10
Φd Φd

Fig. 4. Variation of (1) tensile strength, (2) rule of mixture, (3) NN model, (4) porosity model, (5) BP model with different vol-
ume fraction of blends (a) PLATPU and (b) PLMTPU.

Tensile modulus, MPa Tensile modulus, MPa

(a) 1 (b) 1
3200 2 3200 2
3 3
4 4
5 5

3000 3000

2800 2800

2600 2600

0.02 0.04 0.06 0.08 0.10 0.02 0.04 0.06 0.08 0.10
Φd Φd

Fig. 5. Variation of (1) tensile modulus, (2) rule of mixture, (3) foam model, (4) KUT model-Adh, (5) KUT model-NonAdh with
different volume fraction of blends (a) PLATPU and (b) PLMTPU.

models so as to evaluate the blend structure. Rule of phase as a non-interacting phase equivalent to a void
mixture (Eq. (7)) considers perfect adhesion and per- or pore whereby, Ed /Em is rendered negligible [44].
fect dispersion of the spherical inclusions, dispersed
phase, in the continuous phase [47]. Eb
= [1 − Φ d ].
2/3
(8)
E b  Ed  Em
= × Φ d + 1, (7)
Em ( Em − 1) The Kerner–Uernura–Takayanagi (KUT) model
where Eb and Em are modulus value of blend system considers the blends as spherical inclusions of discrete
and PLA matrix respectively. Ed value corresponds to phase in a continuous matrix with Poisson’s ratio
the modulus value of ATPU and MTPU. (νm ) = 0.5 and with two boundary conditions of per-
On the other hand, Foam model (Eq. (8)), pro- fect adhesion at blend interface (Eq. (9)) and that of
posed by Cohen and Ishai, considers the dispersed no-adhesion (Eq. (10)) [48].

E b (7 − 5νm )Em − (8 − 10νm )Ed − (7 − 5νm )( Em − Ed )Φ d

= , (9)
Em (7 − 5νm )Em + (8 − 10νm )Ed + (8 − 10νm )( Em − Ed )Φ d

POLYMER SCIENCE, SERIES A Vol. 63 Suppl. 1 2021

S54 RAJESH et al.

8 8
10 (a) 10 (b)

εBlend/χBlend/εMatrix/χMatrix

εBlend/χBlend/εMatrix/χMatrix
1
2
8 8 6 6
εBlend/εMatrix

εBlend/εMatrix
1
6 2 6
4 4
4 4

2 2
2 2
0 0
0.02 0.04 0.06 0.08 0.10 0.02 0.04 0.06 0.08 0.10
Φd Φd

Fig. 6. Variation of (1) relative and (2) normalized elongation at break of blends (a) PLATPU and (b) PLMTPU.

Eb (7 − 5νm )Em − (7 − 5νm ) EmΦd

= . (10)
Em (7 − 5νm )Em + (8 − 10νm ) EmΦ d

Figure 5 represents the variations of tensile modu- ening and improved flexibility of the blend.The results
lus of blends to their prediction models. The initial suggest a positive interaction between the grafted
tensile modulus values of Φd = 0.03 for both PLATPU Acrylonitrile group of TPU with PLA matrix and leads
and PLMTPU follows the foam model, indicating that to a decrease in normalized elongation at break. The
the dispersed phases, compatibilized TPU, were act- effect of matrix softening and flexibility introduced by
ing as a non-interacting phase with the continuous the discrete phase (compatibilized TPU) analyzed
phase, PLA, viz. as a void or pore. However, for with the normalized elongation at break. Similarly, in
increasing Φd values, both blends are found to follow the case of PLMTPU, the decreased elongation with
KUT model for perfect adhesion between the blend increasing Φd values may be the result of positive inter-
components closely reaching for the rule of mixture, actions of the maleated TPU and PLA matrix. The
indicating an improvement in interaction and compat- results revealed a less effective matrix softening and
ibilization achieved. At Φd = 0.08, the modulus values flexibility by MTPU.
for PLATPU blend indicate the blend components Impact strength of PLATPU and PLMTPU blends
again following the foam model and thereby indicating and their percent increase are presented in Table 2.
a corresponding decline in the magnitude of positive The variance of relative notched impact strength of
interaction between the blend components whereas PLATPU and PLMTPU blends and normalized
the moduli values of PLMTPU indicate an enhanced impact strength denoting the enhancement of relative
adhesion mechanism for the moduli values follow the impact strength sans the effect of PLA matrix crystal-
rule mixture closely. linity, are shown in Fig. 7.
The variance of elongation at break for PLATPU The relative notched impact strength values of both
and PLMTPU blends were shown in Table 2. The PLATPU and PLMTPU blends are found to be higher
elongation at break values for both PLATPU and than that of the virgin matrix PLA. However, the
PLMTPU blends were found to be improved in com- increasing trend on relative impact strength were
parison to virgin PLA, as shown in Fig. 6. This is observed up to Φd value of 0.08 and then decrease for
attributed to the increased PLA amorphization and Φd of 0.10. This may be due to the combined effects of
flexibility introduced by the compatibilized TPU moi- matrix softening and flexibility imparted by the dis-
eties. crete phase and positive interactions between the com-
In the context of PLATPU, the values showed an patibilized moieties viz. Acrylonitrile grafts and male-
initial increase till Φ d = 0.05 and then decrease, sug- ate groups on TPU, with PLA matrix.
gesting the reason for improvement of elongation val- Similarly, the normalized impact strength values
ues from that of the matrix to be matrix softening, as showed no significant variation to a near linear trend
indicated by the decrease in corresponding moduli with the first significant decrease witnessed only for
values, whereas the variance in elongation with respect Φd of 0.10. This may be due to the enhanced ductility
to Φd values was attributed to the effect of matrix soft- of the blend. Even though under impact condition, the

POLYMER SCIENCE, SERIES A Vol. 63 Suppl. 1 2021

 EFFECT OF COMPATIBILIZATION OF THERMOPLASTIC POLYURETHANE S55

(a) (b)
4 4 4 4

IBlend/Blend/IMatrix/Matrix

IBlend/Blend/IMatrix/Matrix
1
2
3 1 3 3 3
IBlend/IMatrix

IBlend/IMatrix
2
2 2 2 2

1 1 1 1

0 0 0 0
0.02 0.04 0.06 0.08 0.10 0.02 0.04 0.06 0.08 0.10
d d

Fig. 7. Variation of (1) relative and (2) normalized impact strength of blends (a) PLATPU and (b) PLMTPU.

Fibrillation

(а) (b) (c)

(d) (e) (f)

Crazing

Fibrillation Crazing

(g) (h) (i)

Fig. 8. SEM images of (a) PLA, (b) 2.5PLATPU, (c) 5PLATPU, (d) 7.5PLATPU, and (e) 10PLATPU; (f) 2.5PLATPU,
(g) 5PLATPU, (h) 7.5PLATPU, and (i) 10PLATPU with magnification 100×.

percent crystallinity of the blend increases, the flexi- blends and it can be connected to its high impact
bility introduced by the TPU moieties increased the strength. Whitened regions in the blends can be con-
extent of shear yielding and also improved the cavita- nected with the partial miscibility of the blend compo-
tion owing to the high compatibilization effect. nents and it can be due to the yielding of TPU phase at
The impact fractured microstructures of PLA, the interface region which dissipates energy indicating
PLATPU, and PLMTPU blends were investigated by plastic deformation of PLA matrix with shear yielding
SEM. As shown in Fig. 8, PLA exhibits typical brittle [49]. It was also evident from the micrographs that dif-
fracture surfaces. Whereas, obvious toughening mech- ferent degrees of interfacial debonding led to the for-
anism initiated by crazing, fibrillation, and shear mation of voids, deforming the surrounding matrix
yielding can be seen in the PLATPU and PLMTPU (i.e. crazing). Crazing and fibrillation are more evi-

POLYMER SCIENCE, SERIES A Vol. 63 Suppl. 1 2021

S56 RAJESH et al.

dent in the blend system especially on the PLATPU 4. M. Allahdady, S. Hedjazi, M. Jonoobi, A. Abdulkhani,
blends [50]. Impact energy was dissipated by crazing and L. Jamalirad, Nord. Pulp Pap. Res. J. 34 (3), 239
wherein the fibrils absorbed energy until they ruptured (2019).
and this leads to improvement in the impact toughness 5. K. Oksman, M. Skrifvars, and J.-F. Selin, Compos. Sci.
of the blends [48]. The cross-section images showed Technol. 63(9), 1317 (2003).
more uniform distribution of two phases that may 6. A. Pappu, K. L. Pickering, and V. K. Thakur, Ind.
prove the high compatibilization. This is an effect of Crops Prod. 137, 260 (2019).
flexibilization of PLA imparted by TPU component, 7. B. Asaithambi, G. Ganesan, and S. A. Kumar, Fibers
and the effective stress transfer mechanism brought Polym. 15, 847 (2014).
forward by the compatibilization effect. 8. H. Kyutoku, N. Maeda, H. Sakamoto, H. Nishimura,
and K. Yamada, Carbohydr. Polym. 203, 95 (2019).
9. D. Vrsaljko, D. Macut, and V. Kovačević, J. Appl.
CONCLUSIONS Polym. Sci. 132 (6), 41414 (2015).
In this study, we reported for the first time blending 10. T.-W. Lee and Y. G. Jeong, Compos. Sci. Technol. 103,
of PLA with acrylonitrile and maleic anhydride 78 (2014).
grafted TPU. The PLA was successfully toughened 11. A. K. Mohapatra, S. Mohanty, and S. Nayak, Polym.
with very low volume fractions of ATPU and MTPU Compos. 35, 283 (2014).
via reactive melt blending technique. The modified 12. K. Pongtanayut, C. Thongpin, and O. Santawitee, En-
TPU acted as a flexibilizing agent and the grafted moi- ergy Procedia 34, 888 (2013).
eties effected positive interactions with PLA, resulting 13. N. Ljungberg, D. Colombini, and B. Wesslén, J. Appl.
in improved mechanical properties without adversely Polym. Sci. 96 (4), 992 (2005).
affecting any inherent properties. The PLATPU 14. F. Jing and M. A. Hillmyer, J. Am. Chem. Soc. 130
blends exhibited a maximum increase of 89% in (42), 13826 (2008).
15. L. Labrecque, R. Kumar, V. Dave, R. Gross, and
impact strength for Φ d = 0.08 composition, 266% S. McCarthy, J. Appl. Polym. Sci. 66 (8), 1507 (1997).
increase in elongation at break for Φ d = 0.05 and 18% 16. B. H. Li and M. C. Yang, Polym. Adv. Technol. 17 (6),
increase in tensile strength for Φ d = 0.03 , whereas, 439 (2006).
PLMTPU blends exhibited maximum increase of 28% 17. M. L. Robertson, K. Chang, W. M. Gramlich, and
in impact strength for Φ d = 0.08 , 311% increase in M. A. Hillmyer, Macromolecules 43 (4), 1807 (2010).
elongation at break and 35% increase in tensile 18. H. Li and M. A. Huneault, Polymer 48 (23), 6855
strength for Φ d = 0.03 compositions. Meanwhile it (2007).
was noted that the decrease in tensile modulus was in 19. X. Zhao, H. Hu, X. Wang, X. Yu, W. Zhou, and
tolerable limits in comparison to virgin PLA. Further S. Peng, RSC Adv. 10 (22), 13316 (2020).
the mechanical performance of blends was compared 20. X. Zheng, C. Zhang, C. Luo, G. Tian, L. Wang, and
with various theoretical models, so as to evaluate the Y. Li, Ind. Eng. Chem. Res. 55 (11), 2983 (2016).
extent of the effected compatibilization between PLA 21. S. K. Dogan, E. A. Reyes, S. Rastogi, and G. Ozkoc,
and TPU. The compatibilization of the blends was also J. Appl. Polym. Sci. 131 (10), 40251 (2014).
obvious with the decrease in the Tg, and improvement 22. H. Hong, J. Wei, Y. Yuan, F. P. Chen, J. Wang, X. Qu,
in the thermal stability. The interactions between the and C. S. Liu, J. Appl. Polym. Sci. 121 (2), 855 (2011).
grafted moieties and PLA were also confirmed by the 23. F. Feng and L. Ye, J. Appl. Polym. Sci. 119 (5), 2778
degree of crystallinity of the blends. The observations (2011).
were further substantiated by morphology analysis. 24. H. Hong, J. Wei, Y. Yuan, F. P. Chen, J. Wang, X. Qu,
The proposed blend system of PLA is proven by its and C. S. Liu, J. Appl. Polym. Sci. 121 (2), 855 (2011).
higher mechanical properties, thermal stability and 25. Y. Kahraman, B. Özdemir, V. Kılıç, Y. A. Goksu, and
flexibility and this allow its use in many fields espe- M. Nofar, J. Appl. Polym. Sci. 138 (20), 50457 (2021).
cially as a potential aspirant in 3D printing. 26. N. T. Kilic, B. N. Can, M. Kodal, and G. Özkoç, Prog.
Rubber, Plast. Recycl. Technol. 37 (4), 301 (2021).
27. X. Su, S. Jia, L. Cao, and D. Yu, J. Appl. Polym. Sci.
CONFLICT OF INTEREST 138 (3), 51014 (2021).
The authors declare that they have no conflict of interest. 28. S. M. Kang, M. S. Kang, S. H. Kwon, H. Park, and
B. K. Kim, J. Polym. Eng. 34 (6), 555 (2014).
29. T. Sehgal and S. Rattan, Int. J. Polym. Sci. 2010,
REFERENCES 147581 (2010).
30. E. Baştürk, S. Madakbaş, and M. V. Kahraman, Mater.
1. A. Lasprilla, G. Martinez, B. N. H. Lunelli, A. L. Jar- Res. 19, 434 (2016).
dini, and R. M. Filho, Biotechnol. Adv. 30, 321 (2012).
31. L. Xing, L. Liu, X. Wang, and Y. Huang, “Preparation
2. M. Bijarimi, S. Ahmad, and A. M. Alam, Polym. Bull. of Aramid/bn Reinforced Self-Healable Nanocompos-
74 (8), 3301 (2017). ites and Their Performance,” in Proceedings of 21st In-
3. K. Coskun, A. Mutlu, M. Dogan, and E. Bozacı, ternational Conference on Composite Materials, Xi’an,
J. Thermoplast. Compos. Mater. 34 (8), 1066 (2021). China, 2017 (Xi’an, 2017).

POLYMER SCIENCE, SERIES A Vol. 63 Suppl. 1 2021

 EFFECT OF COMPATIBILIZATION OF THERMOPLASTIC POLYURETHANE S57

32. A. De León, A. Domínguez-Calvo, and S. Molina, 41. N. T. Kilic, B. N. Can, M. Kodal, and G. Ozkoc, AIP
Mater. Des. 182, 108044 (2019). Conf. Proc. 1914, 070005 (2017).
33. J. Lisperguer, C. Nunez, and P. Perez-Guerrero, 42. Y. G. Devrim, Z. M. Rzaev, and E. Pişkin, Polym. Bull.
J. Chil. Chem. Soc. 58 (4), 1937 (2013). 59 (4), 447 (2007).
34. D. Stewart, Ind. Crops Prod. 27(2), 202 (2008). 43. N. F. Alias and H. Ismail, Polym.-Plast. Technol. Ma-
ter. 58 (13), 1399 (2019).
35. E. Ruiz-Silva, M. Rodríguez-Ortega, L. C. Rosales-
Rivera, F. J. Moscoso-Sánchez, D. Rodrigue, and 44. N. Tomar and S. Maiti, J. Appl. Polym. Sci. 104 (3),
R. González-Núñez, Polymers 13 (2), 217 (2021). 1807 (2007).
45. A. Kiss, E. Fekete, and B. Pukánszky, Compos. Sci.
36. Y. S. Lee and K. Ha, J. Elastomers Plast. 53 (5), 402 Technol. 67 (7-8), 1574 (2007).
(2021).
46. V. L. Finkenstadt, C.-K. Liu, R. Evangelista, L. Liu,
37. Y. S. Lee and K. R. Ha, World J. Text. Eng. Technol. 5, S. C. Cermak, M. Hojilla-Evangelista, and J. Willett,
77 (2019). Ind. Crops Prod. 26 (1), 36 (2007).
38. L. C. Arruda, M. Magaton, R. E. S. Bretas, and 47. J. H. Mina, A. V. González, and M. F. Muñoz-Vélez,
M. M. Ueki, Polym. Test. 43, 27 (2015). Polymers 12 (1), 58 (2020).
39. A. U. Birnin-Yauri, N. A. Ibrahim, N. Zainuddin, 48. M. Broz, D. L. VanderHart, and N. Washburn, Bioma-
K. Abdan, Y. Y. Then, and B. W. Chieng, Polymers 9 terials 24 (43), 4181 (2003).
(5), 165 (2017). 49. K. A. Afrifah and L. M. Matuana, Macromol. Mater.
40. Y. Zhou, L. Luo, W. Liu, G. Zeng, and Y. Chen, Adv. Eng. 295 (10), 802 (2010).
Mater. Sci. Eng. 2015, 393582 (2015). 50. F. Yu and H.-X. Huang, Polym. Test. 45, 107 (2015).

POLYMER SCIENCE, SERIES A Vol. 63 Suppl. 1 2021