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Bioresource Technology 100 (2009) 1246–1251

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

A plant fiber reinforced polymer composite prepared by a twin-screw extruder

G. Sui a,b, M.A. Fuqua a, C.A. Ulven a, W.H. Zhong a,*
Department of Mechanical Engineering and Applied Mechanics, North Dakota State University, Fargo, ND 58105, USA
The Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China

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

Article history: Polypropylene (PP) composites reinforced using a novel plant fiber, sunflower hull sanding dust (SHSD),
Received 2 March 2007 were prepared using a twin-screw extruder. Thermal and mechanical properties of the SHSD/PP compos-
Received in revised form 6 March 2008 ites were characterized and compared to an organically modified clay (organo-clay)/PP composite. Differ-
Accepted 6 March 2008
ential scanning calorimetry (DSC) analysis showed that the crystallization temperature and the degree of
Available online 7 October 2008
crystallinity of PP exhibited changes with addition of SHSD and organo-clay. Mechanical properties of the
PP were enhanced with the addition of SHSDs. Both the flexural strength and flexural modulus of the PP
composites containing 5% (w/w) SHSD were comparable to that of the 5% (w/w) organo-clay reinforced
PP. Scanning electron microscope (SEM) observation showed that no obvious agglomeration of SHSD
Crystallization existed in the PP matrix. Compared to the neat PP and organo-clay/PP, the SHSD/PP composites exhibited
Flexural properties a relatively decreasing rate of thermal degradation with increase in temperature. Experimental results
suggest that SHSD, as a sunflower processing byproduct, may find promising applications in composite
Ó 2008 Published by Elsevier Ltd.

1. Introduction (Modesti et al., 2005; Yang et al., 2006; Fang et al., 2006; Zhao
et al., 2006; Zhuang et al., 2007). After extensive exploratory exper-
Polymer reinforced composites have demonstrated a marked iments, the optimal processing parameters for extruding SHSD/PP
improvement in the physical properties of polymeric materials. composites were obtained. The effects of SHSD on the crystalliza-
With low fiber yields, nanocomposites can be both efficient and tion, mechanical and thermal properties of the PP matrix were
economical materials that hold promise for broad application. Nat- studied. To analyze the blending and bonding potential of the
ural fillers, such as clay, silica, calcium carbonate, hemp fiber and unprocessed SHSD on the polymer matrix, the fiber surface did
wood fiber have already been demonstrated to yield many desir- not undergo any chemical treatments. Compared to neat PP and
able properties when utilized as reinforcement agents in polymer organo-clay reinforced PP composites, the resulting SHSD/PP com-
composites (Bledzki et al., 2005; Zuiderduin et al., 2003; Ray posites exhibited optimal comprehensive properties.
et al., 2006; Karmarkar et al., 2007; Pickering et al., 2007;
Vladimirov et al., 2006). By further exploring the potential use of 2. Methods
recycled and waste byproducts, exploration of new natural fibers
such as sunflower hull fibers has become an important approach 2.1. Materials
to resolving resource shortages and environmental pollution issues
(Rouilly et al., 2006). PP with a density of 0.91 kg/m3 was supplied by Formosa Plas-
In order to take full advantage of the natural agricultural pro- tics Corporaftion (Point Comfort, TX, USA) under the trade name of
cessing byproduct, a new plant fiber – sunflower hull sanding dust Formolene 5100H. SHSD were obtained from Red River Commodi-
(SHSD) was comminuted and compounded in a polypropylene (PP) ties, Inc. (Fargo, ND, USA). An organo-clay, Cloisite 15A, which is
matrix using a micro-18 mm twin-screw extruder in this work. montmorillonite modified with a dimethyl, dehydrogenated tallow
Twin-screw extrusion has been demonstrated to be an effective quaternary ammonium ion, was purchased from Southern Clay
melt blending process for producing thermoplastic composites, be- Products (Gonzales, TX, USA).
cause the process provides uniform, high shear compounding. This
results in parts which have higher mechanical properties than
2.2. Preparation of the PP composites
those compounded in a two-roll mill or a high-speed mixer

The SHSD and Cloisite 15A were dried at 100 °C for 24 h in a

* Corresponding author. Tel.: +1 (701) 231 7139; fax: +1 (701) 231 8913. vacuum oven to remove moisture prior to use. The SHSD and clay
E-mail address: Katie.Zhong@ndsu.edu (W.H. Zhong). loading of all specimens was set at 5% (w/w). Both the SHSD/PP and

0960-8524/$ - see front matter Ó 2008 Published by Elsevier Ltd.

G. Sui et al. / Bioresource Technology 100 (2009) 1246–1251 1247

clay/PP composites were melt-compounded in a co-rotating twin-

screw extruder (Leistritz Micro-18/GL-40D). The screw rotation
speed was set at 75 rpm, and the temperature profile of barrel sec-
tions from hopper to die was as follows: 182, 188, 193, 199, 204,
210, 210, and 210 °C. The extruded PP and composites were pellet-

ized and then compression molded at 200 °C to obtain test speci-
mens with 3 mm thickness. 8
67 9
3 45
2.3. Characterizations of the materials
Fourier transform infrared spectroscopy (FT-IR) analyses of
SHSD specimens were conducted in a 2000 FT-IR spectrometer
manufactured by Pekin–Elmer (Waltham, MA, USA). SHSD speci-
mens were prepared by mixing a small amount of SHSD with KBr
4000 3500 3000 2500 2000 1500 1000 500
then cold pressed to form discs. The morphology of the fracture
Wavenumber (cm-1)
interface of the neat PP and composite specimens was observed
using a JSM-6300 scanning electron microscope (SEM), manufac- Fig. 1. FT-IR spectrum of SHSD (the band numbers correspond to those shown in
tured by JEOL (Tokyo, Japan). Differential scanning calorimetry Table 1.).
(DSC) analysis was performed using a Q1000 DSC manufactured
by TA Instruments (New Castle, DE, USA) in a nitrogen atmosphere. to the functional groups of the fibers obtained from FT-IR spectrum
In the non-isothermal experiments the specimens were heated at a are listed in Table 1. It is clear that functional groups such as hy-
rate of 10 °C/min from room temperature to 250 °C to eliminate droxyl, carbonyl, and amino groups exist in SHSDs, which may re-
any previous thermal history and then cooled down to ÿ40 °C at sult in interaction between the SHSDs and polymers.
a rate of 10 °C/min. Subsequently the specimens were again heated Images of the SHSD’s microstructure demonstrate that the sun-
to 250 °C at a rate of 10 °C/min. The dynamic mechanical property flower hulls consist of micron-scale fibers and fragments, as shown
of the neat PP and the composites was analyzed using a Dynamic in Fig. 2a. In a higher resolution image (Fig. 2b), many grooves on
Mechanical Analyzer (DMA) (TA Instruments, model 2980) in dual the surface of the SHSDs were observed, which can improve the
cantilever beam mode at a frequency of 1 Hz. The specimens were specific surface area of the fibers and facilitate adhesion with a
heated from room temperature to 200 °C at a heating rate of 5 °C/ polymer matrix.
min. The thermal stability of specimens was tested using Thermo-
gravimetric Analysis (TGA) (TA Instruments, model 2960) from 3.2. DSC analyses
room temperature to 600 °C at a heating rate of 20 °C/min under
nitrogen purge. Each sample of the above instrumental analysis The crystallization and melting patterns of the PP and PP com-
was tested in duplicate to validate the repeatability of experimen- posites were obtained during the cooling and heating processes of
tal results. non-isothermal DSC measurements. From the DSC thermogram of
Flexural analysis was performed through three-point bend test- the cooling process (Fig. 3a), the Tp (peak temperature of crystalli-
ing as specified in Procedure A of ASTM D790, using a load frame zation), Tc (temperature at the intercept of the tangent at the base-
manufactured by MTS Systems Corporation (Minneapolis, MN, line and the high temperature side of the exotherm peak) and DW
USA). The speed of the cross-head was 1 mm/min. Five specimens (width at half-height of the exotherm peak) were obtained and are
were measured for each sample. The mean value and standard devi- listed in Table 2. The cooling process shows an increase in the crys-
ation of flexural stress and flexural modulus was calculated for each tallization temperature of PP with the addition of fillers, which is
sample set. Flexural stress was calculated from Eq. (1) (ASTM D790): suspected to be the result of the fibers being effectively dispersed
3PL throughout the PP matrix, promoting heterogeneous nucleation.
rf ¼ 2
ð1Þ Meanwhile, the values of TC ÿ TP show a decrease for the SHSD
composites when compared to neat PP, indicating that the crystal-
where P is the peak load applied, L is the length of span, b and d are lization rate of the PP matrix was increased with the addition of the
the width and thickness of the specimens, respectively. sunflower hull fibers. The width at half-height of the exotherm
Flexural modulus was calculated from Eq. (2) (ASTM D790): peak, DW, also shows a slight decrease, signifying that the crystal-
L3 m lite size distribution in the SHSD reinforced PP composites is nar-
Ef ¼ 3
ð2Þ rower than that of neat PP.
A DSC thermogram of the second heating process is shown in
where m is the slope of the tangent to the initial straight-line por- Fig. 3b. From this, the peak temperature of crystallization melting
tion of the load–deflection curve.
Thermal conductivity of the samples was measured using a Table 1
Characteristic functional groups of SHSD in FT-IR spectrum
Mathis TC-30 Thermal Conductivity Instrument at room tempera-
ture. Ten specimens were measured for each sample. The mean va- Wave number (cmÿ1) Characteristic group
lue and standard deviation of thermal conductivity and thermal 1 3410 –O–H
effusivity was calculated for each sample set. 2 2911 –C–H
3 1743 –C@O
4 1655 –C@O, –C@C
5 1614 –N–H, –C@C
3. Results and discussion 6 1520 –N–H
7 1425 –CH2
3.1. Structural characteristics of the SHSD 8 1330 –CH3
9 1246 –CH2
10 1056 –C–O
Structural characteristics of the SHSD were analyzed using FT-IR
11 653 –C@C
spectrum analysis, shown in Fig. 1. The characteristic peaks related
1248 G. Sui et al. / Bioresource Technology 100 (2009) 1246–1251


Exothermal Heat Flow


Neat PP

0 50 100 150 200 250

Temperature (°C)
(a) Cooling process

Neat PP

Exothermal Heat Flow SHSD/PP


50 100 150 200 250

Temperature (°C)
(b) Heating process
Fig. 2. The microstructure of SHSDs.
Fig. 3. DSC curves of the neat PP and PP composites.

(Tm) and melting heat of crystallization (DHm) were obtained

Table 2
(Table 3). Using this information, the degree of supercooling (the Non-isothermal crystallization parameters in cooling process of neat PP and PP
difference in the melting peak temperature and crystallization composites
peak temperature) was then obtained. The degree of crystallinity
Specimen TP (°C) TC (°C) TC ÿ TP (°C) DW (°C)
of specimens was calculated from the melting heat of crystalliza-
tion according to the following equation: Neat PP 108.07 115.14 7.07 8.2
SHSD/PP 117.44 118.67 1.23 7.1
X c ¼ DHm =DH0 ð3Þ Organo-clay/PP 114.47 117.96 3.49 7.5

where DH0 = 207.1 J/g is the melting heat of 100% crystalline PP

(Wunderlich, 1990).
There was no marked change seen for the peak temperature of Table 3
Non-isothermal crystallization parameters in heating process of neat PP and PP
crystallization among these different specimens. The degree of composites
supercooling required for the crystallization of PP was reduced
with the presence of the fillers, which is found to be consistent Specimen Tm (°C) Tm ÿ TP (°C) DHm (J/g) Xc (%)

with previously reported analysis (Li et al., 2003). As the 5% (w/ Neat PP 165.39 57.32 87.46 42.23
w) fillers were added to the PP matrix, the fillers were found to ob- SHSD/PP 163.66 46.22 75.04 36.23
Organo-clay/PP 165.47 51.00 63.52 30.67
struct the mobilization of the PP macromolecular chain and pre-
vent the macromolecular segment from obtaining ordered
alignment of the crystal lattice. Thus, the degree of crystallinity
of the specimens decreased accordingly, although this phenome- 3.3. Mechanical properties
non was observed to a greater extent with the organo-clay com-
posite compared to the SHSD composites. It is speculated that Results of three-point bend testing of the neat PP and PP com-
not only the fillers themselves, but the crystalline structures will posites are shown in Table 4. It can be observed that the SHSD pro-
also affect the mechanical properties. vides a significant reinforcing effect to the PP matrix, one which is
G. Sui et al. / Bioresource Technology 100 (2009) 1246–1251 1249

Table 4 rials. Wider series of studies on the SHSD reinforced polymer com-
Flexural properties of neat PP and PP composites posites need to be conducted.
rf /MPa (increase percentage Ef/GPa (increase percentage The fracture surface morphology of the PP, SHSD/PP and org-
versus neat PP) versus neat PP) ano-clay/PP composites after the three-point bending tests are
Neat PP 40.7 ± 0.7 (0%) 1.39 ± 0.12 (0%) shown in Fig. 4. Compared to the characteristic features of neat
SHSD/PP 51.5 ± 2.1 (27%) 1.57 ± 0.09 (13%) PP material, more definitive plastic deformation was observed in
Organo- 49.4 ± 3.9 (21%) 1.51 ± 0.07 (9%) the fracture morphology of the PP composites. The reason for this
phenomenon is speculated to be the strong reinforcing effect of the
fibers in the polymer, as well as higher amorphous portions of the
PP inside the composites, which allowed increased deformation
beyond the elastic behavior. At the same time, no obvious agglom-
comparable to the effect of organo-clay loading. After the addition erations of the fillers were found in the composites, indicating that
of the fillers, the flexural strength and modulus of the PP compos- blending by means of the twin-screw extruder was an effective
ites were noticeably improved. Enhancements of 27% and 13% in method for dispersing the SHSD fillers uniformly in the PP matrix.
flexural strength and flexural modulus for the PP matrix, respec-
tively, were obtained after adding 5% (w/w) SHSD. This was found 3.4. Dynamic mechanical properties
to be equivalent to the enhancements gained from composites con-
taining 5% (w/w) organo-clay (Table 4). It is known that the raw The effects of the SHSDs and the organo-clay on the dynamic
clay is inexpensive. However, organo treatment to clay is needed mechanical properties of the PP material were also examined.
in order to achieve a reinforced effect in polymer composites, The storage modulus ðE0 Þ of the neat PP and PP composites as func-
which results in increased cost. Therefore, the enhancements in tions of temperature are shown in Fig. 5. Although the storage
flexural strength and modulus obtained with the SHSDs in this modulus of all the specimens manifested declining trends with
study implied that SHSDs as an agricultural processing byproduct increasing temperature, it is apparent that E0 of the PP composites
are very promising to be used as reinforcement for polymer mate- increases above room temperature due to the additions of the

Fig. 4. Fracture morphology of the neat PP and PP composites after three-point bending tests.
1250 G. Sui et al. / Bioresource Technology 100 (2009) 1246–1251

1.5 3.5. Thermal conductivity and stability

The thermal conductivity properties of the PP and the PP com-

posites were measured and shown in Table 5. Because the SHSDs
Storage Modulus (GPa)

and organo-clay are heat insulators, the addition of these fillers re-
1.0 sulted in a decrease of the thermal conductivity and thermal effu-
sivity of the PP matrix. This demonstrates that the SHSD holds
potential as a filler to yield polymers for heat insulation
The thermal stability of the composites was studied by TGA.
0.5 TGA curves of the neat PP and PP composites are shown in
Fig. 6. By comparing the weight loss as a function of tempera-
ture, the effects of the two kinds of fillers, SHSD and organo-clay,
Neat PP
SHSD/PP on the thermal stability of the PP material were analyzed. There
Organo-clay/PP was a slight decrease at the onset temperature of thermal degra-
dation for SHSD-filled specimens compared to the neat PP. With
0 50 100 150 200 the increasing temperature, the thermal degradation rate of the
Temperature (°C) SHSD-filled specimens gradually decreased compared to that of
the neat PP. The SHSD composites exhibited the highest temper-
Fig. 5. Storage modulus of neat PP and PP composites. ature for the entire thermal degradation. Generally, the SHSD
composite has a similar thermal stability level to the organo-clay
reinforced composite. However, the adhesion between clay and
polymer is poor if no compatibilizer and/or surface treating
Table 5 agent is used.
Thermal conductivity and thermal effusivity of neat PP and PP composites
Thermal conductivity (w/m k) Thermal effusivity ðW S=m2 kÞ 4. Conclusions
Neat PP 0.229 ± 0.012 502.3 ± 13.9
SHSD/PP 0.219 ± 0.011 477.1 ± 10.6 The sunflower hull sanding dust, SHSD, can be dispersed uni-
Organo-clay/PP 0.198 ± 0.006 436.7 ± 8.9
formly throughout a PP matrix by melt mixing using a twin-screw
extruder. After adding the SHSDs, the crystallization behavior of
the composite system was influenced; crystallization temperature
SHSD and organo-clay. The sunflower fibers influence the mobili- of the PP matrix was increased, while the melting temperature re-
zation of PP macromolecular chains and transfer the stress mained constant. Although the degree of crystallinity of PP exhib-
throughout the PP matrix. As a result, the stiffness of the material ited a decrease with the addition of SHSDs, the mechanical
is enhanced. With increase in temperature, the mobilization of PP properties of the SHSD composites showed marked improvements.
macromolecular chains became more active, and the crystalline Compared to the neat PP, the SHSD/PP composites also displayed
domains had an obvious influence on the modulus of the speci- better heat insulation properties and thermal stability at high tem-
mens. Considering the results of DSC, the degree of crystallinity perature stages. Overall, the use of a natural agricultural processing
of the SHSD composites is higher than that of the organo-clay byproduct, SHSD, shows a potential for promising applications due
composites. Therefore, the storage modulus of the SHSD-filled PP to their ability to yield improved mechanical and thermal proper-
composite gradually and slightly surpassed the modulus of the ties in a cost-effective manner.
organo-clay filled specimen at the stage of high temperatures.

The authors gratefully acknowledge the support from NSF

through NIRT Grant 0506531 and DMR Instrumentation Grant
0413967. This work is also partially supported by NASA through
Grant NNM04AA62G.


ASTM D790M-93. Standard test methods for flexural properties of unreinforced and
Weight (%)

60 reinforced plastics and electrical insulating materials.

Bledzki, A.K., Letman, M., Viksne, A., Rence, L., 2005. A comparison of compounding
processes and wood type for wood fibre-PP composites. Composites Part A 36,
40 Fang, L., Leng, Y., Gao, P., 2006. Processing and mechanical properties of HA/
UHMWPE nanocomposites. Biomaterials 27 (20), 3701–3707.
Karmarkar, A., Chauhan, S.S., Modak, J.M., Chanda, M., 2007. Mechanical properties
Neat PP of wood–fiber reinforced polypropylene composites: effect of a novel
20 SHSD/PP compatibilizer with isocyanate functional group. Composites Part A 38 (2),
Organo-clay/PP 227–233.
Li, J., Zhou, C., Gang, W., 2003. Study on nonisothermal crystallization of maleic
anhydride grafted polypropylene/montmorillonite nanocomposite. Polymer
0 Testing 22, 217–223.
0 100 200 300 400 500 600 Modesti, M., Lorenzetti, A., Bon, D., Besco, S., 2005. Effect of processing conditions on
morphology and mechanical properties of compatibilized polypropylene
Temperature (°C) nanocomposites. Polymer 46, 10237–10245.
Pickering, K.L., Beckermann, G.W., Alam, S.N., Foreman, N.J., 2007. Optimising
Fig. 6. TGA curves of neat PP and PP composites. industrial hemp fibre for composites. Composites Part A 38 (2), 461–468.
G. Sui et al. / Bioresource Technology 100 (2009) 1246–1251 1251

Ray, D., Sengupta, S., Sengupta, S.P., Mohanty, A.K., Misra, M., 2006. Preparation and Yang, H.S., Wolcott, M.P., Kim, H.S., Kim, S., Kim, H.J., 2006. Properties of
properties of vinylester resin/clay nanocomposites. Macromolecules Materials lignocellulosic material filled polypropylene bio-composites made with
and Engineering 291, 1513–1520. different manufacturing processes. Polymer Testing 25 (5), 668–676.
Rouilly, A., Orliac, O., Silvestre, F., Rigal, L., 2006. New natural injection-moldable Zhao, Y., Wang, K., Zhu, F., Xue, P., Jia, M., 2006. Properties of poly (vinyl chloride)/
composite material from sunflower oil cake. Bioresource Technology 97, 553– wood flour/montmorillonite composites: effects of coupling agents and layered
561. silicate. Polymer Degradation and Stability 91 (12), 2874–2883.
Vladimirov, V., Betchev, C., Vassiliou, A., Papageorgiou, G., Bikiaris, D., 2006. Zhuang, G.S., Sui, G.X., Meng, H., Sun, Z.S., Yang, R., 2007. Mechanical properties of
Dynamic mechanical and morphological studies of isotactic polypropylene/ potassium titanate whiskers reinforced poly(ether ether ketone) composites
fumed silica nanocomposites with enhanced gas barrier properties. Composites using different compounding processes. Composites Science and Technology 67
Science and Technology 66, 2935–2944. (6), 1172–1181.
Wunderlich, B., 1990. Thermal Analysis. Academic Press, New York, p. Zuiderduin, W.C.J., Westzaan, C., Huétink, J., Gaymans, R.J., 2003. Toughening of
418. polypropylene with calcium carbonate particles. Polymer 44, 261–275.