All-Cellulose Hierarchical

Composites:
Using Bacterial Cellulose
To Modify Sisal Fibres
A. Abbott, J. Juntaro & A. Bismarck
Polymer & Composite Engineering (PaCE) Group
Department of Chemical Engineering

Outline
Need for renewable materials
Composite philosophy
Innovative modification of natural

fibres
Cellulose matrix processing
Route towards green composites
Truly green hierarchical composites
Possible applications
2

Driving Forces To Green...

Growing environmental awareness
Stringent EOL legislation in the EU
Limitation of landfill capacity
Landfills count over 40% of plastic wastes
Endangering of wild life
Most plastics are not Biodegradable !

Legislation & Materials

EU agreed on a sustainable politic
End-of-life Vehicle directive 2000/53/EC
Legislation to encourage re-use, recycling and
other forms of recovery of ELVs

Landfill directive 1999/31/EC

Legislation to prevent or reduce negative effects
on the environment from land filling of waste

WEEE directive 2002/96/EC

Legislation to tackle rapidly increasing waste
stream of EEE by recycling of EEE and limitation of
wastes.

The Green Future

Strong need for new and reliable
materials
Requirements:
Be recyclable, re-usable and biodegradable
Obtained from sustainable resources
Yield properties comparable to common plastics
Be produced at low cost
Be resistant to weathering

A possible solution would be the use

of cellulose based composite
materials!
5

Composite Architecture (1)

Composite have at least 2 constituents
Fillers
Different purposes: reinforcement, fire-retardant,
colour, cost reduction, additives, etc...
Different sizes: from mesoscale to nanoscale

Polymer matrix
Aim: transfer load to fillers, hold and protect fillers
Type: thermosets, thermoplastics

Interface
Impact on composite properties

Composite Architecture (2)

Cross-section of randomly reinforced
biodegradable composite
Polymeric matrix

Interface
7

Natural fibre

Composite Philosophy

Hierarchical Composites

N-N Dimethylacetamide (DMAc), Lithium Chloride (LiCl), Sodium

Bacterial cellulose (BC)

Green Fibre Modification

Gluconobacter
fermentation
for
1

(1)
week

Strain BRP 2001(suitable for dynamic culture)

Modification during cellulose

production

Bioflow culture conditions: temp 37C ; pH 5.5 ; agitation 700 rpm ; aeration 5 l/min ; carbon source fructose

Green Fibre Modification

(2)

Green Fibre Modification

(3)

Fibre extraction from organic mass in 0.1 M NaOH 80C 20 min

Modification & Fibre

No
significant
mechanical
properties

Properties
loss after grafting procedure

Fibre conditioned @ 20C and 50% RH; test performed @ 1mm/min, gauge length 20mm

Modification & Fibre

Overall crystallinity increase after BC grafting
Crystallinity
Surface fibre modified by green grafting process

Crystallinity evaluated with Segals

Cellulose Matrix Processing

Matrix system obtained from MCC
Properties tailoring f(processing time)
Brittle to ductile type behaviour

Short fibres incorporation after

suitable dissolution time

Dissolution mechanism presented by MacCormick

N-N Dimethylacetamide (DMAc), Lithium

Matrix Crystallinity vs.

Processing

Matrix Toughness vs.

Processing

All-Cellulose Composites
Prop.(1)

Testing Standards ISO 527-2 @ 1mm/min

All-Cellulose Composites
Prop.(2)

Testing Standards ISO 527-2 @ 1mm/min

All-Cellulose Composites
Prop.(3)

Test configuration: single cantilever

Heating rate 5OC/min @ 1Hz in nitrogen

SEM All-Cellulose
Composite

SEM micrograph post cryo-fracture

SEM Hierarchical
Composite

SEM micrograph post cryo-fracture

SEM Hierarchical
Composite

SEM micrograph post cryo-fracture

Conclusion
Effective fibre surface modification with BC
Grafted fibre bulk properties unchanged
Improved interfacial adhesion & stress
transfer
100% cellulose composite
Hierarchical composite structure
Principle transferable to other systems
Fibre functionalization by cellulose
chemistry
2

Potential Applications

Adapted from book: Natural fibers, Biopolymer and Biocomposites; Mohanty

Acknowledgements
Dr Sakis Mantalaris (Head of Biological Systems Engineering
Laboratory)

Thanks For Listening!

Any Questions ?

Matrix & Thermal

Degradation

Heating rate 5oC/min under nitrogen

Bacterial Synthesised
Products(1)
Reinforcement: Bacterial Cellulose
(BC)

Highly crystalline, pure cellulose compound

Tayloring BC properties during fermentation

Czaja, et. al, Biomaterials 2006

Bacterial Synthesised
BC produced by Gluconobacter and
Products(2)

others
Ribbon-shape fibrils 8-50 nm diameter
Chemically identical to plant cellulose

Jonas & farah 1998

BC Production (2)

Youngs modulus of single

nanofibril:
78 GPa (similar to glass fibres)
(Guhasos et al.,2005)

89% Crystallinity
(Czaja et al.,2004)

BC network & Bacteria

3