Cold Temperature Performance of Guayule

Cold Temperature Performance of
Guayule (Parthenium argentatum)

Natural Rubber
By Griffin M. Bates, Graduate Research Associate, The Ohio State University
and Katrina Cornish
Overview
Natural Rubber
Hevea and Guayule
Cold Temperature Performance
Conclusions
24
Natural
Rubber
25
Natural Rubber (NR) is an elastomeric polymer with
the chemical name cis-1,4-polyisoprene.
Elastomers are utilized for enhanced flexibility,

toughness, and resistance to permanent deformation
under stress.
NR is extracted from rubber-producing plants,

primarily Hevea brasiliensis.
NR is utilized in over 40,000 commercial products

and is highly employed by the automotive industry.
Synthetic rubbers are available, but do not match the

mechanical properties of natural rubber. 26
Est. World NR consumption by 2025: 17 MT.
Expected global natural rubber shortage of 1.5-3.0 MT by 2020.
Over 2,500 plant species produce NR, but the commercial industry is dependent
upon Hevea brasiliensis.
Economic growth in BRIC emerging economies is driving increasing demand for
NR.
Hevea plantations converted for crops with earlier maturation age and lower
labor requirements (e.g. palm oil).
Cents per pound Price of Natural Rubber from 1981-2011
Total Global Production of World Natural Rubber in Thousands of

Tons (Source: International Rubber Study Group) 27
Hevea and
Guayule
28
Hevea Guayule
Tropical species of tree Desert-dwelling shrub species
Limited to warm, humid locales Cold tolerant; requires well-drained soils
Rubber contained within laticifers in the bark Rubber contained within individual bark
tissue. parenchyma cells
Tapped for rubber on plantations in a labor- Harvested for rubber in a mechanized process
intensive process Contains 1.1% of the protein found in Hevea
Hevea latex proteins are the cause of Type I Proteins do not cross-react with Hevea
latex allergy antibodies
29
Hevea Guayule
Rubber molecule has a highly-branched Rubber molecule tends to form linear polymer
polymer chain. chains.
High branching and high molecular weight Grafting can be used to increase branching and
allow for cross-linking during processing for formulations can be made to mimic Hevea
increased strength of material. mechanical properties.
Linear molecules permit longer elongation, lower

modulus, and increased flexibility.
30
Previous Research
Cornish and Wood (2002) in Journal of Polymers and the Environment.
Intact Hevea and Guayule rubber particles flash-frozen between metal plates at -196C, pulled
apart.
Images taken using SEM at the USDA in Albany, California.
Hevea rubber particles underwent shear fracture while Guayule rubber particles underwent
ductile fracture.
Hevea Guayule
Note: Scale bar in each image (bottom right) is one micrometer 31

Guayule rubber particles photographed after top freeze-fracture plates were removed to induce a fracture plane. Key: a,b
particles are in situ in bark parenchyma (bars = 3um); c, particles purified from the plant in Tris buffer (bar = 2um); d,
particles purified in 0.2% ammonium hydroxide (bar = 1um). 32
Cold
Performance
33
Purpose and Objectives
Determine the effects and mechanisms of cold temperature

performance of Guayule natural rubber in comparison to Hevea natural
rubber
Determine the effects of both rubber and non-rubber components of

each source to better understand each components' role in the physical
and mechanical properties of natural rubber, paritcularly in cold
performance.
Use modern manufacturing techniques and products to determine

what effects processability and product design have on cold
temperature performance 34
Equipment and Techniques TA Instruments DMA Q800 was used to determine
the glass transition temperature (Tg) of the
materials (boundary between plastic and elastomer
behavior)
Temperature sweep using a tension clamp at 1 Hz

down to -100C (some to -150C)
Three means of determining Tg:
Storage Modulus (stored energy)
Loss Modulus (energy dissipated

as heat)
Tan Delta (loss rate of energy) 35

Results
In Latex Dipped Films: Guayule Films
Protein included Protein removed
6 6
Guayule has a slightly lower
Modulus (Mpa)
Modulus (Mpa)
5 5
Tg and storage modulus than 4

3
4
3
Hevea. 2 2
1 1
-120 -100 -80 -60 -40 -20 0 -120 -100 -80 -60 -40 -20 0
Protein removal decreased Temperature (C) Temperature (C)
modulus (increased flexibility)

Hevea Films
in both Hevea and Guayule. Protein included Protein removed
6 6
Modulus (Mpa)
Modulus (Mpa)
Modulus is inversely 5
4
5
4
correlated to protein content. 3 3
2 2
1 1
Deproteinized Guayule has -120 -100 -80 -60 -40 -20 0 -120 -100 -80 -60 -40 -20 0
the lowest modulus. Temperature (C) Temperature (C)
36
Results
Guayule Hevea
Key:
GNR = Guayule NR
PRGNR = Protein removed
MRGNR = Membrane removed
HNR = Hevea NR
Gel-free = Hevea w/o gel
37
Key:
GNR = Guayule NR
HNR = Hevea NR
Guayule Hevea 38
Guayule Hevea
Key:
GNR = Guayule NR
HNR = Hevea NR
39
Key:
GNR = Guayule NR
HNR = Hevea NR
Guayule Hevea 40
Conclusions
41
Summary of Results
Guayule is more flexible than Hevea under cold temperatures.
Guayule has a lower glass transition temperature (Tg) as
evidenced in both latex films and solvent-casted films.
Removing protein lowers the modulus (increases
flexibility/decreases stiffness) of both Hevea and Guayule natural
rubber in dipped latex films.
In solvent-cast samples, removing membranes had a minimal
effect on Tg but increased the storage modulus.
Lowering the molecular weight lowers the storage moduli of
both Hevea and Guayule films.
42
Conclusions
Guayule retains elastomeric properties to -196C
Protein content is correlated to storage modulus
Protein content is involved in rubber memory
A protein threshold may exist for significant differences of
Storage Modulus
Glass transition temperature (Tg) may be affected by
lipids
43
Future Work
Standard Formulations
Protein Gradients
Guayule/Hevea Blends
Comparison of Latex & Rubber Products
Synthetics Comparisons
44
Acknowledgements
Thank you to the conference organizers for this opportunity

This work was supported by an OARDC SEED grant, the Institute of
Materials Research at The Ohio State University, and The Ohio Third
Frontier.
This work is also supported by the USDA National Institute of Food,
Agriculture, Hatch project 230837.
Thanks to J. Lauren Slutzky for rubber knowledge, latex films, and
DMA expertise.
Thanks to Eun Hyang Han and Shirin Mohammad Ali Monadjemi for
preparing natural rubber samples; as well as Jared Baisden for some
initial work on this project.
45
References
1. Cornish, Katrina (2001) Similarities and differences in rubber biochemistry among plant
species. Phytochemistry. 57. 1123-1134.
2. Cornish, Katrina and Wood, Delilah F. (2002) Visualization of the malleability of the rubber
core of rubber particles from Parthenium argentatum gray and other rubber-producing
species under extremely cold temperatures. J. Polym. Environ. 10.4, 155-62.
3. D.J. Siler, K. Cornish, R.G. Hamilton (1996) Absence of reactivity of IgE antibodies from
Hevea brasiliensis latex allergic subjects with a new source of natural rubber latex from
guayule (Parthenium argentatum). J. Allergy Clin. Immunol. 98, 895-902.
4. Cornish, K., & Blakeslee, J. (2011, November 2). Rubber Biosynthesis in Plants. Retrieved
January 6, 2015, from http://lipidlibrary.aocs.org/plantbio/rubber/index.htm.
46
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Cold Temperature Performance of Guayule

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Cold Temperature Performance of

Guayule (Parthenium argentatum)

Hevea and Guayule

Cold Temperature Performance

Elastomers are utilized for enhanced flexibility,

NR is extracted from rubber-producing plants,

NR is utilized in over 40,000 commercial products

Synthetic rubbers are available, but do not match the

Total Global Production of World Natural Rubber in Thousands of

Linear molecules permit longer elongation, lower

Note: Scale bar in each image (bottom right) is one micrometer 31

Determine the effects and mechanisms of cold temperature

Determine the effects of both rubber and non-rubber components of

Use modern manufacturing techniques and products to determine

Temperature sweep using a tension clamp at 1 Hz

Storage Modulus (stored energy)

Loss Modulus (energy dissipated

Tan Delta (loss rate of energy) 35

Tg and storage modulus than 4

modulus (increased flexibility)

Comparison of Latex & Rubber Products

Thank you to the conference organizers for this opportunity

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