Dr. Rob Elias

Environment Centre Wales, Bangor University

July 14th 2009

What’s a pretty biopolymer?

Composites and Biopolymers

• What’s a pretty biopolymer?– Types

– Markets

– Applications

• New equipment for KTC

• Information on biopolymers and regulations– Websites

– Standards

Biopolymers- some definitions

• Based on renewable raw materials– Agricultural resources: sugar, starch, vegetable oils, cellulose

– Food residues

• Degradable polymers according to standards– Synthetic oil-based polymers with

– Certain degrees of inherent biodegradability

– Or chemically modified plastics

Biopolymers

• Biodegradable and bio-based

– Polylactide acid (PLA) from NatureWorks LLC

– Starch based materials: mater-bi from Novamont

– Polyhydroxyalkanoates: PHA/PHB from Mirel, Tianan

– cellulosed based materials: NatureFlex films from Innovia

– PLA/Starch blends: Ecoflex from BASF

Biopolymers

• Biodegradable but not bio-based

– Polyesters (BASF)

– Polyvinylalcohol

– Polycaprolactone (Perstorp)

Biopolymers

• Bio-based but non-biodegradable

– Not in the market yet but will come soon

– Polyethylene

– Polyvinyl chloride

Market situation

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500000

750000

1000000

1990 1995 2000 2005 2010 2015

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cap

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(Bioplastics 2007/2008,Processing parameters and technical characteristics)

Market situation

• Very small fraction (less than 0.5%) of the global plasticmarket

– Bioplastics: 750,000-1,000,000 tonnes in 2008

– Plastics: 48,000,000 tonnes

• Very fast growing market

– Over 20% per year

– Expanding of current existing biopolymers

– Establishing of new bio-based polymer plants

Commercial available biopolymers

• Aliphatic polyesters (e.g. Polylactic acid (PLA))

• Starch polymers (e.g. Mater-bi)

• Cellulosic and whole crop polymers (e.g. Cellophane)

• Microbially synthesised polyhydroxy alkanoates(e.g.Poly-3-hydroxybutyrate (PHB))

Polylactic acid

• Produced by the fermentation of carbohydrate material

• Glucose derived by hydrolysis from starch

• Two stereoisomers:

– L-Lactic acid, naturally in numerous organisms

– D-Lactic acid, very rare in nature

• Different grades available depending on molecularweight, macromolecular structure & degree ofcrystallisation

Polylactic acid

• Has the highest modulus of elasticity of all the polymers,similar to PP

• Leading producer: Natureworks (Cargill)

• Price at $2-2.50/Kg with possibility to improve by 2010

• Not suitable for home composting

• Compostable by industrial processes only

Polylactic acid

N/a50 (2004)Toyota-Eco-PlasticToyota

3.0FibrolonGermanyFKUR

N/aN/aLaceaJapanMitsui ToatsuChemicals

1.8-2.91Hycail HM, Hycail LMHycail

N/aN/aMirelUSMetabolix

1.8-2.4140Natureworks(Mitsui Lacea in Japan)

USNatureworks(Cargill)

N/aN/aBiopearlsNetherlandBiopearls

4.8N/aEcovioGermanyBASF

10–120.05Biomer

Price (€/kg)Capacity(kt pa)

Trade nameRegionProducer

Starch polymers

• Starch polymers are based on gelatinized starch frompotato, corn, wheat or tapioca.

• Two natural polymers in starch: amylopectin and amylose

• Pure starch provides brittle and friable materials

• Can be improved increasing degree of amorphous regionsor by blending with other polymers, nanofillers, plasticisersand fibres.

Starch polymers

• Leading producer: Novamont Spa in Novara, Italy• Started research in 1989 with capacity of production to

20,000tpa.• Average price at €2–3 per kg• The cost of starch is higher in Europe than in the rest of

the world.• Rodenburg’s polymer: Solanyl, at €1 per kg

– Cheaper raw materials: potato waste– Simpler process

Starch polymers

naVegematFranceVegeplast

140SolanylNetherlandRodenburgbiopolymers

1.4-4.212Starpol, BioplastUKStanelco

NANAEcoFoamUSNational Starch andChemical

1.3-4NAPearlsEuropeBioPearls

1.50-4.520a)Mater-BiItalyNovamont

3.50-4.5Envar, Bioplast,Bioflex,

GermanyBiotec

2-310(17 in 2007, 100 in

2015)

BioparGermanyBiop BiopolymerTechnologies

2006Price

(€/kg)

2006Capacity (kt pa)

Trade nameRegionProducer

a)in-house production in 2002 was 12 kilo tonnes (kt); licensed production elsewhere 13 kt

Cellulosic polymers

• High price of €3-4/kg due to complicated productionprocess

• Could drop by developing bacterially produced cellulose

• Leading producer: Innovia, a UK-based company

• The brand name NatureFlex

• High barriers to gases and aromas

Whole – crop polymers

• High in natural polymers:starch/cellulose/hemicellulose/lignin

• Can be extruded to a plastic material

• Leading producer: Vegemat, in the south France

• Very cheap, €1/kg

• high flexural modulus

Cellulosic and whole – crop polymers

1AsiaEcopack

1AsiaGrenidea

15VegematFranceVegemat,

20CellulonUSWeyerhauser,

2.1-4.5BioFlexGermanyFKuR

3.3NatureflexUKInnovia

5.0BiocettaItalyMazzuccheli

NaTeniteUSEastman

Price(€/kg)

Capacity(kt p.a.)

Trade nameRegionProducer

Polyhydroxy alcanoates (PHA)

• Expensive: €10-12/kg

– High raw material costs,

– High processing costs

– Small production volumes

• Best studied polymer: polyhydroxybutyrate (PHB)

• High mechanical and barrier properties

• Market focus for medical implants etc

• Could be used in packaging

Polyhydroxy alcanoates

N/a160N/aN/aGermanyGoodfellow

N/aN/aN/aN/abiopolUSMonsanto

N/a6.5N/aN/aEnmatChineseTianan BiologicMaterial

9100.05USPHB Industrial

10-150.50.5GermanyBiomer

N/a0.8-1.5N/aN/aNodaxUSProcter & Gamble

2.510-1250,0005USMetabolix & ADM

2015Price

(€/kg)

2006Price

(€/kg)

2015Capacity(kt p.a)

2006Capacity(kt p.a)

Tradename

RegionProducer

Mechanical properties of polymers

103150PS

501500PVC

6001500PP

650100LDPE

500750HDPE

750750

450500PBS a)

701500

223000Cellophane

203250PHB

500350

300500

202500Mater-bi

503500PLA

Elongation, %Modulus, MPaPolymers

a) Polybutylene succinate

Applications

Applications in packaging

By processing method Thermoformed trays and pots for food & non-food; Blow moulded bottles and pots; Pulp moulded trays; Injection moulded trays and cups Bags; Flexible films included twist film, shrink wrap, flower wrap; Coating Loose fill or moulded protection; Other applications.

Pulp moulded trays from AgroResin(Grenidea, Singapore)

Bags made from Mater-Bi (Novamont)

Films (Innovia, UK) for muesli

APPLICATIONS BEYOND PACKAGING

• Medicine (PHB/PHA)

• Automobile: tyres, brake pedal and door case

• Construction

• Aerospace: carbon fibre/PLA composites

• Thermal and acoustic insulation

• Furniture

• Garden products

• Mobile phone cases

• Clothes/bedding

Bioplastics for Medicine

• Biocompatability withhuman tissues and organs

• Bioresorbable anddegradation in the body

• Controllable for drugrelease

• Short lifetime

• disposable

surgical sutures

modified cardiostimulatorsfor cardio-vascular surgery

Bioplastics for automobile: brake pedal

• Natural fibre composites

• Increase the strengthsignificantly

• Passed all the pedal tests

• Suitable for other parts:door panel, gear box

The compostable and biodegradable E-Tray

www.modo.co.uk

‘we now have a product thatticks all the right boxesfrom an environmental

and commercial point of view.’

Source: MEDIAPACK SUMMER 2008

Made from starch

Roof tiles: cellulose polymer composites

(imported by GeoRoof Danmark)

Carbon fibre/PLA composite for aerospace

• Fibre volume fraction: 40% (weight)• To increase composite’s strength over

70%• To add durability• To result in a higher heat conductivity

than stainless steel• Used in aircraft parts, high-performance

vehicles

EMEGA Soy-Based Foam Insulation

• Manufactured from soy beans& isocyanate

• Expands to 100 times itsvolume

• Completely fill every space• Void creating a barrier and

thermal seal

http://www.emegabuild.com/

keeps your heating and cooling costs low

Chair made from biocomposite materials

Fabricated atRisø National Laboratory,

Denmark

Made from 100% plant material

Garden products

Highly transparent wrappermade from PLA

Biolice product,Made from whole cereal grains

Mobile phone cases

Made of PLA bioplastics reinforcedwith kenaf fibres

by NEC, UNITIKA and NTTDoCoMo

FOMA(TM) N701iECO phone

Clothes/bedding

Made from PLA, NatureWorks

Challenges

• Many biopolymers need to have improved

– Barrier properties to gases

– Strength (more flexiable)

• Need to develop new processing additives

Equipment

Melt Flow Indexer (MFI)

• A measure of the ease of flow of the meltof a thermoplastic polymer• Measures the Melt-Flow Rate (MFR) andMelt-Volumetric Rate (MVR)• Provides 20 test results over the selectedtravel distance:

-Density at test temperature,-Viscosity-Shear stress

• Most widely used parameters forthe quality control of polymers

26 mm co-rotating twin screw extruder

• Modular Clam Shell Barrel• Barrel length at 40 (L/D)• 15KW motor• RPM of 800

Barrier characterisation equipment

• Oxygen permeation (OTR)

• Water vapour permeation instruments(WVTR)

• Gas permeability tester

Oxygen permeation instrument

• Test range: 0.05 to 2000 cc/m2/day

• Temperature controlled: 10-40OC

• RH controlled: 0%, and 35%to 90%

• Standard Testing:

Film: dry or ambient

Packages: dry or ambient

Water vapour transmission rate (WVTR)

• One station WVTR tester• Simply to use• Testing range: 0.1-1000gm/m2/day• Repeatability: ±0.05gm/m2/dayabsolute or ±2% relative• Temperature range: 10-40OC

Gas permeability tester

• Capable of detecting Air,Oxygen, Nitrogen, Carbon Dioxide,light Hydrocarbons and inert gases• For testing film, foils, laminates,paper from 0.01-2mm• Mearsuring range:1-10,000 ml/m2 day

Information and regulation

Useful website

• http://wales.gov.uk (WAG)• http:// www.defra.gov.uk• http://www.berr.gov.uk/• http:// www.nnfcc.co.uk• http://www.innovateuk.org/ (TSB )• http://www.bioplastics24.com/• http://www.biopolymer.net/• http://www.packagingknowledge.com/

EU Regulations

• DIRECTIVE 94/62/EC (1994):EUROPEAN PARLIAMENT AND COUNCIL DIRECTIVE 94/62/ECof 20December 1994 on packaging and packaging waste

• Amended by:► Regulation (EC) No 1882/2003 of the European Parliament and ofthe Council of 29 September 2003► Directive 2004/12/EC of the European Parliament and of the Councilof 11 February 2004► Directive 2005/20/EC of the European Parliament and of the Councilof 9 March 2005

UK Regulations

• BERR leads on single market aspects

• DEFRA leads on UK waste policy and all other aspects

• Packaging (Essential Requirements) Regulations 2003

• Amended by► Regulations 2004 (SI 2004 No 1188)

► Regulations 2006 (SI 2006 No 1492)

Standards

• EN 13427:2004: Packaging and the environment• EN 13429:2004: Packaging – Reuse• EN 13430:2004: Packaging - Requirements for packaging: recoverable by

material recycling

• EN 13432:2000: Packaging - Requirements for packaging:recoverable through composting and biodegradation

• EN 13431:2004: Requirements for packaging: recoverable in the form ofenergy

• EN 13428:2004: Packaging - Requirements specific to manufacturing andcomposition

• CEN/CR 13695-1:2000 Packaging – Requirements, part 1• CEN/TR 13695- 2:2004 Packaging – Requirements, part 2

Thankswww. bc.bangor.ac.uk