Mechanical and thermal properties of vulcanized

natural rubber reinforced with bio-based fillers

C.S. Barrera, K. Cornish.
Ohio Agricultural Research and Development Center, Department of Food,
Agricultural and Biological Engineering
The Ohio State University.
 Natural Rubber
Rubber is used as raw material for the manufacture of over 40,000 products.
Unique properties of NR: malleability, resilience, heat dispersion, strain induced
m crystallization.
Produced by over 2,000 plant species.

51
 Need for alternative
sources to satisfy the
increasing global
demand and fillers to
reduce amounts of
rubber needed.

Source: Malaysian Rubber Board. Natural rubber

statistics 2013.

52
 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
53
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.

54
 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.

55
 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

56
 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

waste dry macro

sieved
stream milled filler

waste wet dry micro

dried sieved
stream milled milled filler

57
Macro sized fillers particle size distribution. CFA: 89.32 m, ES: 241.46 m, GB: 279.33
m, TP: 179.02 m.
58
Micro sized fillers particle size distribution. CFA: 12.12 m, ES: 23.19 m, GB: 54.75 m,
TP: 26.95 m.
59
 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

60
 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.

35 phr 5 phr 10 phr 20 phr 35 phr

carbon filler + 30 filler + 25 filler + 15 filler
black phr carbon phr carbon phr carbon
black black black

61
 Composites testing

Evaluation of the tensile mechanical properties was performed using

a tensiometer (Instron) following ASTM D 412. Five dumbbell
specimens of each composite were cut and tested.
TGA was performed using a scan range from 30 0C to 900 0C at
heating rate of 10 0C/min.

62
 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)
63
 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

64
 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)

66
 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

Stress at 300% 500

elongation decreases as the alternative filler loading
increases, except0
0 for
10 tomato
20 30 0 peels,
10 20 which
30 0 10 shows
20 30 an
0 increase
10 20 30 on modulus
Waste Filler (phr)
at 10 phr for micro35 size
25 15 particles.
5 35 25 15 5 35 25 15 5 35 25 15 5
Carbon Black (phr)

67
 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)

Ultimate elongation increased as the alternative filler loading increased 68

 Thermal Behaviour
TGA Results: Guayule Rubber
Carbon black
5 phr
35 phr

69
 TGA Results: Guayule Rubber
Sample Beginning mass Major mass loss % Loss
loss (c) range (c)

Guayule+carbon black 135.49 296.33 - 437.41 70.40

Guayule+CFA, micro, 5phr 148.90 292.52 - 442.48 70.87
Guayule+CFA, micro, 35phr 172.13 302.63 - 437.88 74.43
Guayule+ES, micro, 5phr 169.31 296.78 - 437.06 72.57
Guayule+ES, micro, 35phr 159.73 288.12 - 413.06 66.65
Guayule+GB, micro, 5phr 128.19 257.53 - 420.30 70.09
Guayule+GB, micro, 35phr 114.43 251.65 - 426.02 85.35
Guayule+TP, micro, 5phr 130.58 276.72 - 435.42 71.49
Guayule+TP, micro, 35phr 139.47 277.86 - 456.15 72.35

70
TGA Results: Hevea Rubber

Unfilled Hevea
Carbon black
5 phr
35 phr (Except
TP, 10 phr)

71
 TGA Results: Hevea Rubber
Sample Beginning mass Major mass loss range % Loss
loss (c) (c)

Unfilled Hevea 191.01 309.33 - 425.19 81.62

Hevea+carbon black 192.45 319.61 - 431.22 70.09
Hevea+CFA, micro, 5phr 174.17 294.55 - 444.82 71.43
Hevea+CFA, micro, 35phr 192.86 310.88 - 440.58 75.73
Hevea+ES , micro, 5phr 136.49 293.39 - 438.67 71.04
Hevea+ES , micro, 35phr 140.52 273.35 - 437.50 72.37
Hevea+GB, micro, 5phr 174.24 304.82 - 423.61 72.93
Hevea+GB, micro, 35phr 95.99 270.52 - 420.47 83.78
Hevea+TP, micro, 5phr 154.81 315.21 - 430.15 70.72
Hevea+TP, micro, 10phr 122.75 301.91 - 432.94 72.3
72
 Conclusion
The partial replacement of carbon black in natural rubber composites by
agricultural and industrial waste-derived materials reinforced the materials and
improved thermal stability.
Reduction of particle size increased ultimate elongation as well as stress at
300% elongation and tensile strength.
The increase of alternative filler loading in the composites increased ultimate
elongation but decreased stress at 300% elongation and tensile strength in
most cases.
Composites with superior or similar mechanical and thermal properties than
those of pure carbon black composites were obtained.

73
 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.

74