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Abstract
The feasibility of manufacturing woodrubber functional composite panels with a polymeric methylene diphenyl diisocyanate
(PMDI) and urea-formaldehyde (UF) combination binder system was investigated. Mechanisms of interacted independent variables
(board density, pressing time and pressing temperature) for eect on board properties were opened out. The board performance was
evaluated by measuring internal bond (IB) strength, modulus of rupture (MOR) and modulus of elasticity (MOE). The test results were
statistically analyzed by using response surface method (RSM) of Design-Expert software to determine the signicant independent variables that inuenced board properties. A mathematical simulation or response surface models were developed to predict the board properties (MOR, MOE and IB). The results showed that board density and some interactions between the experimental variables were
signicant factors that inuenced board mechanical properties. The suggested optimal board manufacturing conditions were about
170 C, for pressing temperature, 300 s for pressing time, and 1000 g cm3 for board density.
2007 Elsevier Ltd. All rights reserved.
Keywords: Woodrubber composite; PMDI/UF resin; Processing optimization
1. Introduction
With the rapid development of the economy worldwide
and the increasing demand of automobiles, people will confront a severe problem the dilemma between environmental
pollution from waste tires and the shortage of rubber
resources. A statistic analysis indicates that approximately
1.5 billion tires are discarded every year worldwide (Jiang,
2003). The ever-increasing environmental hazard from the
waste tires has emerged. To protect environment by reducing black pollution and save resources have become an
important issue for every country. Eectively recycling
waste tires such as manufacturing woodrubber based
composites could be one of the solutions
The woodrubber composite panel is a relatively new
type of composite materials in which PMDI resin is commonly used as binder and waste tire rubber crumbs and
*
0960-8524/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.05.031
2385
2. Methods
2.1. Experimental materials
Wood particle species used in this study was larch (Larlx
gmelini) obtained from Xing An Mountain, Inner Mongolia of China. An analysis of particle geometry indicated
that particle length ranged from 3 to 25 mm, width from
1.0 to 2.5 mm, and thickness from 0.2 to 0.8 mm. Rubber
particles were prepared from waste tires with reinforced
tendons being mechanically removed prior to grinding.
The length of rubber particles varied between 1 and 7 mm.
Both commercial PMDI and UF resins were used as binder in this work. PMDI was provided by Wan Hua Polyurethanes Co. LTD in China; UF resin was provided by
Bell Co. LTD in Beijing. Catalyst for UF resin was 20%
ammonium chloride (NH4Cl) aqueous solution. The
NH4Cl solution was applied at a level of 0.5% based on
solid weight of UF resin. An emulsion wax at solid content
of UF was used as waterproof agent. The wax was applied
at a level of 1% based on solid weight of UF resin. Both
catalyst and wax were pre-mixed with UF resin prior to
application. The catalyst was provided by Shanghai Chemistry Reagent Corporation in China. Emulsion wax was
provided by Yan Shan Chemical Plant in Beijing.
2.2. Experimental procedures
PMDI and UF resins were applied separately. A 6%
PMDI for rubber crumbs and a 10% UF (solid basis) for
wood particles were used through the experiment. The
weight ratio of wood particles to rubber crumbs was
60:40. First of all the required amount of wood particles
was loaded into a drum blender. UF resin was applied to
the particle via spraying. After uniformly mixing, the resinated particles were discharged, followed by loading rubber
crumbs. The PMDI resin was mixed with more than 40%
acetone based on the resin weight. After PMDI application,
the resinated wood particles were reloaded into the blender
and mixed with the resinated rubber crumbs afterwards.
The mixed wood particle and rubber crumbs were manually formed into a mat of 300 mm by 300 mm in a wooden
box. The mat was pre-pressed at 1.5 MPa for 30 s and then
hot-pressed at the pressure of 48.0 MPa to 12 mm of the
target thickness. To prevent board sticking to hot platens,
silicon oil was coated on the surfaces of top and bottom
platens. In addition, waxed papers were also placed at
the bottom and on the top of the mat. The hot press temperature was in range of 160180 C, the hot press time in
180420 s, and board density in 8001200 g cm3.
2.3. Experimental methods
Box-Behnken design of RSM (Response Surface
Method) in Design-Expert 7.01 software was used in experimental design to determine the signicant variables that
inuenced board performance (Bloor and England, 1991).
2386
Table 1
Factors and corresponding levels for response surface design
Table 2
Experimental design and test results
Factors
ID
Unit
Experiment A
run no.
Temperature
(C)
B
Time
(s)
C
Density
(g cm3)
MOR MOE
(MPa) (MPa)
IB
(MPa)
Temperature
Time
Density
A
B
C
C
s
g cm3
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
300
180
180
300
300
180
180
420
300
420
300
300
420
300
300
300
420
1000
800
1000
800
1000
1200
1000
800
1200
1000
800
1000
1200
1000
1200
1000
1000
15.0
8.7
10.9
8.1
15.0
13.6
13.4
9.1
14.9
12.2
7.5
15.0
15.3
15.0
14.3
15.0
13.2
1.09
0.50
0.59
0.52
1.09
0.62
0.73
0.48
0.91
0.82
0.57
1.09
0.65
1.09
0.93
1.09
0.92
Level
Low ()
Medium (0)
High (+)
160
180
800
170
300
1000
180
420
1200
170
170
160
160
170
170
180
170
160
180
180
170
170
170
180
170
160
2350
860
1534
855
2351
2140
1870
1540
2110
2110
1429
2350
2210
2350
2077
2350
1990
MOR (P < 0.0001) at the 95% condence level. The pressing temperature and time were not signicant model terms
for MOR. There was an interaction between pressing temperature and time, which was a signicant model term for
MOR. This observation agreed to the ndings by Wang
and Lu (2004) who observed that pressing temperature
and time were interacted when mixed adhesives of MID
and UF were used in manufacturing wood-based particleboard. Regarding MOE property, all single factors (press
temperature, time and board density) and the interactions
between any two of them were signicant model terms.
With respect to IB strength, only board density was the signicant model term. All interactions between press temperature, time and board density did not signicantly aect IB.
Table 3
ANOVA for response surface quadratic model of MOR
D. Sources
Sum of squares
df
Mean square
F-value
p-value
Model
A-Temperature
B-Time
C-Density
AB
AC
BC
122.820
0.0312
1.125
75.031
3.062
0
0.562
9
1
1
1
1
1
1
13.6466
0.0312
1.12
75.0312
3.062
0
0.5625
61.1369
0.14
5.04
336.14
13.72
0
2.52
<0.0001
0.7194
0.0596
<0.0001
0.0076
1.0000
0.1564
Table 4
ANOVA for response surface quadratic model of MOE
D. Sources
Sum of squares
df
Mean square
F-value
p-value
Model
A-Temperature
B-Time
C-Density
AB
AC
BC
3951285
124251.1
261364.5
1855701
11664
92112.25
93025
9
1
1
1
1
1
1
439031.7
124251.1
261364.5
1855701
11664
92112.25
93025
1989.72
563.1141
1184.521
8410.157
52.862
417.4586
421.5953
<0.0001
<0.0001
<0.0001
<0.0001
0.0002
<0.0001
<0.0001
2387
Table 5
ANOVA for response surface quadratic model of IB
D. Source
Sum of squares
df
Mean square
F-value
p-value
Model
A-Temperature
B-Time
C-Density
AB
AC
BC
0.843849
0.001513
0.023113
0.1352
0.0144
0.000225
0.000625
9
1
1
1
1
1
1
0.093761
0.001513
0.023113
0.1352
0.0144
0.000225
0.000625
13.79562
0.222543
3.400683
19.8928
2.11876
0.033106
0.09196
0.0011
0.6515
0.1077
0.0029
0.1888
0.8608
0.7705
0.9675
IB (MPa)
1.1
0.835
0.7025
0.57
420
180
360
175
300
170
240
B: Time (s)
165
180
160
A: Temperature (C)
2400
14.05
2177.5
MOE (MPa)
MOR (MPa)
b
15.1
13
11.95
1955
1732.5
1510
10.9
420
180
360
175
300
B: Time (s)
170
240
165
180
160
A: Tempereture (C)
420
180
360
175
300
B: Time (s)
170
240
165
180
A: Tempreture (C)
160
Fig. 1. 3D graphic surface optimization of MOR and MOE as inuenced by hot press time and temperature.
2388
2389
Table 6
The mechanical properties of wood/rubber composite panel made with dierent amounts of resins
No.
Target density
(g/m3)
Actual density
(g/cm3)
1
2
3
4
5
800
800
800
800
800
789
798
799
807
802
UF content (%)
6
8
10
12
14
6
8
8
10
10
Wood/Rubber
ratios
MOR
(MPa)
MOE
(MPa)
IB
(MPa)
60/40
60/40
60/40
60/40
60/40
3.5
4.5
6.0
7.5
9.5
533
618
750
800
917
0.58
0.78
0.85
0.88
0.95
Chinese Standard GB/T4897.1 7 2003. Requirements of average particleboards under dry condition: MOR P 12.5 MPa, IB P 0.28 MPa; Requirements of furniture and decorative materials: MOR P 14.0 MPa, MOE P 1800 MPa, IB P 0.40 MPa.
a
16.1
2400
13.95
1850
MOE (MPa)
MOR (MPa)
11.8
9.65
7.5
1300
750
200
1200
180
1100
175
1000
170
165
1200
180
1100
175
1000
A: Tempereture (C)
800 160
C: Density (g cm-3)
170
900
165
A: Temperature (C)
800 160
Fig. 4. 3D graphic surface optimization of MOR and MOE as inuenced by board density and press temperature.
1.12
IB (MPa)
0.97
0.82
0.67
0.52
1200
180
1100
175
1000
170
165
A: Temperature (C)
800 160
reached its maximum at 1000 g cm3. The press temperature had a less inuence on IB strength.
Fig. 4a and b and Fig. 5 show that higher density had a
negative impact MOR and MOE (>1100 g cm3) and IB
(>1000 g cm3), which was likely due to the damage of
wood bers. Unlike the wood particles, the rubber crumbs
may not be signicantly damaged at the high pressure, but
the stress concentration could take place, the rubber
crumbs absorb a large amount of energy during the deformation. Rubber consists of long exible chain-link molecules with many repeating units which can rotate freely
about their backbone bonds. The stress concentration will
reduce bending strength properties. In general, wood particles play a critical role in improving mechanical properties
of composites due to their greater strength compared to
rubber crumbs. In this study, the rubber crumbs were lled
between wood particles and expected to make only a little
contribution to the strength of the composites because of
their low strength and large deformation. Above a certain
limit of board density, the load may not be eectively transferred from the interface zone of woodrubber to wood
particles and result in an interface breakage. Therefore,
MOR, MOE and IB of composites could drop when density surpasses the limitation.
An analysis of panel density and hot press temperature
that aected board mechanical properties, the density at
1000 g cm3 and press temperature at 170175 C were
2390
Table 7
Summary of experiment optimization for MOR, MOE and IB
Factors
Optimized value to IB
Lowest value
Highest value
Temp. (C)
Time (s)
Density (g cm3)
Result (MPa)
169.758
295.2
1023.32
15.615
170.54
303
1030
2409.6
169.26
291.7
1015.16
1.092
160
180
800
180
420
1200
4. Conclusions
The experiment was conducted to determine the feasibility of manufacturing of woodrubber composites. The
interaction between experimental variables and their inuence on board performance were explored. The test results
indicated that press temperature and time signicantly
impact on MOR and board density signicantly inuences
all board properties (IB and MOE, and MOR). The interactions of variables also have signicant eects on MOE.
The signicant conicoid regression model equations were
established for IB, MOR and MOE. An ANOVA analysis
shows that the optimal composite manufacturing variables
for making high quality woodrubber panel would are
about 170 C for press temperature, about 300 s for press
time, and about 1000 g cm3 for board density.
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