www.certech.be - [email protected]
An interface between R&D and applications
May 28 & 29, 2013Brussels, BELGIUM
Certech is member of
From Biobased Polymers to Bioplastics
Green polymer chemistry - New materials and additives - Innovative process or applications - Product development issues - Market developments
and expectations - Ecological performance - End of life options …
materials formulation & technology
centre
en chimiehe
alth
Cata
lysi
s
outstanding performance
Innovative reaction media
Green chemistry
Pilo
t pla
nts
renewable originhybrid materials so
l gel
tech
nolo
giqu
escertech
processintensification
environment
de ressources
& safetyEnergy from chemistry
Microtechnologies
recycling
www.certech.be - [email protected]
An interface between R&D and applications
May 28 & 29, 2013Brussels, BELGIUM
Green polymer chemistry - New materials and additives - Innovative process or applications - Product development issues - Market developments
and expectations - Ecological performance - End of life options …
Certech is member of
From Biobased Polymers to Bioplastics
2 From Biobased Polymers to Bioplastics 2013
The Centre of Technological Resources in Chemistry (Certech) is a contract research organiza-
tion offering a wide range of services to industries directly or indirectly involved with chemical
technology, such as automotive, building & construction, packaging, food, agriculture, personal
care, pharmaceutical, medical, energy, environment, etc.
Certech’s mission is to provide help, support and services to small and large industrial enter-
prises, by offering adequate analysis and measurements, problem-solving, contract research,
product and process development capabilities.
Certech has three different fields of activities having chemistry and sustainable development as
a common theme, namely Environment, Materials technology and Process intensification.
Environment
For more than 30 years, Certech has been developing a wide expertise in the fields of gas emis-
sion, optimisation of processes and improvement of materials to reduce their environmental
impact.
Certech is recognised as an independent and reliable research institute, dedicated to companies,
authorities and citizens.
Our R&D developments in the field of environment are mainly related to:
• Health & Safety: evaluation of the quality of air, risks assessment and environmental impact
• Energy: advanced materials, sustainable technologies, renewable resources
• Recycling: management of wastes and its valorisation into material and/or energy.
As a multidisciplinary research centre, Certech takes advantage from its other fields of expertise,
such as material science or process intensification, to develop synergies and deliver innovative
solutions to its customers.
Certech is looking for C2C (cradle to cradle) processes, working according to the green chemistry
concepts.
Certech is accredited for the measurement of odours and is approved for the control of atmos-
pheric pollution by regional authorities. Certech is active in 11 standardisation committees such
as AFNOR, EN or ISO.
3From Biobased Polymers to Bioplastics 2013
Materials formulation and technology
Certech expertise ranges from materials development (formulation, synthesis, blends,...) to
transformation and forming processes, allowing us to offer a large and diverse technical and
scientific support to our partners and customers looking for a global expertise in the field of
material science.
Among the different materials studied at Certech, polymers and composites as well as sol-gels
constitute the major part of our activity. A complete set of processing equipments along with
large advanced analytical capabilities are available.
As green management has become a major topic for industrials within the last years, Certech has
developed a strong expertise in materials and processes with a reduced environmental impact,
ranging from biobased materials to plastics and composites recycling processes.
Process intensification
Process Intensification is a relatively new approach in the chemical industry.
The use of extreme reaction conditions is the key to this new technology (very high temperature
and pressures, short reaction times, continuous processes). It leads to a substantially smaller,
faster, cleaner and more energy-efficient technology. It is a multidisciplinary opportunity to im-
prove both process technology and underlying chemistry at the same time.
Certech also provides an expertise in the field of catalysis and synthesis. Certech services cover
various domains:
Customised organic and inorganic synthesis (for a scale going from grams to kilograms),
Improvement of synthetic pathways and process development, thanks to automated synthesis
workstations, which make possible the run of high throuput experiments.
www.certech.be
4 From Biobased Polymers to Bioplastics 2013
Certech skills in polymer synthesis as well as in com-
pounding are also proposed to customers.
The division of Bio- and Soft Matter (BSMA) of the Institute
of Condensed Matter and Nanosciences (IMCN) of the Uni-
versity of Louvain (UCLouvain) hosts about 100 research-
ers and technicians active in the field of soft matter taken
in its broader meaning.
Structure of research in IMCN/BSMA.
More information on www.uclouvain.be/bsma.html
From living micro-organisms studied as a particular state of matter, to hybrid or even purely
inorganic nanowires integrated in prototypic devices, the activities of BSMA cover scientific top-
ics as diverse as self-assembly, biosensing and biointerfaces, polymer science, surface science,
(nano)composites, organic electronics, or even spintronics, for applications in medicine, elec-
tronics and information technology, materials, or energy.
5From Biobased Polymers to Bioplastics 2013
The three main lines of research of BSMA are:
1. tailoring and characterization of surfaces and interfaces;
2. fabrication and characterization of materials and devices at the nanometer scale;
3. synthesis, processing and characterization of macromolecular (polymer) materials.
These lines of research are supported by a strong expertise in synthesis, nanofabrication and
processing, as well as in the characterization of surfaces, materials and devices. Importantly,
these research lines are also based on a strong expertise in fabrication and characterization of
(nano)materials and (nano)devices.
Obviously, there is no strict division between these three lines of research, which interact as in
the triangle above. For instance,
• nanocomposite materials are polymer-based materials, rich in tailored interfaces, which
have to be characterized at the nanometer scale;
• controlling the growth of bacteria on surfaces involves tailoring the surface at the sub-mi-
crometer scale, using bio-macromolecules such as proteins or polysaccharides;
• a biosensor based on hybrid nanowires requires skills in nanofabrication, is based on bio-
logical interactions at the nanowire surface, involves synthesis during its fabrication, and
requires advanced physical characterization techniques to understand its function.
A wide range of techniques of fabrication and characterization is available in BSMA. These tools
serve to synthesize, process, or provide a picture as complete as possible of, the complex systems
and nanosystems engineered in BSMA. This uniquely wide expertise is also made available to
external scientists or industrial companies. Some of these techniques are grouped in technologi-
cal platforms managed at the level of the IMCN institute.
A complete list of equipment is available at http://www.uclouvain.be/en-329587.html.
www.uclouvain.be/bsma.html
@uclouvain.be
6 From Biobased Polymers to Bioplastics 2013
Tuesday 28th May
8h30 Welcome coffee and registration
9h00 Introduction to the conference
Thierry Randoux, Certech
9h15 Opening Lecture: Future prospects for Bioplastics
James Philp, OECD
9h45 Invited Lecture: Bioplastics: Basics and the technical/scientific trends
Prof. Luc Avérous, Strasbourg University
10h15 Minefield in the patent landscape
Paul-André Gollier, Pronovem
10h35 Q&A session
10h45 Coffee break - Poster session and exhibition
11h15 Experiences on 20 years of biopolymer testing and
certification: challenges and new developments
Sam Deconinck, Organic Waste Systems
11h35 VALORIA: Preindustrial scale implementation of
wasterwater treatment sludge valorization route through
polyhydroxyalkanoate (PHA) production
Maria Albuquerque, VEOLIA Environnement Recherche et Innovation
11h55 Environmental performance of bio-based polymers –
Bringing LCA down to earth
Roland Essel, nova-Institut
12h15 Q&A session
12h25 Lunch
7From Biobased Polymers to Bioplastics 2013
14h00 Invited Lecture: Are bio-sourced polymers an opportunity for SEB ?
Nathalie Pécoul, Groupe SEB
14h30 Roquette Biorefinery: Today and tomorrow
Vincent Berthé, Roquette Frères
14h50 Biobased PLA: the heat is on! A biobased replacement for PS,
PET and PP in high temperature applications
François de Bie, PURAC
15h10 Bisphenol A substitution in structural adhesive by a bio-based component:
Evaluation of the adhesive, water resistance and thermo-mechanical
properties
Pierre Verge, Centre de Recherche Public Henri Tudor
15h30 Q&A session
15h45 Coffee break - Poster session and exhibition
16h15 Materials sell by properties! What sells PHB? Is there anything PHB can do
better than other bioplasts / thermoplasts ?
Urs Hänggi, BIOMER
16h35 SOLANYL and FLOURPLAST thermoplastic starch based plastics and
OPTINYL masterbatches:
Creating new opportunities for the bioplastic industry
Jeroen van Soest, Rodenburg Biopolymers
16h55 Biopolymer textile applications: shifting stability properties using
functional additives
Luc Ruys, CENTEXBEL
17h15 Q&A session
17h30 Summary and conclusions from first day
17h45 End of day one followed by event and dinner
8 From Biobased Polymers to Bioplastics 2013
Wednesday 29th May
9h30 Invited Lecture: Bio-sourced materials:
risks or opportunities for automotive applications
Gérard Liraut, Renault
10h00 Biobased adhesives: when green chemistry meets the material science of
sticky things
Richard Vendamme, NITTO DENKO Europe
10h20 Emissions from PLA materials: food packaging and automotive applications
Annabelle Cingöz, CERTECH
10h40 Q&A session
10h50 Coffee break - Poster session and exhibition
11h20 Reducing the Environmental Footprint of Polyurethanes using
Biosuccinium™ based Polyester Polyols
Luc Leemans, DSM
11h40 New renewable molecules for bio-based polymers
Stéphane Bernard, Oléon
12h00 Bioprepolymer for the use of automotive seating foam
Christophe Ponce, Huntsman Polyurethanes
12h20 Q&A session
12h30 Lunch
9From Biobased Polymers to Bioplastics 2013
14h00 Invited Lecture: Packaging for food or food for packaging ?
The role of bioplastics in the Nestlé packaging portfolio.
Lars Lundquist, Nestlé
14h30 New renewable polyurethane adhesive for flexible packaging
Olivier Laferté, BOSTIK
14h50 Life cycle thinking approach for sustainable feedstock design
Houshang Kheradmand, The Dow Chemical Company
15h10 Agroboost: a collaborative project on biobased textiles with controlled
biodegradation
Denis Couvret, IFTH
15h30 Towards fully green composites ?
Naïma Sallem, Université Catholique de Louvain
15h50 Q&A session
16h10 Concluding remarks
André Luciani, Certech
16h30 End of day two and farewell coffee
10 From Biobased Polymers to Bioplastics 2013
Abstract
FUTURE PROSPECTS FOR BIOPLASTICS
James Philp - OECD
Society is fundamentally ambivalent to the use of plastics. On the one hand, plastics are unique-
ly flexible materials that have seen them occupy a huge range of functions, from simple packing
materials to complex engineering components. On the other, their durability has raised concerns
about their end-of-life disposal. When that disposal route is landfill, their invulnerability to mi-
crobial decomposition, combined with relatively low density and high bulk, means that plastics
will occupy increasing amounts of landfill space in a world where available suitable landfill sites
is shrinking. An environmental dilemma with more far-reaching implications is climate change.
The need for rapid and deep greenhouse gas (GHG) emissions cuts is one of the drivers for the
resurgence of industrial biotechnology generally.
The search for biodegradable plastics and their introduction to the marketplace would appear
to be a suitable amelioration strategy which fits with the growing call for a future bioeconomy.
And yet the uptake of biodegradable plastics has been slow. Now the pattern of production is
shifting from the true biodegradable plastics to the biobased plastics, and that trend is likely to
persist into the future.
It is often said that the bioplastics, and also biobased chemicals, suffer from a lack of a favour-
able policy regime when compared to the wide-ranging policy instruments that are available for
biofuels production. This situation is likely to result in the uneven development of a bioeconomy
if not addressed. The OECD is currently working on investigating policy measures that might
redress the balance.
11From Biobased Polymers to Bioplastics 2013
Notes
12 From Biobased Polymers to Bioplastics 2013
Abstract
BIOPLASTICS: BASICS AND THE TECHNICAL/SCIENTIFIC TRENDS
Pr. Luc Avérous - Strasbourg University, France
Over the last decades, international research has led to the strong development of materials
from biomass, for non-food and polymer applications. These materials are biobased but also
they could be biodegradable. Biodegradable means capable of undergoing decomposition into
carbon dioxide, methane, water, inorganic compounds, and biomass. The predominant mecha-
nism is the enzymatic action of micro-organisms.
Currently, bioplastics (plastics from renewable source – from biomass) represent enormous po-
tential. This is mainly due to a growing societal demand for more friendly and environmental
materials. These materials can be (i) for short term applications (packaging, leisure, agriculture,
catering, hygiene, biomedical, ), since the biodegradable polymers can easily be degraded and
bio-assimilated and (ii) for durable and long terms applications (building, automotive …).
The worldwide demand for the biobased and biodegradable polymers (Bioplastics) has steadily
grown over the last ten years at an annual rate of between 10 and 20% per year. The market
share, however, is very modest in terms of actual fraction of the total plastics market. According
to the association European Bioplastics, the worldwide production capacity of the biodegrad-
able and biobased polymers for material applications was around 1161 kTonnes in 201. The cor-
responding worlwide plastic production was 280 Mio Tons.
Up to now, the limited growth of the bioplastics can be explained by diifrent parameters such
as: limited performance properties, high prices, limited legislative attention, the fact that bio-
degradability can be an added functional property not immediately perceived and the lack of
composting infrastructure…
However excitingly new environmental materials, have begun to address these major issues.
Replacing petroleum-based raw materials with renewable resources is now a major concern.
The great majority of these polymers are developed for environmental purposes in order for
instance, to improve the LCA (Life cycle analysis)[1].
Ref.: [1] Book: S. Kalia & L. Avérous. “Biopolymers: Biomedical and Environmental applications”. John Wiley & Scrivener Publishing. Pub. July 2011. 642 p
13From Biobased Polymers to Bioplastics 2013
Notes
14 From Biobased Polymers to Bioplastics 2013
Abstract
MINEFIELD IN THE PATENT LANDSCAPE
Paul-André Gollier - Pronovem - Office Van Malderen, Belgium
Biobased polymers are currently having an increasing interest in R&D. Some products are al-
ready on the market and new applications are discovered every day. Patent applications are
usually published before commercialization of a product, sometimes a few years before such
commercialization, so that patent landscape analysis can be a powerful tool to understand long
term market evolution, and make early detection of emergence of new market players.
In this presentation, we will show statistical data about patent applications regarding biobased
polymers, both for their synthesis and their potential applications. Particular attention will be
given to relevant patent classification thereby developing several searching strategies in the
worldwide patent databases. We will further analyze the market trends in view of those statisti-
cal data.
15From Biobased Polymers to Bioplastics 2013
Notes
16 From Biobased Polymers to Bioplastics 2013
Abstract
EXPERIENCES ON 20 YEARS OF BIOPOLYMER TESTING AND CERTIFICATION:
CHALLENGES AND NEW DEVELOPMENTS
Sam Deconinck*, Bruno De Wilde - Organic Waste System (OWS), Belgium
This presentation will start with an overview of the different norms on industrial compostabil-
ity and will make the distinction between biodegradability and compostability. Next, different
aspects playing a considerable role in determining the correct set of tests will be tackled. Aspects
like concentration of individual components, variations in composition, use of masterbatches
and inks, but also the value of certification schemes, by-laws and positive lists will be discussed.
Also some suggestions will be formulated how to further improve the system and make it more
efficient and cost-effective.
Currently, 6 major certification systems exist worldwide with regard to compostability: DIN
CERTCO, Vinçotte and European Bioplastics (Europe), BPI (USA), JBPA (Japan) and ABA (Aus-
tralia). These systems are all based on the same international standards (EN 13432, ASTM D6400
and ISO 17088) with similar requirements, but nevertheless show some minor and sometimes
relevant differences. Some make a difference between materials and products, others require
more testing and some others have also systems for the certification of individual additives for
compostable products.
Finally, also some other environments will be discussed, sketching the similarities and the dif-
ferences which are mostly related to temperature and microbial population. More in particular,
biodegradation in home composting, soil and fresh and marine water will be discussed, as well
as biodegradation in anaerobic digestion and landfill conditions, with again focus on test meth-
ods as well as criteria. Also a brief overview will be given on the standards existing in these
fields.
17From Biobased Polymers to Bioplastics 2013
Notes
18 From Biobased Polymers to Bioplastics 2013
Abstract
VALORIA: PREINDUSTRIAL SCALE IMPLEMENTATION OF WASTEWATER TREATMENT SLUDGE
VALORIZATION ROUTE THROUGH POLYHYDROXYALKANOATE (PHA) PRODUCTION
Maria Albuquerque*, D. Cirne, A-S. Lepeuple
Veolia Environnement Recherche et Innovation, France
The development of new valorization routes for wastewater treatment sludge is a critical chal-
lenge for the wastewater treatment industry and society. Every year more than 10 Million tons of
wastewater treatment sludge (dry solids) are produced in the EU (source EU, 2010), 1.5 M tons in
France alone (source: FNADE, 2006). Furthermore, this value is rising. It is estimated that sludge
production in France increased by 50% between 1991 and 2003 (source: Office Parlementaire
d’Evaluation des Choix Scientifiques et Techniques). This significant increase is due on one hand
to stricter regulatory standards for discharged treated water as well as to increasing human activ-
ity (urban development, industry). The wastewater treatment industry is technically able to meet
the new standards. However, to do so, an increasing amount of organic pollution is transferred
from the liquid phase to the dry solids generated in wastewater treatment. In simple terms, the
better the pollution removal efficiency, the higher the amount of dry solids produced. Currently,
several routes exist for treatment and valorization of wastewater treatment generated sludge:
incineration (15-20%); underground storage (20-25%), land spreading (60%) and methanisation.
The development of alternative valorization routes is thus an important challenge for the waste-
water treatment industry as well as for our society, which deals with an increasing production of
waste and contaminated effluents. If properly used, wastewater treatment generated wastes and
by-products can be considered as a source of renewable organic carbon and minerals, which can
be further valorized into chemicals and polymers constituting a possible replacement for their
petrochemically derived equivalents.
The VALORIA project’s main goal consisted in the development and preindustrial scale implementa-
tion of a full sludge to PHA valorization route. Polyhydroxyalkanoates (PHA) are microbial synthe-
sized polyesters which are both biobased and biodegradable while presenting similar thermal and
mechanical properties to some conventional oil based polyesters. PHA have therefore a high technical
replacement potential relative to conventional polyolefins as polypropylene. However, so far the re-
placement of the later by PHA has been delayed by their high production costs (over 4 times that of
synthesis polymers). Their production from sludge using open microbial culture systems could signifi-
cantly decrease their production costs, thus providing a cost competitive approach to PHA production.
19From Biobased Polymers to Bioplastics 2013
Notes
20 From Biobased Polymers to Bioplastics 2013
Abstract
ENVIRONMENTAL PERFORMANCE OF BIO-BASED POLYMERS
BRINGING LCA DOWN TO EARTH
Roland Essel - Nova-Institut GmbH, Germany
Life cycle assessment (LCA) is an internationally standardized and widely applied methodology
to assess the environmental impacts associated with products and production processes. How-
ever, the application of LCA for bio-based materials is challenging. Bio-based plastics offer the
opportunity to store atmospheric carbon in contrast to their petroleum based counterparts. Fur-
thermore, the possibility for cascade utilization makes it possible to reduce their environmental
impacts. These and other specific characteristics of LCAs for bio-based materials are explained
and critically reviewed. Finally, new solutions for the communication of LCA results are given
that bridge the way to policy related decision-making.
21From Biobased Polymers to Bioplastics 2013
Notes
22 From Biobased Polymers to Bioplastics 2013
Abstract
ARE BIO-SOURCED POLYMERS AN OPPORTUNITY FOR SEB ?
Nathalie Pécoul - Groupe SEB, France
A large variety of plastic materials (PP, ABS, PBT, PC, PA…) is used for SDA (Small Domestic Ap-
pliances) applications. These plastics are mainly “conventional” ones, i.e. based on crude oil. But
the biobased plastics offer is increasingly broad and diverse, with a global production capacity
for bioplastics that should be increased fivefold between 2011 and 2016.
SEB wants to be an active player in sustainable development and considers that the “green
materials” could be an opportunity to reduce pressure on natural resources. The use of these
materials, however, raises a number of questions. For example, are we sure to decrease the
environmental impact? Or, are these new materials free of any hazardous substance? This pres-
entation will give an overview of the questions asked and the issues encountered to develop the
biosourced polymers in SEB’s products.
23From Biobased Polymers to Bioplastics 2013
Notes
24 From Biobased Polymers to Bioplastics 2013
Abstract
ROQUETTE BIOREFINERY: TODAY AND TOMORROW
Vincent Berthé - ROQUETTE FRERES, France
Raw materials from renewable vegetal origin are promising development areas for (new)
sustainable chemicals. Even though chemical industries remain mainly focus on common fos-
sil resource based products, there is room for new actors. Not only rarefaction of petro based
resources or crude oil price fluctuations account for integrated biorefineries progress. Indeed,
progressive changes to renewable moieties and building blocks are actually mainly driven by the
new properties and functionalities they bring.
In 2006, Roquette started new open innovation-driven R&D projects focused on plant-based
chemistry through notably the BIOHUB® innovation program. Both isosorbide and succinic
acid, two chemical building blocks, underwent fast developments thanks to fruitful international
cooperations.
The BioHub® program which seeks to develop new channels of production for chemical prod-
ucts based on renewable agricultural raw materials such as cereals leads to promising develop-
ments in the field of engineered biobased polymers. As example of result, Isosorbide can cost
effectively replace fossil based chemicals for polymers, and it’s unique chemical structure can
also bring outstanding properties of the new polymers. A heat-stable grade of isosorbide POLY-
SORB® P is now available in industrial quantities for the production of new copolyesters or
polycarbonates. All these materials offer improved heat and chemical resistance, very good opti-
cal and mechanical properties.
25From Biobased Polymers to Bioplastics 2013
Notes
26 From Biobased Polymers to Bioplastics 2013
Abstract
BIOBASED PLA: THE HEAT IS ON!
A BIOBASED REPLACEMENT FOR PS, PET AND PP IN HIGH TEMPERATURE APPLICATIONS
François de Bie - Purac, The Netherlands
PLA Biobased plastics in the packaging industry have, until now, been limited to cold food pack-
aging and disposable applications like soft-drink cups and fresh fruit containers. Purac, a Dutch
Lactide producer with 80 years of experience in Lactic Acid production, has successfully devel-
oped groundbreaking, heat resistant PLA technology that unlock a vast market potential as a
biobased replacement for PS, PET and PP.
PLA is made from natural, renewable resources such as sugarcane or corn, PLA bioplastics pro-
vides packaging producers with a reliable, biobased solution that can be recycled or composted
after use. The specific sustainability benefits of PLA will be highlighted and various end of life
options will be compared. Special focus will be to highlight the recyclability of PLA
PLA based on PURALACT Lactides can withstand peak temperatures of up to 250°F / 120°C mak-
ing it suitable for hot food and beverage containers. Thermoformed cups made from PURALACT
are able to contain boiling water without any sign of distortion. Injection molded parts can take
even higher temperatures.
The heat resistance PLA also opens up opportunities for durable applications like for example in
the automotive and consumer electronics / consumer appliances markets.
4 different applications examples, made from high heat PLA will be shown:
- Thermoformed – single use – PLA hot beverage cup
- Injection molded – single use – high heat PLA cutlery
- Injection molded PLA for automotive parts
- Injection molded PLA for durable consumer goods/appliances
R&D is a cornerstone of Purac’s business strategy and towards the end of the presentation an
overview of Purac’s future innovation will be shared.
27From Biobased Polymers to Bioplastics 2013
Notes
28 From Biobased Polymers to Bioplastics 2013
Abstract
BISPHENOL A SUBSTITUTION IN STRUCTURAL ADHESIVE BY A BIO-BASED COMPONENT:
EVALUATION OF THE ADHESIVE WATER RESISTANCE AND THERMO-MECHANICAL PROPERTIES
Pierre Verge*, Joao A.S. Bomfim, Valérie Toniazzo, David Ruch
Advanced Materials & Structures, Centre de Recherche Public Henri Tudor, Luxembourg
Bisphenol A [or BPA] is an important industrial chemical that is primarily used as an intermedi-
ate in the production of polycarbonate (PC) and epoxy resins. Due to its toxicity and release, a
strong urgency appears to its substitution by more eco and human friendly compounds.
In this presentation, we will expose the potential of a derivative of cashew nutshell liquid
(CNSL) as an alternative to BPA-derived epoxy. CNSL, which main constituent is Cardanol - an
unsaturated alkylphenol, is a by-product from the processing of cashew nutshells. We tested a
di-functional glycidyl ether Cardanol-based epoxy resin (CNSL-dGE), whom chemical structure
affords a higher flexibility (due to C8 alkyl chain separating the aromatic groups) and water re-
sistance (due to the C7pending alkyl chain) than traditional BPA thermosets epoxy.
The adhesive, water resistance and thermochemical properties of neat CNSL-dGE and DGEBA/
CNSLdGEco-network with different rates of DGEBA substitution by CNSL-dGE have been evalu-
ated, evidencing a strong increase of the adhesive strength (from 3.5MPa to 6MPa respectively
for DGEBA and CNSL-dGE networks). Moreover, the bio-sourced adhesive performs better than
neat DGEBA. As the latter loses 35% of its adhesive strength (dropping its “stress to break”to 2,2
MPa), CNSL-dGE adhesive only loses 21% of its initial strength, with a stress to break around 4,5
MPa, still higher than the initial value of DGEBA.
While CNSL-dGE adhesive clearly present the drawback of limited temperature applications, the
DGEBA/ CNSL-dGE co-networks are an excellent compromise even with 70%wt DGEBA substi-
tuted, with adhesive and water resistance properties higher than those of DGEBA adhesive, and
a Tg higher than 100°C. Finally, the impact of some traditional epoxy fillers like mineral clays
onto DGEBA/ CNSLdGE co-networks was evaluated, evidencing some additional advantages of
using the bio-based DGEBA substitute.
29From Biobased Polymers to Bioplastics 2013
Notes
30 From Biobased Polymers to Bioplastics 2013
Abstract
MATERIALS SELL BY PROPERTIES! WHAT SELLS PHB!
IS THERE ANYTHING PHB CAN DO BETTER THAN OTHER BIOPLASTS/THERMOPLASTS ?
Urs J. Hänggi - Biomer, Germany
Both, native PVC and native PHB (polyhydroxybutyrate) have thermoplastic properties, but are
not useful for thermoprocessing. Only after transforming the native PVC by compounding with
the proper additives, PVC emerges as a high performance thermoplast which excels in medical
tubing, in window frames, or in pipes. The same is true for PHB.
Native PHB evolved in nature to function inside the cells. There it needs to be absolutely linear,
absolutely isotactic, absolutely regular (C4-subunits), and totally biodegradable. Being abso-
lutely linear means that the molten polymer chains do not entangle like the chains of manmade
thermoplasts. Thus the melt viscosity depends entirely on the temperature settings. Absolutely
isotactic and absolutely regular means that the molten polymer chains have no chance except
to crystallize till there is no free amorphous mass left. In this respect PHB compares to metals.
In other words: once native PHB is compounded with the proper additives, it emerges as a high
performance thermoplast.
The variable melt viscosity, controlled by the temperature settings, can be used to produce parts
with very fine structures (example screw) or to produce parts with surface structures down to
below 0,2 µ (example imprints). This also is possible with liquid crystalline polymers. However
with PHB molding can be done at temperatures as low as 180°C.
The crystallinity allows producing long natural fiber composites with unique impact strength.
Upon crystallization, the matrix recedes from the fibers. However, the hard crystals clamp the
fibers where they are thicker and hold them there like in a vice. Thus the fibers are free to vibrate
between the clamped points and thus to absorb the impact (example composite plate). The high
crystallinity made of hard crystals means creep resistance like in metals. Production by molding
is dramatically less expensive than metalworking. Thus PHB can lower production costs of parts
that could be produced so far by metalworking only (example smoke grenade).
Native PHB was designed by nature to be absolutely linear, absolutely isotactic, and absolutely
regular. No manmade thermoplast matches these properties. Plastic processors can use these
specific properties in compounded PHB to mold parts that can not be formed easily with man-
made thermoplasts. The parts are stable for decades. Being of renewable resources
31From Biobased Polymers to Bioplastics 2013
Notes
32 From Biobased Polymers to Bioplastics 2013
Abstract
SOLANYL AND FLOURPLAST THERMOPLASTIC STARCH BASED PLASTICS AND OPTINYL
MASTERBATCHES: CREATING NEW OPPORTUNITIES FOR THE BIOPLASTIC INDUSTRY.
Jeroen van Soest - Rodenburg Biopolymers B.V, The Netherlands
Rodenburg Biopolymers developed over the last year new bioplastics to add to their portfolio
i.e. FlourPlast precompounds, Solanyl end-compounds and Optinyl masterbatches. This paper
describes the structural features and properties of products made of these new materials. Flour
or purified starches are not thermoplastics. The FlourPlast and Solanyl portfolio of products are
based on thermoplastic flour (TPF) or starch (TPS) and are made by an unique combination of
natural based by-products or reclaimed starch sources from the food processing industry and
a novel compatibilising polymer system making it thermoplastic materials, which can be pro-
cessed on standard processing machines.
The FlourPlast portfolio of products is shown to be highly compatible biodegradable polyesters
but also polyolefins such as polypropylene giving the opportunity to make dedicated bioplastics.
It is shown that improved processing conditions are obtained and enhanced or novel properties
of the end formulations (compounds). By making different combinations of various grades of
FlourPlast (i.e. building block system of precompounds) with other polymers, it is possible to ob-
tain a range of products with different properties and novel functionalities. This made it possible
to process the components into products by the compounding industries suitable for various ap-
plications such as injection molding, extrusion and thermoforming, and film blowing and casting.
The Solanyl’s consist of ready-to-use biodegradable and biobased compounds suitable for
converters to obtain biodegradable or biobased products. The portfolio consist of various com-
pounds suitable for injection moulding (C1*** series), (sheet) extrusion and thermoforming
(C2*** series), and film extrusion (C8*** series). The various compounds offer a complete set
of properties.
Specially designed for FlourPlast, Solanyl or other biopolyester plastics Rodenburg Biopolymers
offer Optinyl masterbatches offer the opportunity for converters to fine tune other properties
such as colour, flow, impact and many more. Some remarkable examples are described.
33From Biobased Polymers to Bioplastics 2013
Notes
34 From Biobased Polymers to Bioplastics 2013
Abstract
BIOPOLYMER TEXTILE APPLICATIONS:
SHIFTING STABILITY PROPERTIES USING FUNCTIONAL ADDITIVES.
Luc Ruys*, Raf Van Olmen - Centexbel, Belgium
Gradually biopolymers find more and more industrial applications in packaging, textiles and
composites. Especially Poly Lactide (PLA) is one of the biopolymers of choice for a series of ap-
plications when higher requirements need to be fulfilled.
For instance in textiles or in composite applications the interest in generating fully biobased
products is high. It is already proven that PLA can be processed into a complete range of different
textile intermediates including, fibre, monofilament, tape, and multifilament and can be further
processed into a range of end products.
An important element regarding the properties of these materials is related to their durability.
It’s well known that PLA grades will be easily degraded under industrial composting conditions.
This property can be considered as an advantages for these applications where composting
offers a good end-of-life possibility. Questions are however raised how the materials will be-
have under less severe biodegradation conditions. Will materials not degrade too fast if used
as ground-cover? Is the material stable enough against UV light? Can the material be used for
products with an expected lifetime for 5 years and more ?
Research was performed regarding the durability of textile products under different conditions
using a range of different additives. Additives were defined that are enhancing the degradation
process for those applications where a faster degradation under environmental conditions is re-
quired. On the other hand additives could be defined as well that are clearly improving polymer
properties as well as stability both during processing as well as under extreme conditions of use.
More details on the approach and properties reached will be given in the presentation.
35From Biobased Polymers to Bioplastics 2013
Notes
36 From Biobased Polymers to Bioplastics 2013
Abstract
BIO-SOURCED MATERIALS:
RISKS OR OPPORTUNITIES FOR AUTOMOTIVE APPLICATIONS ?
Gérard Liraut - Renault, France
Since at least the 1980s, the history of plastic in the automotive applications has been a success
story: about 14% of the automotive is made of plastic. More than 500 different plastic parts are
usually used in an average European car (bumper, fender, instrument panels, trims, headlamp,
air intake manifold, fuel tanks,…) , leading to a large variety of different plastic material (PP,
PA, HDPE, ABS, PC, POM, PBT,…). Even if there is a large diversity of polymers, they are almost
always produced from crude oil. In order to reduce the cost, to improve the environmental foot-
print and to respect some European regulations, some OEMs have been using more and more
recycled plastic materials. However, BIO-sourced materials seem to propose another interesting
option. The present lecture will give an overview of the current applications of bio- plastics used
in a car, will also present some studies and results dealing with BIO-plastics. Then as a conclu-
sion, we will explain the RENAULT philosophy in choosing material for plastic applications.
37From Biobased Polymers to Bioplastics 2013
Notes
38 From Biobased Polymers to Bioplastics 2013
Abstract
BIOBASED ADHESIVES:
WHEN GREEN CHEMISTRY MEETS THE MATERIAL SCIENCE OF STICKY THINGS
Richard Vendamme - Nitto Europe N.V, Belgium
The growing awareness of society towards environmental issues combined with the recent gov-
ernments regulations and incentives towards the reduction of carbon dioxide emissions is push-
ing the chemical and adhesive industries to develop greener products and to find alternative
growth strategies based on more sustainable economical models. Although the use of raw mate-
rials derived from renewable feedstock seems a particularly relevant option, finding sustainable
and efficient ways to transform biofeedstocks into highly functional materials and coatings is
still very challenging.
Pressure sensitive adhesive (PSA) materials are a peculiar class of glues intended to form a
reversible bond simply by the application of a light pressure to marry the adhesive with the
adherent. Conceptually, PSAs must be designed with a subtle balance between flow and resist-
ance to flow: the bond forms because the adhesive is soft enough to wet the adherent, but the
bond also has suitable strength because the adhesive is hard enough to resist the stress of the
debonding stage. To date, most commercial PSA are still based on petroleum resources and there
is an imperious need to develop more sustainable PSA chemistries.
The development of biobased materials is one solution (among others) used by the Nitto Denko
group to tackle environmental problems. In this talk, we would like to demonstrate that Nitto
Denko’s ambition to make a step-forward in the advancement of biobased adhesives take the
form of pragmatic and multi-angle investigations covering both value chain considerations
(monitoring and screening of biobased raw material, performing Life-Cycle-Assessment), tech-
nical aspects (leveraging the performance and reliability of biobased adhesives) and new busi-
ness development (unravelling the full business potential of biobased adhesives). The technical
part of the presentation will be focused on the development of polyester-based pressure sensi-
tive adhesives derived from various renewable biofeedstocks such as plant oils or sugars.
Reference: Interplay Between Viscoelastic and Chemical Tunings in Fatty-Acid-Based Polyester
Adhesives: Engineering Biomass toward Functionalized Step-Growth Polymers and Soft Net-
works. R. Vendamme*, K. Olaerts, M. Gomes, M. Degens, T. Shigematsu, W. Eevers, Biomacromol-
ecules, 13, 1933-1944 (2012)
39From Biobased Polymers to Bioplastics 2013
Notes
40 From Biobased Polymers to Bioplastics 2013
Abstract
EMISSIONS FROM PLA MATERIALS: FOOD PACKAGING AND AUTOMOTIVE APPLICATIONS
Annabelle Cingöz*, A.Borcy, C. Henneuse, Piroëlleaa, C. Courgneaua,b, D. Rusua,b, M.-F. Lacrampea,b,
R. Salazarc, P. Krawczaka,b, V. Ducruetc
Certech asbl, Belgium
aEcole des Mines de Douai, Dept of Polymers and Composites Technology & Mechanical Engi-
neering, France; bUniversité de Lille, France; cINRA UMR 1145 Ingénierie Procédés Aliments, France
Over recent years, much attention has been given to potential applications of poly(lactic acid)
(PLA) as a replacement for petroleum based polymers. PLA has already been approved for food
contact and is now used in short shelf-life food packaging like drinking cups, salad cups, packag-
ing films, and trays. One of the principal functions of food packaging is to protect food product
from external pollution. However, plastic processing can affect properties of the plastic material,
and also generate sensorial and/or healthy issues that could potentially have an impact on the
food quality. The packaging itself is not completely inert in contact with food and additives and
other volatile compounds present in the polymeric packaging material can also migrate into the
food. Therefore, he objective of the present study was to determine the effect of plastic packag-
ing processing (extrusion and thermoforming) on the degradation of PLA by analyzing the evolu-
tion in sensory properties (volatile organic compounds, VOC and odour emissions).
For automotive use, a single niche application of compression molded PLA has been developed.
To meet the performance requirements of car interior materials (tensile, flexural and impact
properties, aging resistance..), the adding of natural fibers (short fiber of cellulose) to PLA allows
on one hand, a reinforcement of the material and on the other hand a weight gain, so a positive
impact on on energy consumption and reduce greenhouse gas emissions. However, these natu-
ral fibers present several drawbacks and especially emission of VOC responsible for off-odor.
The objective of this study was first to estimate the impact of processing and of adding fibers
on global odour and then to remediate to these off-flavour problems by testing different types
of agent added to the process. Once their efficiency proved on the global odour, the physico-
chemical and mechanical characteristics of the remedied biocomposite were studied.
41From Biobased Polymers to Bioplastics 2013
Notes
42 From Biobased Polymers to Bioplastics 2013
Abstract
REDUCING THE ENVIRONMENTAL FOOTPRINT OF POLYURETHANES USING
BIOSUCCINIUM™ BASED POLYESTER POLYOLS
Luc Leemans*, R. Janssen, L. Theunissen - DSM Ahead Materials Sciences R&D, The Netherlands
Biosuccinium™, Reverdia’s™ biobased succinic acid has been successfully evaluated as an al-
ternative for (fossil-based) adipic acid in a number of polyester polyols, which subsequently
have been polymerized into thermoplastic polyurethane formulations. This enables a potential
improvement of the sustainability characteristics of the polyurethane materials because Biosuc-
cinium™ is a 100 % biobased and renewable raw material Both succinate and adipate polyester
polyols have been prepared, with Mn = 2000g/mol, based on either 1,4-butanediol or a combina-
tion of 1,4-butanediol and ethylene glycol. These polyols were subsequently converted to TPU
material by their reaction with stoichiometric amounts of pure MDI and chain extended with
1,4-butanediol.
Industry standard thermoplastic polyurethanes based on adipate polyol were prepared as refer-
ence materials.
It was concluded that Biosuccinium™ based polyester polyols can be formulated into thermo-
plastic polyurethane polymers with a typical degree of hardness (85 and 95 Shore A), without
major changes to existing equipment or processing procedures. A more detailed evaluation of
mechanical and thermal properties is still in progress and will be reported on in a later stage.
43From Biobased Polymers to Bioplastics 2013
Notes
44 From Biobased Polymers to Bioplastics 2013
Abstract
NEW RENEWABLE MOLECULES FOR BIOBASED POLYMERS.
Stéphane BERNARD*, Ward HUYBRECHTS - OLEON NV, Belgium
Biobased polyols for polyurethane market: new oleochemical processes allow the design of re-
newable polyols in line with the technical requirements of different polyurethane markets. By
tuning molecular weight, functionality and crystallinity, Oleon has developed a new range of
polyester and polyether polyols for CASE, flexible or rigid foams. Some of these new renew-
able polyols allow a simple 1:1 replacement of the conventionally used petrochemical polyols.
In CASE applications, where hydrophobicity and flexibility are important, the final PU shows
improved properties in comparison to conventional systems. In foam applications, these renew-
able polyols can be used directly or in a prepolymer system, and reactivity is improved thanks to
the very high content of primary OH.
Biobased propylene glycol for unsaturated polyester resins (UPR): the high quality level of bio-
propylene glycol, made from renewable glycerol, enable the replacement of the conventional
petrochemical based molecule by a sustainable MPG with a reduced environmental footprint.
Calculations show that the developed process to convert glycerol into bio-propylene glycol emits
70% less greenhouse gas compared to fossil propylene glycol.
45From Biobased Polymers to Bioplastics 2013
Notes
46 From Biobased Polymers to Bioplastics 2013
Abstract
BIOPREPOLYMER DEVELOPMENT FOR THE USE OF AUTOMOTIVE SEATING FOAM
Christophe Ponce*, Annelies Vandevelde, Herman Moureau, Joris Pittevils, Veerle Moons
Huntsman Polyurethanes, Belgium
Recently automotive OEMs have published new specifications for automotive components
which require a measurable amount of biobased content based on C14. In order to support this
new requirement Huntsman has developed a flexible foam technology solution which incorpo-
rates an amount of vegetable based raw material in the production of an MDI bio-prepolymer.
The latter will enable Customers to increase the level of biobased content within a MDI based
flexible automotive seating technology. The introduction of biobased content specifically via the
Huntsman bio-prepolymer maintains typical physical foam characteristics. The additional ben-
efit is that the new foam technology can be run on Customers existing seat moulding equipment.
47From Biobased Polymers to Bioplastics 2013
Notes
48 From Biobased Polymers to Bioplastics 2013
Abstract
PACKAGING FOR FOOD OR FOOD FOR PACKAGING ?
THE ROLE OF BIOPLASTICS IN THE NESTLÉ PACKAGING PORTFOLIO
Lars Lundquist - Nestlé Research Center, Switzerland
This presentation will elaborate around the importance of a holistic life cycle-based approach
integrating the role and function of packaging in terms of delivering product protection and pre-
venting waste in determining the environmental credentials of bio-based materials and bioplas-
tics. Important issues related to land use, water scarcity and food security connected to the field
of bio-based materials and bioplastics will be discussed.
49From Biobased Polymers to Bioplastics 2013
Notes
50 From Biobased Polymers to Bioplastics 2013
Abstract
NEW RENEWABLE POLYURETHANE ADHESIVE FOR FLEXIBLE PACKAGING
Olivier Laferté*, Guillaume Michaud - Bostik, France
Continuous innovation is a priority at Bostik to anticipate customer needs and provide them with
fully functional and highly optimised solutions with tangible benefits.
Bostik’s R&D teams worldwide continually focus on designing cost-effective adhesive solutions
to help our customers improve the performance of their products and the productivity of their
processes, while maintaining priority on easy and safe handling as well as minimising environ-
mental impact.
Adhesives for laminating, solvent free two components polyurethane are widely used as glue
for the manufacture of multilayer systems in the field of flexible packaging. Flexible packaging is
used to package a wide variety of products in the food, cosmetics and detergents industries, and
can provide characteristics suitable for flexible packaging:
• A barrier effect to atmospheric moisture or oxygen,
• Food contact,
• Chemical resistance,
• Good resistance to high temperatures, for example in case of pasteurization.
Adhesives for laminating, solvent free two components polyurethanes are widely used for the
manufacture of multilayer systems. In fact, these adhesives contain no organic solvents or water
which gives the advantage of being implemented in lamination industrial operations with very
high line speeds without energy-intensive drying step.
As sustainability is a pillar of our development, Bostik is involved in the development of “green”
chemistry. We are willing to substitute, partly or totally, the use of non-renewable raw materials
based on petroleum-derived fuels by renewable raw materials based on vegetable resources.
This presentation aims at describing a new two-component polyurethane based adhesive for lam-
inating with high properties and in which the isocyanate-based prepolymer is obtained by a pro-
cess using more renewable raw materials. We will focus also on application trials and LCA study.
51From Biobased Polymers to Bioplastics 2013
Notes
52 From Biobased Polymers to Bioplastics 2013
Abstract
LIFE CYCLE THINKING APPROACH FOR SUSTAINABLE FEEDSTOCK DESIGN
Houshang Kheradmand - Dow Chemical Company, France
The key business drivers of any successful company have to encompass sustainable develop-
ment criteria during technology and product design. Such criteria put a focus on sustainable
growth – sustainable competitive advantage leading to sustainable earning power. Sustainabil-
ity as a concept becomes a founding principle for continuous improvement, leading to either
evolutionary or revolutionary innovations.
This presentation will focus on trends and opportunities identification for polymer industries
and methodologies for integrate sustainable development criteria across the product life cycle,
from conception through to recycling and the waste management phase.
Today’s mega-trends (Economic, Ecological and Social), have generated the need for an academic
and industrial revolution in mind-set, processes and product design, resource allocation and the
management of the wastes over the product lifecycle. The growth of population, consumption
and the limit of resources have created constraints for all industries including the dispersion
polymer industry, which presents challenging opportunities requiring invention and innovation.
Monomers are obviously the key raw material for the Coatings industries and the new sources
management is critical for the industry’s future. We will demonstrate via examples the Life Cy-
cle Approach benefits for sustainable coatings design including ecological and socio-economic
impact.
Key words: Acrylic, Monomer, Biomass, Biodiesel, Bioplastics, CFP, Design, Glycerol, Green
Chemistry, Energy, Life Cycle, Polymerization, Propylene, Population, Resources, Socio-Econom-
ic, Solvent, Sugar, Sustainability, Waste.
53From Biobased Polymers to Bioplastics 2013
Notes
54 From Biobased Polymers to Bioplastics 2013
Abstract
AGROBOOST:
A COLLABORATIVE PROJECT ON BIOBASED TEXTILES WITH CONTROLLED BIODEGRADATION
Isabelle FERREIRA - IFTH, France
Agroboost is a funded* French collaborative project which aims to develop new biobased textiles
for specific applications in the field of agrotextiles and geotextiles.
The products covered by the project are the following: textiles and paper mulches, twine and
agricultural guardians, nets packaging for fruit and vegetables, nets for crops and temporary
reinforcement geotextile which are the main fields of application of the Industrial partners of
the project (Bihr, Texinov, Trocme Valllart Emballage and Buitex).
The project was supported and labelized by 4 french competitiveness clusters: Techtera cluster
(textile cluster), Plastipolis cluster (plastics cluster), Fibres cluster and Agro-resources & Indus-
tries clusters.
The innovation of the project is based on the two following aspects:
- controlled biodegradability : the biodegradability of products developed will be monitored and
adapted regarding their different uses.
- solutions will be made to develop products the more biobased.
During the conference will be presented the project (workprogramm, objectives, processes de-
veloped,…) and some results of course non confidential.
* Agroboost is funded by the DGCIS, OSEO, the Rhone Alpes FEDER, the Rhone Alpes Conseil
Regional, the Lorraine FEDER, the Lorraine Conseil Regional, the Vosges Conseil General.
55From Biobased Polymers to Bioplastics 2013
Notes
56 From Biobased Polymers to Bioplastics 2013
Abstract
TOWARDS FULLY GREEN COMPOSITES ?
Naïma Sallem*, Michel Sclavons, Jacques Devaux - Université Catholique de Louvain
IMCN/BSMA, Belgium
“Green composites” in material science do not have nowadays to look as strange as “Little green
men” on earth. Indeed, “Green chemistry” cannot be limited to chemistry from vegetal sources,
but, more generally, includes processes allowing to produce chemicals by more “environment –
friendly” methods. In this presentation, a process will be presented, the main characteristics of
which being that it uses water as processing aid in thermoplastic extrusion.
Such a process, by decreasing the temperature during composite processing, allows to incorpo-
rate more easily biosourced fillers while limiting their degradation.
Perspectives will also be presented towards (nano)composites where both the filler and the ma-
trix are biosourced.
57From Biobased Polymers to Bioplastics 2013
Notes
58 From Biobased Polymers to Bioplastics 2013
Poster
Initial trials at Constar showed that bottle blowing with
/ Department of Chemical Engineering and Chemistry
/Laboratory of Polymer Materials (SPM)
Producing a PLAstic bottlevia strain-induced crystallization of poly(lactic acid)Pim Lohmeijer, Han GoossensEindhoven University of Technology, Laboratory of Polymer Materials, P.O. Box 513, 5600 MB, Eindhoven, The NetherlandsEmail: [email protected] Office: STO 0.44 Phone: (040-247) 4930
Acknowledgments This work is part of the Biobased Performance Materials research programme, project no. BPM-130 “PLAstic Bottle”, and financially supported by the Dutch Ministry of Economic Affairs, Agriculture and Innovation.
Strain-induced crystallization (SIC) Development of crystal structures during deformation in poly(lactic acid) (PLA) is an important aspect during processing. Therefore, understanding deformation mechanisms to tune product properties is essential in order to enhance the application range and competitiveness of PLA. Conventional amorphous injection-molded PLA has low barrier properties for vapor and water, however molecular orientation and strain-induced crystallites introduced during the injection-stretch blow molding (ISBM) process, applied in bottle production, will impede the passage of small molecules through the PLA matrix. The final goal of this project is to produce a PLA bottle with comparable performance to its oil-based counterpart.
Injection stretch blow molding (ISBM) of a PLA bottle (Lim et al., Prog. Polym. Sci., 2008, 33, p820-852)
70 80 90 100 11005
1015202530354045
150 kDa, DR 3150 kDa, DR 4.580 kDa, DR 380 kDa, DR 4.5
Crys
tallin
ity (%
)
Stretching temperature (oC)
1) Material parameters Deformation parameters
2) Strain-induced crystallization (SIC) and morphology
3) Properties -Barrier -Mechanical -Optical
Again a morphology gradient was observed, but the inhomogeneity might have originated from the rather ill-controlled heating method. Therefore a setup with PID-controlled IR heaters was designed and installed to ensure good temperature control.
In subsequent trials increasing the blow mold temperature
Outlook • Preform morphology investigation • Barrier properties measurements • 1D deformation with improved IR-setup • Orientation determination of amorphous phase via FTIR spectroscopy • Controlled 2D-stretching (in combination with FBR) • In-situ crystallinity development during 1D-stretching (at ESRF, Grenoble)
1D deformation • Injection molded tensile bar, thickness ~ 3.3 mm
Injection stretch blow molding • Injection molded bottle preform, thickness ~ 4.2 mm
The ISBM process is highly complex, therefore in order to do
• Stretching temperature dependence: interplay between
• Rapid specimen heating to 70-130 °C (with heat guns) • Stretching up to DR ~ 6, stretch rate up to 50 %/s
Synterra PLLA grades from Synbra is possible. With the blow mold at room temperature a low crystallinity of 8% in the sidewall was determined via WAXD. SEM images revealed many voids in the material.
resulted in bottle crystallinities of 20-25%. However, this also appeared to promote a morphology gradient through the sidewall thickness. This can be explained by both the inhomogeneous cooling of the thick preform during injection molding, as well as the one-sided heating during the blowing step.
a fundamental study of SIC of PLA a simplification to 1D deformation under well-controlled conditions is required.
For this study two Synterra PLLA grades from Synbra of different molecular weight were injection molded and stretched uniaxially after a rapid heating step using two heat guns, similar to the ISBM process. This allowed for studying various influential parameters on crystallinity and orientation in the materials:
crystallinity, chain orientation and relaxation • Molecular weight effects: limited range for stretching low MW: T < 90 °C: fracture; T > 100 °C: flow
• Draw ratio influence: crystalline order disturbed at DR 4.5
• Rapid preform heating (with IR) to 90-100 °C • Very rapid stretch rod insertion ( > 1500 %/s), air pressure ~ 38 bar, to DR 2.7×4.5 • Blow mold temperatures: 20 °C and 100 °C
59From Biobased Polymers to Bioplastics 2013
Poster
APPLICATION OF BIOBASED MATERIALS AS FOOD PACKAGING
Nanou Peelman1,2, Peter Ragaert1,2, Angelique Vandemoortele1,2, Elien Verguldt1,
Bruno De Meulenaer2, Frank Devlieghere1
1Laboratory of Food Microbiology and Food Preservation and 2Research Group Food Chemistry
and Human Nutrition, Department of Food Safety and Food Quality, Ghent University, Coupure
Links 653, 9000 Ghent, Belgium
The possible application of several multilayered biobased materials for packing different food
products, ranging from short to long shelf life products, was investigated. Some transparent and
metalized cellulose based film, a cellulose/PLA based film, a xylan based film and PLA trays
with a PLA based film, a cellulose/PLA based film and a paper/PLA based film as topfilm were
examined. The investigated food products were tomatoes, steak, French fries, ham sausage, filet
de saxe (a raw cured pork meat product) grated cheese, tortillachips, rice cakes, speculoos and
potato flakes all packaged under air or modified atmosphere packaging (MAP). The food prod-
ucts were stored at refrigerated (under alternately 12h light/12h dark) or room temperature and
analyzed at certain points during their shelf life. For the short shelf life products, microbiological
analysis (total plate count, lactic acid bacteria and yeast and moulds), gas composition of the
headspace, color, aw and pH were followed and those quality parameters were each time com-
pared with their evolution in the conventionally packaged food products. For the medium shelf
life products also hydrolytic and oxidative lipid rancidity were monitored. For the long shelf life
products no microbiological analysis was performed. Furthermore, sensory characteristics of the
different food products were evaluated as well as printability and migration. Finally, also case
studies at the companies were performed.
From the storage experiments it could be concluded that most investigated biobased materi-
als are good functional substitutes for the conventional packaging materials currently used. For
example, the oxygen and carbon dioxide concentrations followed the same trend as in the refer-
ence film and the concentrations remained below the maximum limit or above the minimal limit
during the entire shelf life of the food products.
60 From Biobased Polymers to Bioplastics 2013
Poster
CHARACTERISATION OF VOLATILE COMPONENTS IN BIODEGRADABLE POLYMERS USING
STEAM DISTILLATION-EXTRACTION-GAS CHROMATOGRAPHY-MASS SPECTROMETRY
I. DIRINCK
SENSTECH, Flemish Advice Centre for Sensory Quality of Food Products and Food Contact Mate-
rials, Technologiepark 3, IIC, BE-9052 Gent (Zwijnaarde)
Gas chromatography-mass spectrometry (GC-MS) is the analytical technique of choice for analy-
sis of volatile organic compounds (VOCs) in all kind of food contact materials. Depending on the
purpose of the analysis and the matrix different isolation techniques for volatile compounds
can be used.
Simultaneous steam distillation-extraction (SDE or Likens-Nickerson extraction) is a ‘total vola-
tile’ extraction technique, which can be used for characterisation of volatile organic compounds
(VOCs) in various materials (paper, cardboard, can, polymers, …).
The chemical structures and the amounts of VOCs present in food contact materials, together
with the odour threshold values, can give an estimation about the odour characteristics of food
contact materials. The GC-MS analysis of VOCs in packaging materials also gives an idea about
the possible migration of volatile packaging components from a packaging material towards a
packed food product, eventually influencing the sensory properties of the food product. Often
packaging-related off-flavours in foods result in claims and expensive recalls, which can affect
consumer confidence and damage the company image.
Although many commercially-available bioplastics have good organoleptic properties, bioplas-
tics from different origins and manufacturers can have different VOCs contents and therefore
influence the sensory properties of packed food products to a greater or lesser extent.
In this study four biodegradable materials were analysed using steam distillation-extraction-
gas chromatography-mass spectrometry (SDE-GC-MS) in order to characterise the volatile com-
pounds in the bioplastics:
61From Biobased Polymers to Bioplastics 2013
- polyhydroxybutyrate (PHB) type 1 (manufacturer A)
- polyhydroxybutyrate (PHB) type 2 (manufacturer A)
- polylactic acid (PLA) + co-polyester type (manufacturer B)
- starch-based type (manufacturer C)
Biodegradable drink cups were produced by standardised injection moulding procedures using
four master batches of pellets or granulates and analysed with SDE-GC-MS. The ‘total volatile’
profiles of the different biodegradable materials were explored and volatile organic compounds
were identified using mass spectral libraries. The volatile profiles of the different biodegradable
materials were compared and odour-active compounds were assigned.
SDE-GC-MS can be applied to evaluate the volatile content of biodegradable materials from dif-
ferent bio-based origins, as well as to highlight the organoleptic differences between master
batches from different manufactures. This valuable ‘total volatile’ analysis technique can also be
used for monitoring the variability between different production batches from the same manu-
facturer, the influence between different production sites and the performance of a recycling
process for biodegradable packaging materials with regard to volatile contaminants.
62 From Biobased Polymers to Bioplastics 2013
Poster
PHBOTTLE PROJECT:
NEW SUSTAINABLE, FUNCTIONALIZED AND COMPETITIVE PHB MATERIAL BASED IN FRUIT BY-
PRODUCTS GETTING ADVANCED SOLUTIONS FOR PACKAGING AND NON-PACKAGING APPLICATIONS
Lurdes Soares ([email protected] )
AIJN - European Fruit Juice Association, Rue de la Loi 221 box 5, B-1040 Brussels, Belgium
On the one hand, packaging waste is a pressing environmental, social and economic issue. In-
crease in packaged food consumption and a developing economy continue to generate large
amounts of waste1. The generation of packaging waste per capita in the EU was set at 157 kg/
capita in 20102. On the other hand, fruit juice and nectars consumption in the EU stood at 10.7
billion litres in 2011. Nearly 65% of the total volume consumed was packaged with carton and
24,6% with plastic3 .
The fruit juice industry generates enormous amounts of wastewater (24–30 m3/batch4). Such
wastewater effluents contain high concentrations of valuable organic matter.
The objective of the PHBOTTLE project is to develop a new sustainable bottle (body, cap and
sleeve) which is made from organic matter (sugars, residues rich in carbon, oxygen and nitrogen)
present in the wastewater from the fruit juice industry. The new packaging will be biodegrad-
able, have antioxidant properties and will be used for applications in the food packaging sector,
mainly juice industry.
PHBOTTLE research is focused on PHB (polyhydroxybutyrate) bioproduction using juice indus-
try by-products as culture medium. Functional materials (cellulose microfibers and encapsulat-
ed ingredients) will be used to improve the packaging material properties’. The industrial appli-
cability of the new material will be tested and the impact on the environment will be addressed
via Life Cycle Assessment (LCA).
PHBOTTLE is an International Project funded by the European Union’s Seventh Framework
Programme [FP7/2007-2013] under grant agreement n. 280831.
1 http://www.eea.europa.eu/themes/waste1 http://www.eea.europa.eu/data-and-maps/indicators/generation-and-recycling-of-packaging-waste/generation-and-recycling-of-packaging-4
3 AIJN 2012, Liquid Fruit Market Report4 Treatment of high strength wastewater from fruit juice industry using integrated anaerobic/aerobic system. H. El-Kamah, A. Tawfik, M. Mahmoud, H. Abdel-Halim. Desalination. Volume 253, issues 1-3. April 2010, Pages 158–163.
63From Biobased Polymers to Bioplastics 2013
Poster
SYNTHESIS OF BIOBASED THERMOSETS RESINS FOR INDUSTRIAL APPLICATIONS
Julien Estager, Certech asbl, Zone industrielle C, Rue Jules Bordet B-7180 Seneffe Belgium
Petroleum based chemistry will unambiguously keep on leading the market for the next decades.
However, due to a strong lobbying from associations and customers, it becomes more and more
difficult for companies to ignore biobased chemistry if they want to promote their brands. As
these new products are directly in competition with traditional plastics, they must remain com-
petitive in term of properties and prices.
In this perspective, Certech has taken part into a joint-venture regrouping SMEs and universities
to develop biobased thermoset resins. As the objective is to obtain a commercial formulation,
this consortium gathers all the aspects of development from the synthesis of monomers to the
full scale test on an industrial site.
Different pathways have been investigated to fulfil the requirements of our industrial partners.
The use of vegetable oil appeared to be a valuable option, even reinforced by the large produc-
tion of linseed oil in Wallonia. The different formulations led to interesting properties after high
temperature curing.
As our partners are aiming room temperature applications, we have developed new polysac-
charide-based monomers. The resins obtained after formulation exhibit good properties and
polymerise at room temperature.
64 From Biobased Polymers to Bioplastics 2013
Poster
THE ANALYSIS AND CHARACTERIZATION OF BIODEGRADEABLE POLYMERS
BY GEL PERMEATION CHROMATOGRAPHY (GPC)
A Brookes*, B MacCreath - Agilent Technologies, United Kingdom
[email protected], [email protected]
Biodegradation is the degradation of a material by environmental factors such as sunlight, tem-
perature changes or the action of microbes. In polymer science and engineering, the design of
polymers susceptible to biodegradation is of increasing importance for two reasons – polymers
that degrade naturally in the body to harmless products may be used in biological devices and in
drug delivery, and polymers that break down in the environment are significantly ‘greener’ than
traditional plastics.
Biodegradation is key to the suitability of materials for use in drug delivery devices or in tempo-
rary structures within the body, such as sutures. For these applications, the ability of the body
to naturally break down the material used either as part of the application or post-event is very
important, making the removal of the polymer simply a case of allowing the natural process of
degradation to occur.
The landfill crisis has made the production of non-polluting polymers for packaging and engi-
neering uses a high priority. These materials need to be able to perform their function, but also
break down in the environment with time, a difficult proposition. For these materials, the rate of
degradation and therefore the lifetime and performance of the polymer in the natural environ-
ment is related to the length of the polymer chains in the material, with degradation leading to
scission of the polymer chains and a shortening of their length.
Gel permeation chromatography (GPC, also known as size exclusion chromatography, SEC), de-
termines the molecular weight distribution of polymers, is therefore key to studying biodegrad-
able materials by giving an insight into the rate at which a material might degrade, and revealing
the presence of degraded polymer chains in a sample.
This poster shows examples of GPC applications involving different bioplastics and biodegrad-
able polymers.
65From Biobased Polymers to Bioplastics 2013
Notes
66 From Biobased Polymers to Bioplastics 2013
67From Biobased Polymers to Bioplastics 2013
Exhibitor
68 From Biobased Polymers to Bioplastics 2013
METTLER TOLEDO is a global manufacturer and marketer of precision instruments for use in
laboratory, industrial and food retailing applications. The Company has strong worldwide lead-
ership positions. A significant majority of our instrument sales are in segments in which we are
the global leader. In addition to a broad product offering, we have one of the largest global sales
and service organizations among precision instrument companies.
We focus on the high value-added segments of our markets by providing innovative instruments
that often integrate various technologies including application-specific solutions for customers.
We design our instruments not only to gather valuable data but also to facilitate the processing
and transfer of this data into customers’ management information systems.
METTLER TOLEDO is geographically diversified with sales in 2012 derived 34% from Europe,
34% from the Americas and 32% from Asia and other countries. The Company has an extensive
global sales and service organizations with approximately 6,000, or approximately one-half, of
our employees providing sales and service in 36 countries. The Company has a manufacturing
presence in Europe, the United States and China.
69From Biobased Polymers to Bioplastics 2013
Exhibitor
70 From Biobased Polymers to Bioplastics 2013
Notes
materials formulation & technology
centre
en chimiehe
alth
Cata
lysi
s
outstanding performance
Innovative reaction media
Green chemistry
Pilo
t pla
nts
renewable originhybrid materials so
l gel
tech
nolo
giqu
escertech
processintensification
environment
de ressources
& safetyEnergy from chemistry
Microtechnologies
recycling
-
Certech is member of
Certech
Zone industrielle C - Rue Jules Bordet - B-7180 SeneffeTel: +32 64 520 211 - Fax: +32 64 520 210
www.certech.be - [email protected]