Bio-based Composites made from

Agrowaste
Lucas Whale & Suviti Chari
Maastricht Science Programme, NL

Maastricht Science Programme

 Is there a demand for this research?
• Potential to substitute petroleum based product

• Polyolefin/glass fibre composites

(95% of composites)

• Automobile industry;
+ lightweight
density E-glass =2.6g/cm3 , Natural Fibre = 1.3-1.5g/cm3
+ 60% less energy than for glass fiber manufacture
+ reduce concerns on supply chain (hybrid composites)

•
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 Ford Motors Wheat straw/PP composite

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Composites
• Characteristics of each component work synergistically to
give rise to improved properties of the composite when
compared to individual parts.

• Light weight structures with high stiffness and tailored

properties  Save on weight and energy

• Nature remains the ”expert” on composites.

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 Hammering Home a Lesson!

Acceleration= 10,000g
Speed = 23m/s from stationary position
Force = > 700N!!

“MANTIS MURDER SHRIMP (Slow Motion)” Smarter Everyday https://www.youtube.com/watch?v=LXrxCT0NpHo

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 Composites
• Focus on sustainability, renewability and cost-
effectiveness.
• We know what constituents are involved and we can
replace fossil sourced materials with more biobased
materials.
• Biodegradable and do not pollute the environment.

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Biocomposites
Made from natural fibre and petroleum-
derived non-biodegradable polymers

OR Hemp fibers and polyethylene

From synthetic fibre (glass/carbon) and biopolymers

(PLA/PHB)

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 Green Composites
• Derived from plant-derived fiber (natural/biofiber) and
crop/bioderived plastic (biopolymer/bioplastic)
• More ecofriendly and sustainable
• From a renewable source and is completely biodegradable
• Examples found in applications that do not involve very
high stresses, for instance, as non-structural parts for the
automotive and railway industry

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 Green composites- Natural fibers
• cellulose, hemicelluloses, lignin, pectin, and wax
• Composition depends on
geographic location
where the plants are
grown.
• All natural fibers have
the same constituents,
but with different
proportions, which
makes fibers behave
differently.
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 Green composites- Natural
fibers
A closer look
Lignin

Cellulose
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 Green composites- Biopolymers
• Term is used to convey polymer’s biobased source and
biodegradability

• Biopolymer ≠ polymer produced by living organism (e.g.

DNA, Bacterial PE) in this context

• Due to degradability, they are relatively short-lived in their

application

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 Bioplastics – Why PLA?
• In cases where the biodegradable polymer is derived from
renewable resources (i.e., a biopolymer), a further
advantage arises because
Composite is totally derived from renewable raw
materials.

• Lactic acid-based polymers (polylactides) are polyesters

made from lactic acid

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 Natural Fibres
• Mechanical property enhancement relative to the parent
polymer
• Improved thermal stability
• Biodegradability
• Net cost reduction resulting from the partial replacement
of polymer by natural fibers.

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 Agricultural Waste feedstock
• Many other examples of natural fibers exist, another
sustainable source is “agrowaste”.

• Agrowaste- not only plant matter but also wastewater,

manure etc.

• Focus of this presentation is on pineapple leaf fiber

(PALF) and other agrowastes in combination with
polylactic acid.

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 Relevant research papers

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 Origins: Pineapple Leaf Fibres
• Thailand is the world's leading producer of pineapples,
though the fruit is not native to Southeast Asia

• Fibres are obtained from the leaves via shredding by

mechanic blades

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 Fiber properties & predicted effects
• Tensile strength, elongation,
elasticity, degradation and
PALF Wheat
friction properties. Straw
Cellulose 70-80% 75-85%
(including
• Compositions vary slightly hemicellulose)
Lignin 5-12% 10-15%
• Polymers also exhibit these
characteristics.

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Challenges with PALF/PLA and other
agro residue/PLA
• Thermoplastics are non-
polar, hydrophobic whilst
Natural Fibres are polar,
hydrophilic

• Poor adhesion between

mixture components

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 Possible Solution: Coupling Agents
• Substances used in small quantities to treat a surface so
that bonding occurs between it and other surfaces.
• Maleic Anhydride (MA) possess bifunctional groups [-
(CO),O-] that is able to interact with polar [-(OH)] of
cellulose and lignin

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 Additives
Necessary;

Normally
used Radical
Initiator is
TBPB

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Lu JZ, Wu Q, McNabb HSJ (2000)

 Processing routes
Fibres Ground
• PALF simply chopped
• Wheat Straw ground using Cutting Milll
Drying
•PALF & Wheat straw dried (80C, 4hours)

Mixing of Additives
• For PALF/PLA with MA Two Roll Mill used for mixing (140C)

Compounding
• Using Twin Screw Extrusion
• Uniform 120C (PALF), 180C (Wheat Straw)
Sample Specimen for characterization of mechanical properties
•Injection moulding

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 Thermal Stability of PALF (TGA)
• Initial weight loss at 30-100° C  water
• Kaewpirom et. al attributed Cellulose, hemicellulose and
lignin degradation at 250° C
• Non-cellulose decomposition 330° C onwards
• Char residue 10% wt.

362°C

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 Thermal Stability of PLA
• 365 °C  heat resistant additive
in PLA decomposition

• 394 °C  PLA decomposition 394°C

365°C

Tg
Tm

• Semi-crystalline nature
• Necessary to
determine processing
temperatures

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 Thermal Behaviour; PALF/PLA Composite

396°C
350°C

• All composites thermally stable up to 225°C

• Lower PALF content greater thermal stability
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 Tensile Properties
• Increasing tensile strength, Young’s (tensile) modulus and
higher elongation at break with increasing PALF %
• Above a threshold of 40% fibre, tensile strength and
elongation at break drops.
• Poor adhesion  Aggregation of PALF  poor
dispersion

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What’s happening with MA composite?
• Single test on 40% PALF/PLA/MA showed increased
stiffness (E) but decreased strength and lower elongation at
break.
• Concentration ∝ coupling effectiveness
1.Formation of by products
2.Increase in conc. of unreacted MA
3.Interference with coupling reaction

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Maldas, D., Kokta, B., & Daneault, C. (1989).

Kaewpirom et. al vs. Mohanty et. al
• Different PLA grades, processing temperatures used.
Comparative analysis of mechanical properties not
applicable.
• Mohanty et. Al used higher temperatures; no TGA/DSC
analysis on unprocessed PLA and PALF

where Hybrid = 10% soy stalks + 10% corn stover + 10% wheat straw

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 Tensile properties
• Addition of natural
fibers  decrease in
strength and increase in
modulus.
• No significant
difference in the tensile
properties of the
composites.
where A= PLA, B= Soy stover, C=, D= Wheat straw, E= hybrid

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 Tensile properties
• Agricultural residues may
be substituted or
combined without
compromising mechanical
performance

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Relevant Findings
Contribution to the biobased economy?
• Green composites represent a contribution to the
transition to a biobased economy.

• Throughout history we have witnessed the advantages of

combining materials to yield enhanced properties.

• Present day: high demand for high performing, readily

available materials.

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Contribution to the biobased economy?
• Applications do not involve very high stresses, non-
structural parts.

• Consumers may not want to compromise a product’s

functionality.

• Small-scale implementation has proven to be marketable.

Price remains a factor.

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 Outlook?
• Research in genetics, biotechnology and processing of
natural fibers.

• Research into higher tensile strength & heat resistant

biodegradable polymers.

• Depth and timespan of this research does not come close

to that of fossil-based equivalents.

Maastricht Science Programme 1-2

 References
• R. M. N. Arib, S. M. Sapuan, M. A. M. M. Hamdan, M. T. Paridah, and H. M. D. K. Zaman, “A literature review of
pineapple fibre reinforced polymer composites,” Polymers and Polymer Composites, vol. 12, no. 4, pp. 341–348,
2004.
• Lu JZ, Wu Q, McNabb HSJ (2000) Chemical coupling in wood fiber and polymer composites: a review of coupling
agents and treatments. Wood Fiber Science 32:88–104
• Maldas, D., Kokta, B., & Daneault, C. (1989). Influence of coupling agents and treatments on the mechanical
properties of cellulose fiber–polystyrene composites. Journal Of Applied Polymer Science, 37(3), 751-775.
http://dx.doi.org/10.1002/app.1989.070370313

Maastricht Science Programme 1-2

 APPENDIX
Kaewpirom
• Many grammar, analysis errors,
contradictions within results
• Tested effect of MA (interesting
idea) but failed to test different
concentrations which is crucial. No
mention of other additives.
• Pilot product
• Density study missing
& Mohanty
• Useful to do tests on individual
starting products. Only DSC done
on PLA
• Confusing labelling of graphs
• Does not focus on solving
interfacial adhesion
• Writer was knowledgeable about
theory; results matched discussion

Further test on chemical modifications for improvements!

Maastricht Science Programme 1-2
 Variability of results

• Degree of filling – fibre length– fibre morphology – orientation of fibre bundles - degree of
cellulose polymerization.
• Properties of specific polylactide (MM, lactide content) - processing condition (catalyst,
predrying, processing tmemperatures)