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Need for alternative
sources to satisfy the
increasing global
demand and fillers to
reduce amounts of
rubber needed.
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Fillers
Mechanical properties may be improved via reinforcing effects
Particle size
Loading
Surface activity or surface chemistry
Filler shape or structure
Processing and Manufacturing
Reduction of tackiness for mixing and injection mold applications
Qualitative Characteristics
Texture, Color
Diluent cost reduction
Fillers may cost less than the polymer
Modification of thermal properties
Fillers addition can modify thermal stability and shift Tg
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Commonly used NR inorganic mineral fillers:
Advantages
Calcium Carbonate and Talc (Mg3Si4O10(OH)2), improve tear resistance, less
tack, low reinforcing effect, color (white)
Silica and Clays reduce surface friction, reinforcing effect
Carbon Black improves resistance to wear, reinforcing effect
Disadvantages
Carbon Black is derived from petroleum
Silica is polar, and hard to incorporate into non-polar NR.
Calcium carbonate and talc weaken the material properties.
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Objective
Determine the effect of low cost fillers made from different
types of waste-derived, renewable, materials on physical
and thermal properties of cured rubber compounds.
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Materials and Methods
Rubber Material
Hevea rubber, SMR-20 (Centrotrade, U.S)
Guayule natural rubber (OSU).
Filler
Eggshells
Carbon Fly Ash
Guayule Bagasse
Tomato Peels
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Fillers
In this study two different ranges of particle size were used:
Macro size: particles with a diameter less that 300 microns but greater that
38 micron
Micro size :particles with a diameter less that 38 microns
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Macro sized fillers particle size distribution. CFA: 89.32 m, ES: 241.46 m, GB: 279.33
m, TP: 179.02 m.
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Micro sized fillers particle size distribution. CFA: 12.12 m, ES: 23.19 m, GB: 54.75 m,
TP: 26.95 m.
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Compounding Recipe
Material Quantity (phr)
NR 100
Carbon black 35 30 25 15 0
Filler 0 5 10 20 35
Sulfur 3.5
ZnO 5
TBBS 0.75
Stearic acid 1
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Composites Manufacture
The effect of particle size and loading was assessed using
a standard compound in which 35 phr carbon black was
gradually replaced by specific waste-derived fillers (by
weight) until no carbon black remained.
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Composites testing
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Tensile Results: Guayule Rubber
CFA Eggshells Guayule Bagasse Tomato Peel
30
20
Tensile
Strength (MPa)
10
0
4.0
Filler
Stress at 300%
3.0 size
300>d>38 m
Elongation (MPa) 2.0
d<38
1.0 m
0.0
As alternative
Ultimate
filler loading increases, tensile strength decreases.
2000
However higher
Elongation (%) 1500 tensile strength results than those of carbon black
1000
composites, were 500 achieved by composites made with micro size eggshells
at 5 phr,10 phr and 0
0 102020 phr,
30 micro
0 10 size30 tomato
20 0 10 peels
20 30 0 and
10 CFA
20 30 at 5 phr and
Waste Filler (phr)
macro and micro 35 size
25 guayule
15 5 35 bagasse
25 15 5 35at 25 5 phr.
15 5 35 25 15 5
Carbon Black (phr)
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Tensile Results: Guayule Rubber
CFA Eggshells Guayule Bagasse Tomato Peel
30
20
Tensile
Strength (MPa)
10
0
4.0
3.0
Stress at 300%
Elongation (MPa) 2.0
1.0
0.0
Stress atUltimate
300%2000elongation (300% Modulus), decreases as alternative
filler loading increases.
Elongation (%) 1500
1000
Higher modulus values than those of carbon back
composites, were 500 obtained for macro and micro CFA at 5 phr, macro size
0
guayule bagasse 0and 10 tomato
20 30 0 peels
10 20at 30
5 phr 0 and
10 20 10
30 phr
0 and
10 20 micro
30 size
Waste Filler (phr)
tomato peels at 535phr. 25 15 5 35 25 15 5 35 25
Carbon Black (phr)
15 5 35 25 15 5
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Tensile Results: Guayule Rubber
CFA Eggshells Guayule Bagasse Tomato Peel
30
20
Tensile
Strength (MPa)
10
0
4.0
3.0
Stress at 300%
Elongation (MPa) 2.0
1.0
0.0
2000
Ultimate
Elongation (%) 1500
1000
500
0
0 10 20 30 0 10 20 30 0 10 20 30 0 10 20 30
Waste Filler (phr)
35 25 15 5 35 25 15 5 35 25 15 5 35 25 15 5
Carbon Black (phr)
Ultimate elongation increased as the alternative filler loading increased 65
Tensile Results: Hevea Rubber
CFA Eggshells Guayule Bagasse Tomato Peel
30
Tensile
Strength (MPa) 20
10
6
Stress at 300%Filler size
Elongation (MPa) 4
300>d>38 m
2
d<38 m
0
1500
Ultimate
Tensile strength decreases as the alternative filler loading increases.
Elongation (%) 1000
However, tensile
500
strength results for micro size eggshell at 10 and 20
phr and micro size
0
0 10tomato
20 30 peels
0 10 at 10
20 30 0phr 10 are
20 greater
30 0 10 than
20 30tensile
strength at 5 phr.35 25 15 5 35 25 15
Waste Filler (phr)
5 35 25 15 5 35 25 15 5
Carbon Black (phr)
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Tensile Results: Hevea Rubber
CFA Eggshells Guayule Bagasse Tomato Peel
30
Tensile
Strength (MPa) 20
10
6
Stress at 300%
Elongation (MPa) 4
0
1500
Ultimate
Elongation (%) 1000
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Tensile Results: Hevea Rubber
CFA Eggshells Guayule Bagasse Tomato Peel
30
Tensile
Strength (MPa) 20
10
6
Stress at 300%
Elongation (MPa) 4
0
1500
Ultimate
Elongation (%) 1000
500
0
0 10 20 30 0 10 20 30 0 10 20 30 0 10 20 30
Waste Filler (phr)
35 25 15 5 35 25 15 5 35 25 15 5 35 25 15 5
Carbon Black (phr)
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TGA Results: Guayule Rubber
Sample Beginning mass Major mass loss % Loss
loss (c) range (c)
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TGA Results: Hevea Rubber
Unfilled Hevea
Carbon black
5 phr
35 phr (Except
TP, 10 phr)
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TGA Results: Hevea Rubber
Sample Beginning mass Major mass loss range % Loss
loss (c) (c)
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Acknowledgements
We thank Ohio Third Frontier, Ohio Research Scholars Program in
Technology-Enabling and Emergent Materials (TECH 09-026), and
USDA National Institute of Food and Agriculture, (Hatch project
230837) that provided financial support for this project. We also thank
Fulbright for sponsoring our student Cindy Barrera during her PhD.
Program.
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