Bioplastics Compounding

Bioplastics

Plastics which are biodegradable and/or partly or wholly derived from renewable resources

Bioplastics
Many different types
starch, processed starch and starch blends fermentation products from plant sugars and starches polymers produced directly by microbes blends with renewable resource derived polymers PE and PP from renewable resources (sugarcane ethanol)
have identical properties to standard PE and PP

Bioplastics

Bioplastics
Diverse range of polymer types Wide range of characteristics for some bioplastics depending on details of chemistry. e.g.
Isomers (eg l-PLA vs d-PLA) Co-monomers Chain branching vs linear

Starch is processed to produce thermoplastic starch (TPS)

cooking with water plasticization reaction extrusion

Many proprietary blends and patents Generalizations, even for one polymer type, are not possible

Blending Bioplastics
Sustainability
Renewable content Biodegradability Greenhouse gas Energy & water

Performance
Mechanical Water resistance Gas barrier Colour & appearance

Processability
Temp stability Melt strength Rheology

Cost

Blending Bioplastics

Some examples of commercial bioplastic blends

Blending Bioplastics
Example: CeralloyTM Eco HD
50% non-renewable HDPE 50% CerestarchTM thermoplastic starch

kg CO2 eq /kg

Source: www.cerestech.com

Plasticizers

Plasticizers
Addition of plasticizers is often used to lower Tg and melt viscosity Improve processability and properties (impact, low temperature flex) Plasticizers should be:
low molecular weight and high b.p. low viscosity which is not temperature sensitive compatable with base polymer biodegradable made from renewable resources

Plasticizers
Problems can occur with blooming and leaching of very low m.w. or incompatible plasticizers Water is used as a plasticizer for starch
Limits processing temperature Evaporation over time leads to embrittlement

Plasticizers

Some plasticizers used in bioplastics

Processing

Processing
Biodegradable polymers must have relatively low main chain bond strengths to allow breakdown by microbes
e.g. starch amylopectin

This leads to low thermal degradation temperatures

Processing
Generally hygroscopic and moisture content needs to be controlled Degradation can produce corrosive acids Minimize process temperatures and residence times Degradation can occur in extruder dead zones Purge with PE before shut down

Processing

Processing window

Processing
Good mixing required
Twin screw co-rotating extruder

Feeding may be difficult

Hydrophyllic starch surfaces tend to cause powders to clump Control moisture content

Mixing hydrophyllic starch and other bioploymers with hydrophobic polymers (e.g. PP, PE) requires compatibilizers

Processing
liquid injection biopolymer polymer
(non-renewable based)

plasticizers
(renewable based)

mixer

plasticizers
(non-renewable based)

thermoplastic starch fillers

(organic & inorganic)

devolatilization extruder pelletizer compound

Sustainability Performance Processability Cost

additives

Chain Extenders
PLA and other condensation polymers suffer from chain scission due to heat & shear Chain extenders can re-join chains
Improves melt strength Improves rheology Aids recycling

Consider for blown film, thermoforming and foam processes

Chain Extenders
Clariant CESA-extend
Biodegradable Derived form renewable resources

Arkema Biostrength 700

Not biodegradable

Source: Bioplastics 03/08 p35

Mechanical Properties

Property Profiles

Impact Modifiers
Du Pont Biomax Strong 120
FDA compliant toughening agent for PLA packaging

Rohm & Haas Paraloid BPM-500

Improves impact & tear strength of PLA film Maintains clarity Acrylic based

Sukano PLA im S550

Improves resiliance and toughness in transparent PLA

Colour

Colour
Many bioplastics, especially starch based, are opaque with a yellow/brown colour This may be exacerbated with processing High intensity colours will not be possible PLA can have excellent clarity Pigment systems need to maintain biocompostability and be non-toxic

Colour
Clariant Renol-naturTM pigment systems Biodegradable Natural sources:
Orange from tumeric root Yellow from tropical flowers

Lower light resistance than conventional pigments

Colour
PolyOne OnColor BioTM Colorants Suitable for many bioplastics Certified for compostability

Colour
Teknor Colour Company Colour concentrates for PLA bottles, film, sheet, profiles and injection moulding Various carrier types:
Biodegradable PLA Biodegradable (non-renewable) polyester Non degradable PET for durable applications

Other Additives

Other Additives
PolyOne OnCap additives for use in bioplastics Antistat Antiblock UV stabilizers Anti-fog Nucleation should also be considered as slow set-up times are a problem with some bioplastics
e.g. PLA, PHAs

Biocomposites

Biocomposites
Use of renewable and/or biodegradable fillers or fibres to make composites with bioplastics Inorganic fillers e.g. talc, calcium carbonate (chalk)
Small increase in properties Increase in s.g. Acceptable degradation products for compostability tests Reduce renewable content (which is based on carbon)

Organic fillers e.g. wood flour, ground peanut husks

Increase renewable content

Natural Fibres
Addition of natural fibres provides reinforcement and useful increases in strength & stiffness Increased renewable content Natural fibres include:
Flax Hemp Kenaf Sugarcane bagasse Wood Jute

All cellulose based, but with varying amounts of lignin and other materials, including silica

Additives

REINFORCING NATRAL FIBRES

NON WOOD NATURAL/BIOFIBERS WOOD FIBRES
GRASS FIBRES

STRAW FIBRES

BAST

LEAF

SEED/FRUIT

Kenaf, Flax, Jute, Hemp Corn/Wheat Rice Straws

Cotton, Coir

Soft and Hard Woods Bamboo Fibre, Elephant Grass

Sisal, Pineapple Leaf Fibre

Natural Fibres

Specific Youngs Modulus

Source: A.K.Mohanthy et al,Natural Fibres, Biopolymers and Biocomposites,CRC, 2005, and others

Biocomposites
Addition of natural fibre to increase stiffness and strength Natural fibre properties are lower than for E-glass Density is also lower Higher fibre content is required for similar properties Can provide light weight and high renewable content Aim to retain as much fibre length as possible
Downstream feeding Low shear

Effects of additives on mechanical properties

Matrix polymer TPS a) Modulus (MPa) 47.2 Reinforcement Volume fraction (%) 5 Modulus of composite (MPa) 145.5

Ethanolamine activated montmorilonite Medium size fibers b) Medium size fibers Cellulose microfibrils Recycled newspaper flax montmorilonite Waxy maize starch crystals/

TPS TPS TPS PLA PLA TPS TPS

87 87 80 2700 3500 81.5 45

5 12 10 10 30 20 5 d)

190 522 c) 3000 5300 8000 850 298

a) Thermoplastic starch b) 2-3mm in length c) as a comparison the author also reported that HDPE module only increased two times with 12% fibres, d) 20 % glycerol as a plasticiser

Biocomposites
Natural fibres need to be processed to obtain a fibre length range, generally 1 5 mm with low particulate level Surface treatment to improve bonding to matrix
Surface fibrillation, corona, plasma Alkaline swelling Acetylation, silane, isocyanate reactions

The environmental effects of chemical methods needs to be considered!

Biocomposites
Compatibilizers can be used to improve bonding of hydrophobic fibres to hydrophyllic matrixes (e.g. PP) Clariant Licocene PP MA 6452 TP
Maleated PP wax

Biocomposites

Some examples of commercial biocomposites

Biocomposites

PLA/kenaf fibre biocomposites developed by NEC and Unitika Ltd for mobile phone housings
Source: K.Inoue, NEC, Bioplastics 2007 Conference paper

Certification

End-of-Life Environments

Certifying Bioplastics - US
Testing to ASTM D6400 or D6868
Active municipal or commercial composting Inherent biodegradability similar to natural biopolymers over 180 days (or longer with additional tests) Disintegrates into small pieces (<2mm) No ecotoxicity

Reviewed and certified by Biodegradable Products Institute (BPI)

Certifying Bioplastics - Europe

Testing to EN 13432
Controlled composting with elevated temperature and aeration Inherent biodegradability similar to natural biopolymers over 180 days (or longer with additional tests) Disintegrates into small pieces (<2mm) No ecotoxicity

Reviewed and certified by

DIN Certco, or AVI Certest