Erhan Pişkin1, Yeşim Ekinci2, Hülya Yavuz Ersan1, Sinan Eğri1,3,
Gökhan Tezcan1, Koroush Salami1, Özlem Eğri1,4, Zakir Rzaev4,
Sevda İsmailova1, Farzaneh Moghtader4
Hacettepe University
Supported by Turkish Ministry of Science, Technology and Industry
Development of Biobased/Biodegradable/
Compostable Nanocomposite Mulching Films and Active Packaging
PLASTICE October 24-25, 2011, Bologna, Italy
FOSSIL FUELS
0.2 Gtons (3%)
Polymeric Materials
7.3 Gtons
6.5 Gtons (93%)
Energy Production 0.3 Gtons (4%)
Raw Chemicals
Crude Oil
44%
Natural Gas
25%
Coal 31%
Annual Consumption
It is a pity … Fossil Fuels will finish soon … When ??
We need new resources
for energy and POLYMERS
1
10
100
1000
10000
100000
1000000
1 10 100
Price (US Dollars/kg)
Po
lym
er
Pro
du
cti
on
(to
ne
s/y
ea
r)
PP
Epoksiler
PVC LDPE ABS PET PMMA Poliasetaller
Poliamidler PC Silikonlar PPS PES PEEK
POLYMERS: Production-Price
PRODUCTION > 200 Million tones
CONSUMPTION Developed Countries > 100 kg/person/year
Developing Countries > 1-10 kg/person/year
POLYMER - WASTE
ENVIRONMENTAL CONCERNS are increasing
We need effective “waste manegement” strategies
TURKEY
Area: 777 971 km2
Population: > 70 Million
2025 .... > 95 Million 25% leaves in three big cities 60% leaves in cities
Solid waste: 450-750 g/day/person
20 Million tones/year
0
5
10
15
20
25
30
35
40
45
World
Turkey
POLYMERS IN USE
Expected life (year)
Packaging/Mulching <1 Construction 25
Electronic 15
Paints/Coatings 4
Car industry 11
Furniture 10
Industrial machinery 15
POLYMERS IN USE EXPECTED LIFES
Recyclables 13%
Destroyed 24%
Organic
Substances
63%
PLASTICS 21%
Metals 9%
Paper 47%
Glass17%
Others 6%
TURKEY
SOLID WASTE COMPOSITION
WASTE MANAGEMENT STRATEGIES
1. RECYCLING Mechanical Chemical Biological (Composting)
. It is widely used if not mixed with organic waste
. Note that properties of the polymer changes in each processing step
WASTE MANAGEMENT STRATEGIES
COMPOSTING
Microorganisms Oxygen Humidity
Organic/Compostable Materials (Carbon source)
Heat Biodegradation
CO2 + H2O
N, P, K, ...
COMPOST
Reduces significantly chemical fertilizer use; plant diseases; water consumption; erosion, etc.
Increases soil quality; production yield and product quality
Technologies are exist.
Investment cost may be a problem. Preselection is needed. Depends on the waste composition
WASTE MANAGEMENT STRATEGIES
2. INCINERATION 30300 KJ/Kg High investment cost ?
Preselection ? Air polution ? Political concerns ?
WASTE MANAGEMENT STRATEGIES
3. LAND FILLING
Damping (easy but not good)
Samitary Fields (good but expensive)
MULCHING FILMS
MULCH FILM CYCLE
Why we need to use mulching films?
1. Positive heat effects (earlier planting dates
or planting at hot weather)
2. Soil moisture retention (less water)
3. Weed management
4. Reduced fertilizer leakage/use (drip irrigation)
5. Reduced soil compaction and therefore reduced root damage
6. Reduced negatif effects of weather conditions.
MULCHING FILMS
Much Higher Quality & Yield
What we use ? Consumption ? Problems ?
1. Low density polyethylene (LDPE)
2. Use: About 1 million ton/year (worldwide) which results a huge plastics waste
3. Can be used only twice. Recyling is very difficult. They should be collected and disposed (which makes the process expensive)
MULCHING FILMS
Alternative solutions?
Use .......... “Biobased Resources”-
They are ........... ”Renewable”
and “Biodegradable”
MULCHING FILMS
BIOBASED POLYMERS
However they may be more expensive and exhibit lower
mechanical properties comparing to their alternative comodity but-non degradable thermoplastics in many applications including and agro-use
BIOBASED POLYMERS
1. Natural polymers
2. Polymers produced from biobased monomers
FROM BIO-DERIVED MONOMERS
Poly(-hydroxy acids)
e.g. Poly(lactic acid) (PLA)
BIOBASED POLYMERS
LACTIC ACID
The L (+) form is the natural one, and is naturally present in animal and human tissues as well as in numerous food products (meat, milk products, pickles, beer, etc.).
Lactic acid (called also “milk acid”) is a natural product.
Today more than half of the total consumption is produced by fermentation in which several carbohydrate sources such as whey, barley, sugarcane, soybean, milk, corn, sulfite waste liquor and potatoes can be used as substrate. Careful selection of the fermentation bacteria. Industrially used specie is Lactobacillus Delbrueckii with glucose or sucrose as substrate.
With different molecular weights (chain lengths)
with different chain compositions (copolymers)
Therefore with different mechanical properties,
and degradation rates
Poly(glycolide) (R:H)
Poly(L-lactide)
Poly(D-lactide)
Poly(D,L-lactide) a mixture of L-and D-
Poly(glycolide/lactide)
Poly(-hydroxy acids)
O H
R
- O - C - C
n Cargill-NatureWorks LLC, USA
PURAC, The Netherlands
Poly(-hydroxy acids)
Poly(-hydroxy acids)
Poly(-hydroxy acids)
OUR RELATED PRODUCTS
Poly(-hydroxy acids)
MONTHS
______________________________________________
PLLA 18-24
PDLLA 12-16
PGA 2-4
PDLLA/GA-50/50 2
PDLLA/GA-85/75 5
PDLLA/CL-90/10 2
______________________________________________
Approximate degradation time
NATURAL POLYMERS
ANIMAL VEGETAL
Proteins Cellulosics / Lignin
Fats & oils Starches
Polysaccharides Proteins / Fats & oils
Polynucleotides Polynucleotides
MICROBIAL
Polyesters
Polysaccharides
Polyphosphates
Polysulfides
PLANT
MICROBIAL
ANIMAL
PLANT-BASED
3.7 Gtons (62%)
Food-use
6 Gtons
0.3 Gtons (5%)
Non-Food Use 2 Gtons (33%)
Energy & Housing
2 kg/day/person
Annual Consumption
EAT or USE
?
PLANT BASED POLYMERS
POLYSACCARIDES
(a) Starches: wheat; potatoes; maize, etc.
(b) Cellulose : wood, straws, etc.
(c) Others: pectins; chitin/chitosan; gums, etc.
Starch
Polimer Faz Sentez ve Karakterizasyonu
Nişasta
Laktik Asit
Katalizör
Oligo - PLA PLA
Nişasta çözücü
M.Nişasta
Nişastanın Oksitlenme İle Modifikasyonu
Nişasta tekrarlayan birimi Dialdehid nişasta birimi
NANOCOMPOSITES
Barrier improvement primary advantage Platelets are typically about 1 nm thick,
typically 100-2000 nm in length & width
Also .. Increase stiffness, strength Act as nucleating agent in foams Smaller cell size, higher cell density
Act as flame retardants
Based on various types of clay, most common:
montmorillonite, hektorit, saponit, fluoromika, fluorohektorit, vermikulit, kaolinit, magadiit, etc.
CLAY NANOCOMPOSITES
Blending
and
Anneling
Organophilic
Clay
Termoplastic
Polymer “Intercalation”
NH3+
NH3+ NH3
+
NH3+
NH3+ NH3
+
Melt Intercalation
CLAY NANOCOMPOSITES
Intercalating Agents
CLAY NANOCOMPOSITES
MORE ………….
……. Active and Intelligent Packaging
Biobased/biodegradable/antibacterial/ nanocomposite polylactic acid-
thermoplastic starch based flexible food (meat) packaging films carrying intelligent
tags read out by SERS sensors
Unfilled
Filled
Clay content
CLAY NANOCOMPOSITES
