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Polymer International

Polym Int 56 :1440–1447 (2007)

Preparation and characterization of thermoplastic starch/PLA blends by one-step reactive extrusion

Ning Wang, Jiugao Yu and Xiaofei Ma

School of Science, Tianjin Un iversity, Tianjin 300072, China

of Science, Tianjin Un iversity, Tianjin 300072, China Abstract: In the presence of dicumyl per oxide,

Abstract: In the presence of dicumyl per oxide, the compatibility of thermoplastic dry starch (DTPS)/poly(lactic acid) (PLA) blends, using maleic anhydride (MA) as compati bilizer, was investigated. The plasticization of starch and its compatibilizing modification with PLA was accomp lished in a single-screw extruder by one-step reactive extrusion. In the presence of MA, the plasticizatio n of starch in DTPS/PLA blends could be improved and homogeneous DTPS/PLA blends could be achieved as obse rved using scanning electron microscopy. Tensile tests showed that the tensile strength of compatibilized DTPS/PLA blends was about 40.5 MPa higher than that of the original composites. Differential the rmal analysis indicated that the glass transition temperature of DTPS and PLA became closer in the presence of MA than the blend without any additions, which suggested the compatibility between DTPS and PLA was improved. In addition, Fourier transform infrared spectroscopy proved that MA improved the interaction between DTPS and PLA. At the same time, the blend became more thermally stable as shown by thermogravimetric analysis results. A novel decomposition peak at about 450 C was detected in the compatibilized blend, which was higher than those observed for DTPS and PLA. Finally, a rheological study suggested that MA could improve the fluidity of DTPS/PLA blends. 2007 Society of Chemical Industry

Keywords: thermoplastic; starch; poly(lactic acid); one-step extrusion; compatibilizer

INTRODUCTION The improper disposition of petroleum-derived plas- tics leads to environmental pollution and has aroused much interest recently in preparing substitutes. 1 Poly(lactic acid) (PLA) is a promising thermoplastic polymer derived from agricultural resources through bioconversion and polymerization. Its stiffness, tensile strength and gas permeability are comparable to those of synthetic polymers from fossil fuels. 2,3 However, PLA is more expensive than conventional petroleum polymers for disposable or short-term applications and it degrades slowly in the environment over a period of several months to 2 years. 2 Starch of low price derives from abundant and readily available sources. What is more, the biodegradation rate of starch is rapid. 4 Also, its small granule structure makes it good as a particulate filler in polymer blend systems. 4,5 Efforts have been made to develop a biodegradable product from a fully renewable resource by blending starch with PLA. 612 The major problem with this blend system is the poor interfacial interaction between the hydrophilic starch granules and the hydrophobic PLA. So poly(hydroxyester ether) 6 and poly(vinyl alcohol) 7 have been used as the third component to enhance the compatibility between PLA and starch. Also, methylenediphenyl diisocyanate (MDI), 8 PLA- graft- (maleic anhydride), 9 PLA- graft-(acrylic acid) 10 and PLA- graft-starch, 11 which include reactive functional

groups, are widely used as effective compatibilizers to enhance the interfacial interaction of PLA/starch blends. Recently reactive extrusion has been studied widely to prepare starch/polymer blends. 1315 Com- pared to the chemical blending process, the important advantages of reactive extrusion are that it combines several chemical process operations into an extruder and no solvent is needed. In addition, gelatinization of starch is also a good method to enhance the interfacial affinity. 12,16 Starch is gelatinized in order to disinte- grate the granules and overcome the strong crystalline intramolecular forces prior mixing with other poly- mers. In the work reported in this paper, glycerol was used as the plasticizer for dry starch to avoid the depolymerization of hydrophobic PLA during melt processing. In order to enhance the properties of thermoplastic dry starch (DTPS)/PLA blends, low- toxicity maleic anhydride (MA) with dicumyl peroxide (DCP) initiator was used as a compatibilizer to enhance the compatibility between DTPS and PLA. In addition, one-step reactive extrusion 14,15 was used to prepare compatible DTPS/PLA blends.

MATERIALS AND METHODS Materials PLA was purchased from Natureworks LLC (USA). The general molecular weight was about

160 000–220 000. The concentration of the D-isomer was 12.0 ± 1.0%. Cornstarch (12% moisture) was obtained from Langfang Starch Company (Lang- fang, Heibei, China). Glycerol (analytical reagent) was purchased from Tianjin Chemical Reagent Fac- tory (Tianjin, China). MA, purchased from Tianjin Chemical Reagent Factory, was recrystallized twice with CHCl 3 before use. DCP, obtained from Shang- hai Chemical Reagent Co., China Pharmacy Group (Shanghai, China), was recrystallized from absolute alcohol before use.

Sample plasticization Starch was dried in an oven at 135 C for 2 h. Glycerol was used as plasticizer which was mixed (3000 rpm, 2 min) with dry starch using a GH-100Y high-speed mixer (Beijing, China). The mixtures were stored under airtight conditions until homogeneous systems were obtained. These systems were blended with PLA, MA and DCP using the high-speed mixer. Sample designations and components are listed in Table 1. DTPS/PLA blends were prepared as follows. The mixtures were fed into an SJ-25(s) single- screw plastic extruder (Beijing, China; screw diameter ( d ) = 30 mm, screw ratio L/D = 25:1, 15 g min 1 ). The screw speed was 10 rpm. The temperature profile along the extruder barrel was 130, 140, 150 and 130 C (from feed zone to die). The die had three round holes of 3 mm in diameter. The samples were stored under airtight conditions immediately. When the samples reached room temperature (about 20 C), the extruded strips were pressed into sheets with a flat sulfuration machine (Tianjin, China) and cut into tensile bars with certain size and stored in desiccator at room temperature immediately. Properties testing was undertaken after one week.

SEM analysis The microstructure of fracture surfaces of extruded DTPS/PLA strips were examined using s Philips XL- 3 SEM instrument (FEI Company, Hillsboro, OR, USA), operating at an acceleration voltage of 20 kV. The samples were cooled in liquid nitrogen, and then broken. The fracture surfaces were vacuum coated with gold for SEM analysis.

Table 1. Sample designations and rel evant sample components

 

PLA

Dried

Glycerol

MA a

DCP a

Sample

(wt%)

starch (wt%)

(wt%)

(wt%)

(wt%)

1

100

40

2

50

35.7

14.3

3

40

42.9

17.1

4

30

50.0

20.0

5

50

35.7

14.3

0.5

0.05

6

40

42.9

17.1

0.4

0.04

7

30

50.0

20.0

0.3

0.03

a The weight of MA and DCP was based on PLA.

Polym Int 56 :1440–1447 (2007) DOI: 10.1002/pi

Thermoplastic starch/PLA blends

Mechanical testing Samples were pressured with the flat sulfuration machine. A Testometric AX M350-10KN mate- rials testing machine (Testometric Company Ltd, Rochdale, UK) was used and a crosshead speed of 10 mm min 1 was used for tensile testing (ISO 1184–1983). The data were averages of 5–8 speci- mens.

Differential thermal analysis (DMA) DMA using a Mark Netzsch DMA242 analyzer (Bavaria, Germany) was performed on hot-pressed thick specimens (40 × 7 × 2 mm, prepared using the flat sulfuration machine, 5 MPa, 100 C), in a single cantilever bending mode at a frequency of 3.33 Hz and a strain of 2 N, corresponding to a maximum displacement amplitude of 30 µm. DMA compared the stress and strain signals and resolved the strain into the in-phase (storage) and out-of-phase (loss)

components, from which storage or elastic ( E ) and loss ( E ) moduli as well as tan δ = E /E were obtained

as a function of temperature. The range of temperature

was from 120 to 120 C. The standard heating rate used was 3.0 C min 1 . A drop in storage modulus and a peak in tan δ were used as indicators of a glass transition.

Fourier transform infrared (FTIR) spectroscopy FTIR spectra were measured using a BIO-RAD FTS3000 IR spectrum scanner (Hercules, USA). Extruded blend strips were pressured to transparent slices with a thickness of around 0.2 mm using the flat sulfuration machine.

Thermogravimetric analysis The thermal properties of the blends were measured with a ZTY-ZP type thermal analyzer (Beijing University Instrument Factory, Beijing, China). The sample weight varied from 10 to 15 mg. Samples were heated from room temperature to 500 C at

a heating rate of 15 C min 1 . Derivatives of TGA thermograms were obtained using Origin 7.0 analysis software (RockWare Inc., Golden, USA).

Rheology An XYL-II capillary rheometer (Jilin University

Instrument Factory, Jilin, China) was used to determine the viscosity of the blends. The capillary viscometer consists of a barrel into which material was loaded before being pushed by a plunger through

a capillary controlled by a surrounding heating unit.

The radius of the capillary was 1 mm and L/D = 40. The small pieces were placed into the barrel through

a funnel and then packed down with the plunger

until the first extrudate appeared at the capillary exit. The sample was allowed to come to temperature (10–15 min), and was then forced through the capillary by the plunger at pre-selected velocities. The load on the plunger and plunger speed provide the

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N Wang, JG Yu, XF Ma

total pressure drop through the barrel and capillary and the volume flow rate.

RESULTS AND DISCUSSION Blend morphology It is necessary to study the morphology of polymer blends since many properties depend on it, espe- cially the mechanical properties of immiscible blend systems. 17 As shown in Fig. 1, the fracture surface of sample 2 (Fig. 1(B)) was rugged compared to that of pure PLA (Fig. 1(A)). In addition, the average size of starch particles was about 10 µm in Fig. 1(B), whereas the native cornstarch particle was about 15 µm in diameter. 18 So most of the starch was obviously not plasticized and some of it was removed from the fracture surface leaving behind cavities (Fig. 1(B)). Nevertheless, the interface between DTPS and PLA was very clear. At the same time, by increasing the content of DTPS, the diameter of the starch phase increased (Fig. 1(C)). All of these are ascribed to the poor interfacial adhesion between DTPS and PLA. In the presence of MA and DCP, the dispersion between DTPS and PLA improved and the granules size of DTPS decreased dramatically (Figs 1(D) and (E)). Especially, in Fig. 1(D) the fracture surface of sample 5 turned into an evenly continuous phase. Even at a high content of DTPS, homogeneous DTPS/PLA blends still could be achieved. In addition, the fracture surface of the blends became smoother (Fig. 1(E)). The same phenomena had been found in linear low-density polyethylene (LDPE)/starch blends compatibilized with LDPE- graft-MA. 5 The better dispersion and compatibility between PLA and DTPS arise from the formation of branched and crosslinked macromolecules caused by reaction of the carboxyl groups of PLA- graft-MA with the hydroxyl groups of starch. Branched and crosslinked macromolecules contained different parts, each compatible with one

of the two copolymers. The maleation reaction mechanism has been reported in previous work. 19 This resulted in a reduction in interfacial tension during molten blending and a finer dispersion in the compatibilized blends. It had been reported that one- step reactive extrusion could dramatically improve the properties of LDPE/thermoplastic starch blends with MA and DCP as the initiator. 20 The maleation of LDPE, the plasticization of starch and blending could be simplified by one-step reactive extrusion.

Mechanical testing The mechanical properties of pure components showed typical brittle characteristics. The tensile strength and elongation at break of PLA and DTPS were 36.2 MPa and 3.0% and 38.3 MPa and 1.8%, respectively. The mechanical properties of DTPS/PLA blends, as well as these of the pure components were of rigid and fragile materials as shown in Fig. 2. After one-step extrusion of glycerol, dry starch and PLA together, the mechanical properties of DTPS/PLA blends were very poor, especially the

4.0 40 3.8 35 3.6 Sample 2-4 Elongation at break/% 3.4 Sample 5-7 Tensile strength/MPa
4.0
40
3.8
35
3.6
Sample 2-4
Elongation at break/%
3.4
Sample 5-7
Tensile strength/MPa
30
3.2
3.0
25
2.8
2.6
20
2.4
15
2.2
2.0
10
1.8
1.6
5
1.4
1.2
0
30
35
40
45
50
Elongation at break/%
Tensile strength/MPa

The content of PLA/wt%

Figure 2. Mechanical properties of DTPS/PLA blends for different ratios.

properties of DT PS/PLA blends for different ratios. Figure 1. SEM images of pure PLA and

Figure 1. SEM images of pure PLA and DTPS/PLA blends: (A) PLA ( × 2000); (B) sample 2 (× 2000); (C) sample 3 (×2000); (D) sample 5 (× 2000); (E) sample 6 (× 2000).

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Polym Int 56 :1440–1447 (2007) DOI: 10.1002/pi

tensile strength for samples 2–4. On increasing the content of DPTS, the mechanical properties worsened dramatically. This is ascribed to the poor interfacial adhesion between the two phases (as shown in Figs 1(B) and (C)). In addition, on increasing the content of DTPS, the increasing diameter of DTPS phase in DTPS/PLA blend deteriorated the continuous phase of the blends. In the presence of MA and DCP, the mechanical properties of DTPS/PLA blends improved markedly. The maximum tensile strength and elongation at break of sample 5 were 40.5 MPa and 3.5%, respectively. Even on increasing the content of DTPS, the mechanical properties of the blends did not worsen dramatically. It was evident that the mechanical properties of immiscible DTPS/PLA blends depended strongly on the compatibility and the diameter of the starch phase.

DMA study The DMA data, i.e. the storage modulus ( E ) and the loss factor (tan δ), for pure PLA, sample 1, sample 2 and sample 5 are shown in Figs 3 and 4, respectively. E is an important parameter for rigid materials. The values of E of PLA, sample 1, sample 2 and sample 5 could be ranged in the order sample 1 > sample 2 > sample 5 > PLA. This might be ascribed to the plasticization of dry starch. It is known that after excluding water, the polysaccharide chain mobility and orientation were limited, 21 which deteriorated the plasticization of starch. So most residual starch granules embedded in an entangled matrix consisting of amylose and amylopectin might increase the stiffness of the DTPS by physical crosslinks. After blending with PLA, the disintegration of rigid starch granules could be accelerated in DTPS/PLA blends (as shown in Figs 1(B) and (C)). In the presence of MA the plasticization of dry starch could be improved as shown in Fig. 1(D). In mechanical and dielectric relaxation studies of amorphous polymers, the observation of two thermal transitions in a single-phase material is usually assigned

8.8 8.6 8.4 8.2 8.0 7.8 7.6 PLA Sample 1 7.4 Sample 2 Sample 5
8.8
8.6
8.4
8.2
8.0
7.8
7.6
PLA
Sample 1
7.4
Sample 2
Sample 5
7.2
7.0
-150
-100
-50
0
50
100
150
log Storage Modulous (MPa)

Temperature (°C)

Figure 3. Storage modulus versus temperature of PLA, sample 1 and DTPS/PLA blends.

Polym Int 56 :1440–1447 (2007) DOI: 10.1002/pi

Thermoplastic starch/PLA blends

5.0 PLA 4.8 Sample 1 4.6 Sample 2 Sample 5 4.4 4.2 4.0 3.8 3.6
5.0
PLA
4.8
Sample 1
4.6
Sample 2
Sample 5
4.4
4.2
4.0
3.8
3.6
3.4
3.2
3.0
-150
-100
-50
0
50
100
150
log(tan delta)

Temperature (°C)

Figure 4. Tan δ versus temperature of PLA, sample 1 and DTPS/PLA blends.

to primary α-relaxation process associated with the upper transition temperature ( T g u ) and a lower

transition temperature ( T g l ) associated with relatively localized molecular motions. Compared with T g u of

the correlated T g l at about 45.6 C was very

PLA,

small (as shown in Fig. 4) which could be ascribed to the poor mobility of relatively localized molecular of PLA. Two glass transitions were detected in thermoplastic starch materials which were recognized to be phase-separated. 22 T g u is related to the glass transition temperature in starch/water mixtures, and T g l is due to glycerol mixed with a small quantity of polymeric material. So, only T g l of sample 1 can be seen in Fig. 4 after excluding water from the thermoplastic starch system. In the presence of PLA, T g u of DTPS also could not be detected in samples 2 and 5 (Fig. 4). These transition temperatures are summarized in Table 2; T g l of DTPS shifted to high temperature accompanying the T g u of PLA shifting to low temperature in the presence of MA and DCP. This suggests that MA could enhance the compatibility between DTPS and PLA.

FTIR spectroscopy The interaction of polymer blends can be investigated using FTIR spectra. If two polymers form completely immiscible blends, there are no appreciable changes in the FTIR spectra of the blends with respect to the co-addition of each component. 23 However, if two polymers are compatible, a distinct chemical inter- action (a hydrogen bonding or dipolar interaction) exists between the chains of one polymer and those of the other, causing the FTIR spectra of the blends to

Table 2. The glass transition temperatures of PLA and DTPS

Sample

T g u (PLA) ( C)

T g l (DTPS) ( C)

PLA

65.5

Sample 2

65.5

43.9

Sample 5

57.8

40.2

Sample 1

49.6

1443

N Wang, JG Yu, XF Ma

change (e.g. band shifts and broadening). 24 As a result, FTIR spectra can be used identify segment interac- tions and to provide information about the phase behavior of polymer blends. Figure 5 shows the FTIR spectra of pure PLA, dry starch, sample 1, sample 2 and sample 5 in specific stretching regions. The peak band wavenumbers related to hydrogen bonding of PLA, DTPS/PLA blends and starch are listed in Table 3. When dry starch was plasticized by glycerol, the characteristic peaks of starch (the –C–O–bond stretching of –C–O–H group at about 1156 and 1081 cm 1 and the –C–O–bond stretching of –C–O–C–group in the anhydroglucode ring at about 1020 cm 1 ) 25 shifted to low wavenumber and split up into two peaks. This is ascribed to both C–O–H and C–O–C groups in starch forming hydrogen bond interactions with glycerol, which decreased the stretching vibration wavenumbers. It is well known that PLA has a strong car- bonyl stretching absorption at about 1749 cm 1 . With the addition of DTPS, this peak shifted to a lower wavenumber. When this blend was com- patibilized with MA, this peak was shifted to 1745 cm 1 . This means that carbonyl groups also take part in the interaction between PLA and DTPS, resulting in the blue shift of the –C=O vibra- tion of PLA. The same phenomenon was found for –C–O–in –CH–O–(1182 cm 1 ) and –C–O–in

C B A PLA Sample 2 Sample 5 Sample 1 1182 1044 1749 1127 1082
C
B
A
PLA
Sample 2
Sample 5
Sample 1
1182
1044
1749
1127
1082
Starch
1156
1020 1081
800
1000
1200
1400
1600
1800
2000

Wavenumber (cm -1 )

Figure 5. FTIR spectra of PLA, DTPS and DTPS/PLA blends.

–O–C=O (1127, 1082, 1044 cm 1 ) of PLA in DTPS/PLA blends on increasing the dispersion and compatibility between DTPS and PLA.

TGA study TGA was performed for pure PLA, starch, sample 1 and DTPS/PLA blends. The weight loss due to the volatilization of the plasticizers and the degradation products was monitored as a function of temperature, as shown in Fig. 6. T 5% , which is the temperature corresponding to 5% weight loss determined from Fig. 6 is summarized in Table 4. After plasticization with glycerol, T 5% of starch increased dramatically due to the strong interaction between polysaccharide and glycerol. Compared with sample 1, PLA is a thermally stable polymer. T 5% of DTPS/PLA increased by about 31 C compared with DTPS; hence the addition of MA had little influence on the T 5% of DTPS/PLA blends. From Fig. 7, the T max values of pure PLA, starch, sample 1 and DTPS/PLA blends were determined (derivative thermogravimetry, DTG), which are also summarized in Table 4. Here T max is the temperature at the maximum rate of weight loss, that is, the decomposition temperature. T max of DTPS decreased by about 20 C compared with starch, which is ascribed to the disintegration of starch molecules during plasticization at high temperature and shear. After blending with PLA, T max of DTPS in sample 2 decreased compared with sample 1.

0.8 PLA 0.4 0.0 0.8 Sample 2 0.4 0.0 0.8 Sample 5 0.4 0.0 0.8
0.8
PLA
0.4
0.0
0.8
Sample 2
0.4
0.0
0.8
Sample 5
0.4
0.0
0.8
Sample 1
0.4
0.0
0.8
Starch
0.4
0.0
0
100
200
300
400
500
600
Weight Loss (%)

Temperature (°C)

Figure 6. TGA curves for PLA, sample 1, starch and DTPS/PLA blends.

Table 3. The wavenumber related to the hydrogen bonds in FTIR spectra and the change of the force constant f

Vibration wavenumber (cm 1 )

Sample

–C–O of –C–O–H in starch

–C–O of –C–O–C– in starch

Dried starch

1156

1081

1020

Sample 1

1150

1078

1017

994

Blends

–C=O (carbonyl)

–C–O– in –CH–O–

–C–O– in –O–C=O 1127, 1082, 1044 1127, 1080, 1044 1125, 1078, 1042

PLA

1749

1182

Sample 2

1747

1180

Sample 5

1745

1178

Thermoplastic starch/PLA blends

Table 4. Thermogravimetric parameters of PLA , starch, sample1 and DTPS/PLA blends

DTPS

PLA

Sample

T 5% ( C)

DTPS, T max ( C)

PLA, T max ( C)

Slope

E t (kJ mol 1 )

Slope

E t (kJ mol 1 )

PLA

335

397

0.0411

156.6

Sample 2

167

324

393

0.0104

38.8

0.0366

134.6

Sample 5

172

331

391

0.0195

59.2

0.0379

139.3

Sample 1

136

330

0.0109

33.0

Cornstarch

68

349

0.0402

129.3

-1.2 PLA -1.8 -2.4 -3.0 -1.2 Sample 2 -1.8 -2.4 -3.0 -1.4 Sample 5 -2.1
-1.2
PLA
-1.8
-2.4
-3.0
-1.2
Sample 2
-1.8
-2.4
-3.0
-1.4
Sample 5
-2.1
-2.8
-0.7
-1.4
Starch
-2.1
-2.8
-0.7
-1.4
Sample 1
-2.1
-2.8
0
100
200
300
400
500
600
DTG

Temperature (°C)

Figure 7. DTG curves for PLA, sample 1, starch and DTPS/PLA blends.

But T max of DTPS in sample 5 remained nearly the same compared with sample 1. At the same time, T max of PLA in sample 5 shifted to lower temperature. The closeness of these two T max values might be ascribed to the increasing compatibilization between DTPS and PLA. In addition, a new decomposition temperature was detected in DTG at about 459 C in sample 5, which was not found in pure PLA, starch or DTPS/PLA blends without any addition. This suggests that branched and crosslinked macromolecules were formed during the one-step reactive extrusion. The activation energy of decomposition, E t , of the polymer could be calculated from the TGA curves by the integral method proposed by Horowitz and Metzger 26 using the following equation:

ln[ln(1 α) 1 ] = E t θ/RT

2

max

(1)

where α is the decomposed fraction, T is the temperature, θ is T T max and R is the gas constant. From the plots of ln[ln(1 α) 1 ] versus θ , which are shown in Fig. 8, E t could be determined (from the slopes of the straight lines). As demonstrated in Table 4, the E t values of starch decreased dramatically after processing. The addition MA could increase the thermal stability of DTPS in DTPS/PLA blends. E t of DTPS in sample 5 was 59.2 kJ mol 1 , whereas E t of DTPS in sample 2 was only 38.8 kJ mol 1 . However, the influence of MA on E t of PLA was not evident.

Polym Int 56 :1440–1447 (2007) DOI: 10.1002/pi

0.8 PLA 0.4 y=0.2336+0.04111x 0.0 -0.9 DTPS in Sample 2 y=-1.1572+0.0104x -1.2 0.6 PLA in
0.8
PLA
0.4
y=0.2336+0.04111x
0.0
-0.9
DTPS in Sample 2
y=-1.1572+0.0104x
-1.2
0.6
PLA in Sample 2
0.3
y=0.2059+0.03659x
0.0
-0.9
DTPS in Sample 5
y=-1.1346+0.0195x
-1.2
0.6
PLA in Sample 5
0.3
y=0.2564+0.0379x
0.0
Sample 1
-1.0
y=-1.1035+0.0109x
-1.2
-0.6
Starch
-1.2
-1.8
y=-1.4988+0.0402
-10
-5
0
5
10
15
ln[ln(1-α -1 )]

theta (K)

Figure 8. Plots of ln[ln(1 α) 1 )] versus θ for the determination of E t . The straight line is the linear fit of the data points.

Rheology In order to understand the DTPS/PLA processing properties, rheology experiments were carried at 130, 140 and 150 C, which covered the processing temperature range. Shear rate (γ ), shear stress (τ ) and apparent viscosity (η) were calculated by standard methods, which are reported in our previous work. 18 The η γ curves were plotted using a double logarithmic scale (Fig. 9). With increasing shear stress, the viscosity of each blend decreased. Such flow behavior is called shear thinning. At the same time, according to the linear fit equations in Fig. 9, the pure material and blends were more prone to flow with increasing temperature. The flow index n, K and viscous flow activation energy ( E η ) of PLA, sample 1 and DTPS/PLA blends at 130, 140 and 150 C are listed in Table 5. According to our previous work, 18

the linear fit equations are listed in Fig. 9. The slope of the linear fit equation is (1 n) and the intercept is log K . As shown in Table 5, the flow index of PLA is larger than that of sample 1. This is ascribed to the poor fluidity of sample 1. So sample 1 hardly dispersed well in more fluid PLA, which can be seen from Fig. 1(C). When MA was used as the compatibilizer, the flow index n of sample 5 increased which is similar to pure PLA. It is suggested that MA could accelerate the fluidity of sample 1 and increase the dispersion between DTPS and PLA (Fig. 1(E)). In addition, it is well known that the higher the E η value, the more sensitive are the blends to temperature. According

1445

N Wang, JG Yu, XF Ma

Table 5. The flow index n and vicious flow activation energy E η (x = 0) of PLA, sample 1 and DTPS/PLA blends at 130, 140 and 150 C

Sample

PLA

Sample 1

Sample 2

Sample 5

130 C

n

0.49

0.27

0.43

0.50

K

10 2329

3 754 049

56 872

52 735

140 C

n

0.52

0.35

0.50

0.52

K

58 884

1 625 548

23 442

15 852

150 C

n

0.55

0.36

0.52

0.55

K

34 673

838 687

13 375

13 807

E η ( x = 0) (kJ mol 1 )

75.40

106.36

100.25

85.18

5.2 PLA 5.0 4.8 4.6 4.4 4.2 130°C Y = 5.0055-0.5072x 140°C Y = 4.7731-0.4771x
5.2
PLA
5.0
4.8
4.6
4.4
4.2
130°C Y = 5.0055-0.5072x
140°C Y = 4.7731-0.4771x
150°C Y = 4.5437-0.4520x
4.0
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
log η

log γ ω

6.6 Sample 1 6.4 6.2 6.0 5.8 5.6 150°C Y = 5.9236-0.63894x 5.4 140°C Y
6.6
Sample 1
6.4
6.2
6.0
5.8
5.6
150°C Y = 5.9236-0.63894x
5.4
140°C Y = 6.2110-0.6511x
130°C Y = 6.5745-0.7278x
5.2
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
log η

log γ ω

Figure 9. Rheology curves of PLA, sample 1 and DTPS/PLA blends at 130, 140 and 150 C.

to the values of E η ( x = 0) in Table 5, PLA and sample 5 were less sensitive to processing temperature. Therefore, during the thermoplastic processing, the extruder screw speed could effectively adjust the flow behavior of the blends.

CONCLUSIONS The physical properties and compatibility of DTPS/ PLA blends dramatically improved in the presence of MA during one-step reactive extrusion processing. At the same time, MA could also improve the plasticization of dry starch and processing fluidity of DTPS/PLA during one-step extrusion. Hence, the tensile strength of DTPS/PLA blends could be

1446

5.2 Sample 2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 130°C Y = 4.7549-0.5667x
5.2
Sample 2
5.0
4.8
4.6
4.4
4.2
4.0
3.8
3.6
130°C Y = 4.7549-0.5667x
140°C Y = 4.3716-0.4978x
3.4
150°C Y = 4.1263-0.4813x
3.2
-0.6 -0.4 -0.2 0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
log η

log γ ω

5.0 Sample 5 4.8 4.6 4.4 4.2 4.0 3.8 130°C Y = 4.7221-0.4972x 3.6 140°C
5.0
Sample 5
4.8
4.6
4.4
4.2
4.0
3.8
130°C Y = 4.7221-0.4972x
3.6
140°C Y = 4.4758-0.4767x
150°C Y = 4.2001-0.4524x
3.4
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
log η

Figure 9. Continued.

log γ ω

improved accompanied by homogeneous DTPS/PLA blends being achieved. One-step reactive extrusion is a novel and promising way to prepare starch- based plastic materials. After blending with DTPS, the flexibility of DTPS/PLA still was very poor in the work reported here. This work is to be continued.

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