BIOBASED & BIODEGRADABLE PLASTICS 101

Ramani Narayan narayan@msu.edu

& MATERIALS SCIENCE

www.msu.edu/user/narayan
www.ktmindustries.com www.ecosynthetix.com www.biopolymerinnovations.com www.bioplasticpolymers.com
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

MATERIALS FRONTIER
DRIVERS FOR MATERIALS TECHNOLOGY SHIFTS
Traditional Materials Synthetics
Aramids Polyester Nylon Vinyl Nano materials Paradigm shift

Environmentally Responsible Materials

Green design

Industrial Ecology SUSTAINABILITY Life Cycle Assessment (LCA) Life Cycle Costing

Value in Use
Feathers Fur Wool Cotton

Silk

6000 BC

1760

1950

2000

Time
BIOBASED MATERIALS

Natural Ingredients Labor Intensive Attractive Aesthetics

Cheap petroleum Ease of manufacture Low labor input Excellent functionality

Biodegradable

bio based (renewable resource) Recyclabl -- recycling friendly Non-polluting Energy efficient Tailored Functionality

Narayan

BIOBASED PRODUCTS – WHY? WHAT VALUE IN THE SUSTAINABILITY – LIFE CYCLE EQUATION What is the major basic element that is the building block of biobased products, petroleum based products, biotech products, fuels, even life itself ?

CARBON
“ORGANIC” ISSUE – MANAGING CARBON !!!!!
Ramani Narayan, Michigan State University, www.msu.edu/~narayan

msu.BIOBASED PRODUCTS – WHY? WHAT VALUE IN THE SUSTAINABILITY – LIFE CYCLE EQUATION SUSTAINABILITY & SUSTAINABLE DEVELOPMENT CARBON BASED PRODUCTS “ORGANIC” ECOSYSTEM CARBON CYCLES “biological carbon cycle” ISSUE – MANAGING CARBON !!!!! Ramani Narayan.edu/~narayan OF . Michigan State University. www.

GLOBAL CARBON CYCLING THE ECO DRIVER CO2 Biomass/Bio-organics Sunlight energy (CH2O)x + O2 photoautotrophs -. and some bacteria fix inorganic carbon to organic matter (carbohydrates) using sunlight as the energy CO2 + H2O Ramani Narayan.msu. www. plants.algae. Michigan State University.edu/~narayan .

Natural gas) Renewable Carbon CO2 . entrepreneurial business Green polymers & Chemicals Ramani Narayan. & Biomass New Biochemical Industry Small.10 yrs > 106 years Polymers.GLOBAL CARBON CYCLING THE ECO DRIVER CO2 Bio-chemical Industry Biomass/Bio-organics 1 . Chemicals & Fuels Chemical Industry Fossil Resources (petroleum.edu/~narayan .msu. www. Michigan State University.

Photosynthesis chemoautotrophis Combustion Respiration Decay Burning Land use changes Ramani Narayan.edu/~narayan .msu. Michigan State University. www.

Michigan State University.msu.RENEWABLE BIOMASS RESOURCES AGRICULTURAL FEEDSTOCKS BIOBASED MATERIALS • For sustainable development of carbon based polymer materials • Control and even reduce CO2 emissions and help meet global CO2 emissions standards – Kyoto protocol • Improved environmental (LCA) profile • improved strategic security and balance of payments • healthier rural economies • technology export • a sustainable resource supply Ramani Narayan. www.edu/~narayan .

ring.edu/~narayan . www. or other elements in a chain.TERMINOLOGY • Biobased material(s) Organic material(s) in which the carbon comes from contemporary (non-fossil) biological sources CO2 + H2O Organic material(s) (CH2O)x + O2 Material(s) containing carbon based compound(s) in which the carbon is attached to other carbon atom(s). to be classified biobased.msu. hydrogen. the material must be organic and contain recently fixed (new) carbon present in biological sources Ramani Narayan. Michigan State University. oxygen. or three dimensional structure Thus.

www. or biologically) with fossil/old carbon • biobased content. chemically.msu.TERMINOLOGY (Contd) • Biobased materials may contain 100% bio/new carbon or be mixed (physically. Michigan State University. or gross biobased content Amount of biobased carbon in the material or product as fraction weight (mass) or percent weight (mass) of the total organic carbon in the material or product.edu/~narayan . Ramani Narayan.

(12CHO)x . coal) (12CH2)n Ramani Narayan.msu.Identify & Quantify Biobased Content • • How does one distinguish between new (contemporary) and old(fossil) carbon – identify biobased carbon? How does one quantify biobased carbon content? 14CO – Solar radiation 2 Biomass/Bio-organics 12CO 2 (12CH2O)x (14CH2O)x > 106 years C-14 signature forms the basis of Standard test method to quantify biobased content (ASTM D6866) Fossil Resources (petroleum.edu/~narayan . Michigan State University.Standards -. natural gas. www.

Michigan State University.edu/~narayan .msu.Radiocarbon Methods : ASTM D6866-04a Method A CO2 Absorption Method C Benzene Synthesis Method B AMS (Accelerator Mass Spectroscopy) SAMPLE SAMPLE CO2 Lithium Carbide SAMPLE CO2 CO2 Absorbed into Counting Solution Precision <= 5-10% absolute Standard LSC detection Rapid through-put Acetylene Benzene Precision <= 2% absolute) Standard LSC detection Rapid through-put Reduced to Graphite Precision <= 2% absolute) Very small sample requirements Ramani Narayan. www.

EXAMPLES Product ‘O’ is a fiber reinforced composite with the composition 30% biofiber (cellulose fiber) + 70% PLA (biobased material) Product ‘P’ is a fiber reinforced composite with the composition 30% glass fiber + 70% PLA (biobased material Product ‘N’ is a fiber reinforced composite with the composition 30% biofiber (cellulose) + 70% polypropylene (petroleum based organic) 1.17% -. Because biobased content is on a carbon basis – 13.31*100 Ramani Narayan. Product ‘O’ biobased content = 100% 2. organic content only 70% 3. Therefore must define biobased content and organic content! 4.not 30%!!!! 5.BIOBASED CONTENT -.32/73. Product ‘P’ biobased content = 100%.edu/~narayan .msu. Product ‘N’ biobased content = 18. www. Michigan State University.

U. www.edu/~narayan . L. Section 9002 FARM BILL FEDERAL BIOBASED PRODUCTS PREFERRED PROCUREMENT PROGRAM FB4P (www.msu.gov) • • Provides that Federal agencies must purchase biobased products designated by this program Authority for the program included in the Farm Security and Rural Investment Act (FSRIA) of 2002 Ramani Narayan. Michigan State University.oce.biobased. 107-171). Title IX Energy.usda.S. Farm Security and Rural Investment Act of 2002 (P.

content verification. and † assurance that products are available.LCA TOOLS/BEES analysis † To incorporate life cycle costing † performance requirements. diesel fuel additives.edu/~narayan . ASTM D6866 † environmental profile using LCA ASTM Standard † ASTM D7075 "Standard practice for evaluating and reporting environmental performance of biobased products". and bedding. penetrating lubricants. Michigan State University. water tank coatings. urethane roof coatings. Ramani Narayan.S. six items for preferred procurement by Federal agencies: mobile equipment hydraulic fluids. L. Title IX Energy. www.U. -. bed linens. 107-171). Section 9002 FARM BILL n Federal Procurement of Biobased Products develop guidelines for designating biobased products PUBLISHED FEDERAL REGISTER publish a list & issue criteria for a designated biobased products list (DBL) for federal purchase.msu. Farm Security and Rural Investment Act of 2002 (P. and towels n Will include: † Definition.

BIOBASED FEEDSTOCKS Annually Renewable Bio feed stocks Direct Extraction Cellulosics & Lignocellulosics Products: •Cellulose (Cellophane) •Cellulose Derivatives (CA. CAB) •Cellulose graft copolymers & blends •Engineered wood Products Natural Fibers Starches Other Polysaccharides Example: •Pectin •Chitin •Levan •Pullulan Fats & Oils Proteins Examples: •Kenaf •Sisal •Jute •Hemp •Flax Products: •Biofiber Composites Examples: •Corn •Potato Products: •Industrial Starches •Thermoplastic Starch •Starch Foams • Starch graft copolyemrs & reactive blends •Starch nanoparticles Examples: •Soybean •Lesquerella •Rapeseed Products: •Biodiesel •lubricants •Polyols – urethanes •Plasticizers / Process aids Examples: •Zein •Soy protein .

Polyamides Adhesives Succinic acid Adipic acid 1.3-PDO Bio processes Hydrolysis Annually Renewable Bio feed stocks Bio-monomers Sugar macromers “versatile synthon” INKS Chemical processes EG PG & Other Chemicals Direct Extraction Cellulosics & Lignocellulosics Natural Fibers Starches Other Polysaccharides Fats & Oils Proteins .•Polylactic acid Polyesters •Lactic acid Microbial polymers •Polyhydroxyalkanoates •Bacterial cellulose •Xanthan gums •Tailored polysaccharides Veg oils Polyesters.

controlled-life time products Packaging. -. disposable. disposable plastics. short-life.MATERIALS DESIGN PRINCIPLES FOR THE ENVIRONMENT BIOBASED & BIODEGRADABLE Single use.LCA TOOLS †To incorporate life cycle costing Narayan . marine disposable BIOBASED & DURABLE Soy polyurethanes for automotive and farm vehicles Biofiber composites for industrial and automotive Perform LIFE CYCLE ASSESSMENT (LCA) to document positive environmental attributes †ASTM D7075 "Standard practice for evaluating and reporting environmental performance of biobased products". agricultural films.

edu/~narayan .msu. Michigan State University.MATERIALS DESIGN PRINCIPLES FOR THE ENVIRONMENT FEEDSTOCK BIOBASED OR PETROCHEMICAL PROCESS: •Biological •Chemical •hybrid PRODUCT MANUFACTURE Transform into Useful Product ULTIMATE DISPOSABILITY BIODEGRADABILITY RECYCLABILITY “LIFE CYCLE ASSESSMENT – LCA” ASTM D7075 Ramani Narayan. www.

SHORT LIFE DISPOSABLE PACKAGING & CONSUMER GOODS Ramani Narayan. Michigan State University.msu.What does Biodegradable Mean? Polymer Fragments CO 2 Microbes H2O Humus Plastics Polymer fragment Polymer Crosslink residues Degradation/Fragmentation Biodegradation Biodegradability – complete assimilation of the degradaded products as a food source by the soil microorganisms would ensure returning the carbon into the ecosystem safely and effectively APPLICABLE TO SINGLE-USE. www.edu/~narayan TIME!!! & ENVIRONMENT!! .

www.edu/~narayan .msu.Integration of biodegradable plastics with disposal infrastructures Marine environment Anaerobic digestion facility COMPOSTING COMPOSTING FACILITY FACILITY Biodegradable Biodegradable Plastics Plastics INCINERABLE Paper-biopolymer composite RECYCLING RECYCLING FACILITY FACILITY recycling polymeric carbon back to soil LAND APPLICATION WASTE TO ENERGY WASTE TO ENERGY FACILITY FACILITY ENERGY RECYCLED PRODUCTS Ramani Narayan. Michigan State University.

SUPRESSES CROP DISEASES. HOITNIK & KEENER.msu.edu/~narayan .Biodegradation of polymeric materials during composting.COMPOSTING & THE ENVIRONMENT • COMPOSTING IS AN ECOLOGICALLY AND ENVIRONMENTALLY SOUND APPROACH TO TRANSFERRING BIODEGRADABLE WASTE (INCLUDES THE BIODEGRADABLE PLASTICS) TO USEFUL PRODUCT • COMPOSTING IS BIOLOGICAL RECYCLING OF CARBON • COMPOST USE REDUCES CHEMICAL INPUTS. 1993 Narayan -. p. EDS. www. IMPROVES SOIL PRODUCTIVITY “SUSTAINABLE AGRICULTURE” SCIENCE & ENGINEERING OF COMPOSTING. 339 Ramani Narayan. INCREASES WATER & NUTRIENT RETENTION. REPLENISHES ORGANIC CARBON. Michigan State University.

DEGRADABLE VS BIODEGRADABLE .

marine/oceans. out of sight does not make the problem go away Degradable.Major Environmental Problems Designing products to be degradable or partially biodegradable causes irreparable harm to the environment Degraded products may be invisible to the naked eye. biobased. disposable packaging and consumer plastics. Must ensure complete biodegradability in a short defined time frame (determined by the disposal infrastructure like composting) TIME --. soil Narayan . and plastic-paper combination products (non-durable goods) have serious environmental consequences. single-use. anaerobic digestion plants. MAYBE TWO DISPOSAL ENVIRONMENT Composting.ONE GROWING SEASON. However.

WHITE POLLUTION – CHINA .

) • • Plastic debris around the globe can erode (degrade) away and end up as microscopic granular or fiberlike fragments. 2004 Narayan FLOTSAM Lab experiments show that marine animals consume microscopic bits of plastic. © Science 2004 . 838. These include mechanical erosion of nondegradable plastic bottles and packaging.Major Problems/Issues with Degradable Materials/Products (contd. – Science 304. the researchers suggest. as seen here in the digestive tract of an amphipod. nondegradable parts of biodegradable plastics. and that these fragments have been steadily accumulating in the oceans fragments come from several sources. and plastic pieces used as abrasives in cleaning agents.

floating plastic is like a poison pill -endocrine disruptors – From Algalita Marine Research Foundation – www.algalita. – Mato et al Environ. 2001. 318-324 Narayan . As a result.Problems with Degradables – Toxic Chemicals Transport • plastic pieces can attract and hold hydrophobic elements like PCB and DDT up to one million times background levels. DDE.html • • PCBs. and nonylphenols (NP) were detected in high concentrations in degraded polypropylene (PP) resin pellets collected from four Japanese coasts. 35.org/pelagic_plastic. Technol. Sci. Plastic residues function as a transport medium for toxic chemicals in the marine environment.

. sucrose or lactose. (23). Michigan State University. by anchoring minute quantities of glucose. to greatly increase the rates of biodegradation of polyolefins. Ramani Narayan. www. onto functionalized polystyrene (polystyrene-co-maleic anhydride copolymer) and measuring their rates of biodegradation. 2884 .msu. weight loss of only 2-12%. 2002. and successfully tested.edu/~narayan . which were found to be significantly improved • PRESS • Sugar turns plastics biodegradable.2885 – A hypothesis was developed. Commun.BIODEGRADABILITY CLAIMS • Chem. Bacteria make a meal of sweetened polythene and polystyrene.

msu.edu/~narayan .METRICS FOR BIODEGRADABILITY?? Ramani Narayan. Michigan State University. www.

edu/~narayan . ∆G0’ = -686 kcal/mol 2 lactate. Michigan State University.METRICS FOR BIODEGRADABILITY?? Why CO2 as a quantitative measure of biodegradation/bioassimilation? Microorganisms extract chemical energy for use in their life processes by the aerobic oxidation of glucose and other utilizable substrates –BIODEGRADBLE PLASTICS?? AEROBIC Glucose + 6 O2 ANAEROBIC Glucose 6 CO2 + 6 H2O.msu. www. ∆G0’ = -47 kcal/mol R Ramani Narayan.

Michigan State University.edu/~narayan .msu. www.O2 CO2 100 90 80 70 60 50 40 30 20 10 0 % C conversion to CO2 biodegradation curve biodegradation degree 65% Compost & Test Materials lag-phase degradation phase plateau phase 0 4 8 12 16 20 24 28 32 36 40 44 time (d) Ramani Narayan.

Japan. Canada) prescribed threshold assimilation • 60% of carbon conversion to CO2 for homopolymer & 90% carbon conversion to CO2 for block. segmented copolymers.Specification Standard for Biodegradable/Compostable Plastics • ASTM D6400 identified 3 criteria Mineralization (D5338): Disintegration • <10% of test material on 2mm sieve – Safety • No impacts on plants. China. including addition of low MW additives • Same rate as natural materials Leaves. and blends. water & biomass via microbial O2 CO2 Compost & Test Materials Basis for standards in Europe.180 days or less. using OECD Guide 208 • Regulated (heavy) metals less than 50% of EPA (USA. paper. Korea. Taiwan Narayan . grass & food scraps • Time -. if radiolabeled polymer is used 365 days or less • Conversion to carbon dioxide.

www.Paper coatings ASTM D 5988 Soil Soil Mulch film Mulch film Ag appl Ag appl ASTM D 6692 D 6691 Marine & fresh water COMPOSTING COMPOSTING FACILITY FACILITY Biodegradable Biodegradable Materials Materials Anaerobic digestion biogas energy plant ASTM D5511 ISO 15985 recycling polymeric carbon back to soil LAND APPLICATION Ramani Narayan.Cradle to Cradle Concept for Material Design (Integration of Biodegradable Materials with Disposal Infrasructures) ASTM D6400 -.edu/~narayan Waste water Waste water treatment treatment facility facility ASTM D5271 ISO 14851/14852 . Michigan State University.msu.Specification D5338/ISO14855 Test method D6340 C-14 test method EN 13432 specification ISO 16929 ASTM D6868 -.

www.msu.org Memorandum of Understanding Cross Certification Program BPS JAPAN DIN CERTCO GERMANY BPS Brazil Common ISO Standard for Biodegradable Plastics EBPA Taiwan KBPA Korea BPS China Ramani Narayan.Global Standards for Biodegradability Composting Assn UK USA Coming Soon! www. Michigan State University.bpiworld.edu/~narayan .