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Interface Reaction and Molecule Recognition Among Wood Flour, Amino

Silane Coupling Agent and POE-g-MAH Compatibilizer
Sheng-Fei Hua; Min Zhaoa; Chong Zhanga; Chen Wenb
a
School of Chemical and Environmental Engineering, Hubei University of Technology, Wuhan, China
b
School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, China

Online publication date: 19 January 2011

To cite this Article Hu, Sheng-Fei , Zhao, Min , Zhang, Chong and Wen, Chen(2011) 'Interface Reaction and Molecule
Recognition Among Wood Flour, Amino Silane Coupling Agent and POE-g-MAH Compatibilizer', Polymer-Plastics
Technology and Engineering, 50: 1, 47 — 51
To link to this Article: DOI: 10.1080/03602559.2010.512347
URL: http://dx.doi.org/10.1080/03602559.2010.512347

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 Polymer-Plastics Technology and Engineering, 50: 47–51, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 0360-2559 print=1525-6111 online
DOI: 10.1080/03602559.2010.512347
Interface Reaction and Molecule Recognition Among
Wood Flour, Amino Silane Coupling Agent and
POE-g-MAH Compatibilizer
Sheng-Fei Hu1, Min Zhao1, Chong Zhang1, and Chen Wen2
1
School of Chemical and Environmental Engineering, Hubei University of Technology, Wuhan, China
2
School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, China
The interface reaction and molecule recognition among wood
flour, amino silane coupling agent and maleic anhydride grafted
polyolefin compatibilizer were studied by fourier transform infrared
analyzer (FTIR), scanning electron microscope with an energy
dispersive X-ray spectroscopy (SEM-EDS) and X-ray photoelec-
tron spectra (XPS). According to molecule recognition principles,
c-APS in the wood flour surface was identified by SEM-EDS. A
new state of N1 s at 401.33 eV appears in XPS as c-APS and maleic
Downloaded At: 08:30 28 January 2011
anhydride grafted polyolefin compatibilizer are introduced simul-
taneously, which shows the occurrence of reaction between c-APS
and maleic anhydride-grafted polyolefin compatibilizer, and amino
is formed.
Keywords Interface reaction; Molecule recognition; SEM-EDS;
Wood flour; XPS
INTRODUCTION
Wood plastic composites (WPCs) as environmental
friendly materials have emerged in recent decades. They
have such advantages as low density, high specific strength
and Young’s modulus, non-abrasive nature, low cost and
most importantly biodegradability and thus have become
prevalent in many fields, such as building industry, auto-
motive industry, furniture materials etc.[1,2]. However, the
relatively poor mechanical and physical properties pre-
vented a more extended utilization of the WPCs. Like other
inorganic fillers, the hydrophilic nature of wood flours
adversely affects adhesion to a hydrophobic matrix and as
a result, it causes a loss of strength.
It has been proved that pre-treated wood flour with
organosilanes, like c-aminopropyltriethoxysilane (c-APS),
introduces a small amount of functional monomer grafted
polyolefin as compatibilizer, like maleic anhydride (MAH)
grafted polyolefin, can significantly improve the physical
and mechanical properties of the composites[3–6]. And lots
of studies have been done to understand the mechanisms
Address correspondence to Sheng-Fei Hu, School of Chemical
and Environmental Engineering, Hubei University of Tech-
nology, Wuhan 430068, China. E-mail: hghsf@163.com
47
of organosilanes with wood fibers[7–9] and functional
monomer grafted polyolefin with wood fiber[10–12]. The
functional groups of these polymers were shown to interact
strongly or even react chemically with the surface of
wood, while the long alkyl chains diffuse into the matrix,
making stress transfer possible. In recent years, a lot of
efforts have been put into improving the interfacial
adhesion between the polar fillers and nonpolar thermo-
plastic matrix through introducing c-APS and MAH-
grafted polyolefin simultaneously[13,14].
The chemistry mechanisms about the effects of silanes
and polymer compatibilizers on the adhesive strength of
polymers towards inorganic fillers, such as metallic sub-
strates and glass fiber, are well understood[15,16]. However
in WPCs field, the method introducing c-APS and MAH-
grafted polyolefin simultaneously has not been extensively
studied and the mechanisms between c-APS and MAH-
grafted polyolefin have not been determined.
In this study, the interface reaction among wood flour,
amino silane-coupling agent and ethylene-octene copoly-
mer grafted with maleic anhydride (POE-g-MAH) compa-
tibilizers were examined, and c-APS in wood flour surfaces
can be identified according to molecule recognition princi-
ples (SEM-EDS). The results reported in this article will
promote the understanding of the preparation of high
performance of WPCs and the interface reaction of WPCs.
EXPERIMENTAL SECTION
Materials
The materials used in this study were wood flour, a
thermoplastic polymer, polypropylene (PP), and the
coupling agent c-aminopropyltriethoxysilane (c-APS) and
POE-g-MAH, which is ethylene-octene copolymer (POE)
grafted with maleic anhydride (MAH). Polypropylene was
provided as powders by Refinery of Sinopec Jinling
Petrochemical Corp., Ltd. with a melt index of 2.1–4.0 g=
10 min (pp h-xd-045–1). The coupling agent c-APS was
purchased from Wuhan University Silicone New Material
Ltd. Co. POE-g-MAH Fusabond1 MN493D granulates
 48 S.-F. HU ET AL.

from Dupont1. It is a random copolymer grafted (>1%)
with a melting point 48
C, a melt flow rate of 1.6 g=
10 min and a density of 0.87. Commercially produced wood
flour L=R  4.3) of radiate pine was used as filler. Other
materials are commercial products.
Wood Flour Treatment and Composite Preparation
Wood flour was treated with Na(OH) aqueous solution
(20% w=v) for 4 h at room temperature. Then, the wood
flour was washed with distilled water until all the sodium
hydroxide was eliminated; that is, the pH value was natural.
The Na(OH)-treated wood flour then was immersed in a
beaker in 90=10=10 g=g=g ethanol=water=c-APS solution
and by stirring for 1.5 h. The solution was then heated at
130
C for 1 h. Subsequently, the solution was kept at room
temperature 24 h, followed by drying in an oven at 105
C
for 12 h. Composites were prepared by compounding the
dried raw materials using a two-roll mill. Prior to com-
pounding, compositions were poured into the high-speed
mixer and continued mixed for 5 min to obtain the
unloaded mixtures. The processing formulations are shown
in Table 1.
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X-Ray Photoelectron Spectra Analysis
The element composition and interfacial interactions
were further studied using X-ray photoelectron spectra
(XPS). XPS spectra were recorded on a VG Multilab 2000
spectrometer (Thermo Company, USA) using Al Ka
(1486.6 eV) radiation.
RESULTS AND DISCUSSION
In order to examine the surface of the samples, investi-
gation was conducted using the SEM equipped with EDS
(Fig. 1), where (A)–(C) shows the SEM images of the treated
samples and the untreated one, and (A0 )–(B0 ) shows the map-
ping images of silica element, which were obtained by EDS
measurements. The results indicated that after Soxhlet-
extracted with xylene for 48 h both the WF-Si and WF-Si-
MAH still had added silicon in their structure (Fig. 1a and
b), while no silicon was found in the WF structure (Fig. 1c).
Figure 2 shows the FTIR spectra of wood flour surfaces
of WF, WF-Si, WF-Si-MAH, respectively. The spectra
revealed that several changes did occur. After being treated
by c-APS, two absorbing peaks emerged in 3400–3000 cm1
region corresponding to the tension and vibration of NH2.

The components were homogenized in a two-roll mill at The N-H bend-vibration absorbing peak is at 1567.3
180
C for 5 min following by compression molding at 180
C cm1. The typical absorbing peaks of Si-O bond exist at
with 3 min molding time at 10 MPa. Composites cut from 1125.2 cm1 and 1025.8 cm1. A noteworthy point is that
samples without POE-g-MAH and with POE-g-MAH were
Soxhlet-extracted with xylene for 48 h. Residual wood flour
was dried in an oven at 105
C for 12 h.

FTIR Analysis
FTIR spectra were obtained with a Nicolet 5700 spec-
trometer. Samples were scanned using diffuse reflectance
mode, in the DRIFT sample accessory, from 4000 to
500 cm1. KBr pellets were employed for the testing specimen.

Morphological Investigations
A scanning electron microscope (JSM6390 LV) with an
EDS (Energy dispersive X-ray spectroscopy) detector was
used for localizing and measuring the amount of silicon
on the modified wood flour surface. The mapping was
performed on an area displaying the wood flour using an
electron beam accelerating voltage of 30 kV and a current
of 30 mA.

TABLE 1
Processing formulations (weight)
POE-g- Wood
Sample PP (g) MAH (g) flour (g) c-APS (g)
WF 100 0 50 0
WF-Si 100 0 50 5
WF-Si-MAH 80 20 50 5 FIG. 1. c-APS recognition micrograph (SEM-EDS) in wood four sur-
faces (A) WF-Si, (B) WF-Si-MAH, (C) WF.
 INTERFACE REACTION AMONG WOOD PLASTICS 49

FIG. 2. FTIR spectra of wood flours extracted from samples.

FIG. 3. Proposed interfacial reaction between (a) wood flour and
Downloaded At: 08:30 28 January 2011

c-APS, (b) wood flour and POE-g-MAH.

the strength of the characteristic peaks of NH2 in 3400–
3000 cm1 region are weak, resulting from two possible
factors: on the one hand, the concentration of c-APS on Si and N of sample WF-Si are strongest. While POE-g-
the fiber surfaces is poor, on the other hand, bending MAH presents intensities of the peaks of Si and N decrease.
vibration modes derived from the unreactive hydroxyl, This could be ascribed to the fact that the silane-
wood flour surface itself in this region, are intense. containing and amino-containing concentration decreased
One of the most noticeable modifications generated by as POE-g-MAH presents. As illustrated in Figure 4, no sig-
c-APS and POE-g-MAH treatments is the decrease of the nal from Si can be observed in the sample WF, which coin-
peak center at 3415.8 cm1, characteristic of OH. It cides with the SEM-EDS image (Fig. 1). This revealed that
proved that both c-APS and POE-g-MAH could react with the c-APS effectively adsorbed on the wood flour surface.
OH on the wood surface. Interface interactions for the The decrease of silane-containing and amino-containing
c-APS coupling agent systems and MAH-grafted polyolefin
compatibilizer systems had been confirmed in previous
articles[17–21]. The mechanisms are shown in Figure 3.
Otherwise, silanols are also known to condense amongst
themselves during hydrolysis[7,9,21,22]. The peaks at 3400–
3000 cm1, 1567.3 cm1 disappear as POE-g-MAH was
added. The removal of NH2 of the fiber surfaces causes
these peaks to disappear. It could be ascribed to the inter-
facial interactions between function of anhydride groups
on POE-g-MAH and amino groups (NH2) on surface of
the c-APS–treated wood flour. From this analysis, it can
be primarily concluded that there are silane films and
POE-g-MAH chemisorbed on wood flour surface.
XPS was used to further analyze the chemical reaction on
the wood flour surface. Figure 4 provides the wide-scan
XPS spectra of WF, WF-Si, and WF-MAH films. As illu-
strated in Figure 2, signals from Si and N can be observed
on the XPS spectra of surfaces of wood flours for samples
WF-Si, and WF-Si-MAH. Compared to the sample
WF-MAH and the sample WF, intensities of the peaks of FIG. 4. IPS survey spectra of separated surfaces of samples.
 50 S.-F. HU ET AL.
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FIG. 5. N 1s XPS spectra of remaining wood flour surfaces after 48 h
xylene extraction WF-Si.
on the sample WF-Si-MAH surface, compared to WF-Si,
showed the successful surface-initiated POE-g-MAH on
the wood flour surface.
Figure 5 presents the N 1 s curve-fitting spectra from
WF-Si and WF-Si-MAH films. The N 1 s spectrum
FIG. 6. Proposed interfacial reaction between POE-g-MAH and c-APS
modified wood flour.
TABLE 2
Components for curve-fitting of N1 s spectrum in Figure 5
Binding
Sample energy (eV) Chemical State At%
WF-Si 399.50 CH2-NH2 82.07
400.59 OH . . . NH2-CH2 17.93
WF-Si-MAH 399.70 CH2-NH2 62.25
400.55 OH . . . NH2-CH2 23.52
401.33 14.23
(Fig. 5a) of the WF-Si surface is fitted with binding
energies at 399.50 and 400.59 eV. The peak at 399.50 eV
could be assigned to the free amino groups (NH2) of
c-APS film. The peak at 400.59 eV could be attributed to
that of hydrogen-bonded NH2 in OH    NH2CH2–.
While the N 1 s core-level spectrum of the WF-Si-MAH
surface can be curve-fitted into three peak components,
one more peak than that of WF-Si, with binding energies
at 399.70, 400.55 and 401.33 eV. The third peak at
401.33 eV could be assigned to the amide group present
in C(=O)N, which revealed the interfacial interactions
between the functional anhydride group of on POE-g-
MAH and amino groups (NH2) on the surface of the
treated wood flour, which is shown in Figure 6.
Table 2 shows the components for curve fitting of N 1 s
spectrum and the relative quantities of N 1 s in different
chemical states. It can be seen that the content of N in
CH2-NH2 as to samples WF-Si and WF-Si-MAH is
82.07% and 62.25%, respectively. However, the area ratio
of N in -OH . . . NH2CH2 changes a little between the
two samples. This implied that the main chemical reaction
takes place between the free amino groups (CH2-NH2) in
c-APS and the carboxyl group in POE-g-MAH.
CONCLUSIONS
The interface reactions among wood flour, amino
silane-coupling agent and maleic anhydride (MAH) grafted
polyolefin compatibilizers were investigated. The types of
interface reaction were demonstrated by FTIR and XPS
analysis. The results confirmed that the occurrence of
reaction were found between -OH groups of c- APS and
the -OH groups of WF, MAH groups and the -OH groups
of WF, MAH groups and NH2 groups of c-APS. And
according to molecule recognition principles, c-APS in wood
flour surface can be identified by SEM-EDS. These results
also provide a new clue for other molecule recognition.
ACKNOWLEDGMENTS
This work was founded by the natural science foun-
dation of Hubei Province, P.R. China (NO. 2009CDB136).
 INTERFACE REACTION AMONG WOOD PLASTICS 51

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