2008-02

Page 1

ISSN 1862-5258

02 | 2008

Special editorial focus:

bioplastics

magazine

Vol. 3

Automotive Applications Natural Fibres

Improving heat resistance of PLA | 21 Situation in Australia | 34 LCA | 28, 36


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Editorial

dear readers Natural fibres or bio-fibres have been used in the automotive industry (but not only the automotive industry) for many years. They are lightweight, cost effective and offer excellent mechanical and thermal properties. The fact that this aspect is nothing really new, and the fact that they are in most cases combined with conventional, fossil-based plastics such as polypropylene, made us hesitate about including biofibres within the scope of our magazine. However the initial successes in attempting to combine such natural fibres with bioplastics as the matrix resin convinced us that they belong in bioplastics MAGAZINE. In addition to a rather basic introduction to natural fibre composites, in this issue we publish some interesting research results on natural fibre biocomposites. And we also jump back about 50 years, when engineers in former socialist East Germany (DDR) were making made great advances in the production of cotton fibre reinforced exterior car body parts. Some of these ‘Trabis’ (see cover photo) are still running on the streets today. Other topics in this issue include more news from bioplastics applications in the automotive industry, which is happening now in a big way in Japan. We are looking forward with interest to auto manufacturers in Europe, USA and other countries telling us about their experiences and future plans with regard to bioplastics.

ISSN 1862-5258

More and more companies are talking about LCA. The first results and reports are now being published. We are also starting to take a closer look at this subject – from a more general point of view as well as publishing specific reports from individual companies.

02 | 2008

Our ‘Logos’ series features the first article on logos for ‘biobased’ plastics rather than compostable plastics which were covered in the last two years. We hope you enjoy reading this issue of bioplastics MAGAZINE Special editoria l focus: Automotive App lications Natural Fibres

Yours,

MAGAZINE

bioplastics

Publisher

Vol. 3

Michael Thielen

Improving hea t resistance of PLA | 21 Situation in Aus tralia | 34 LCA | 28, 36

bioplastics MAGAZINE [02/08] Vol. 3


bioplastics MAGAZINE [02/08] Vol. 3

bioplastics MAGAZINE tries to use British spelling. However, in articles based on information from the USA, American spelling may also be used.

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bioplastics magazine ISSN 1862-5258

Natural Fibres in Automotive Applications

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Improving heat-resistance of PLA using poly(D-lactide)

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Cereplast’s Biopropylene™ and its application in automobiles

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Impressum Content 03

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42

March 02|2008 Politics

Toyota’s use of Bioplastics in Automotive Applications 7 Responsible Innovation: Reducing Environmental 28 Impact with NatureWorks® Biopolymer

Mazda introduced ‘Biotechmaterial’ for interior applications 8 Towards a bioplastics boom in Australia 34

Opinion

Be careful what you wish for... 36

Basics

‘BiomassPla’ logo of the Japan 38 BioPlastics Association(JBPA)

Materials

21

Processing

26


News

Metabolix to develop advanced industrial oilseed crops for bioplastics Metabolix, Inc., Cambridge, Massachussetts, USA, recently announced that it has initiated a program to develop an advanced industrial oilseed crop to produce bioplastics. Oilseeds are the primary feedstock for the more than 250 million gallons of biodiesel produced annually in the United States and the co-production of bioplastics promises to improve the economics of this crop industry. As part of this initiative, Metabolix has established strategic research collaboration with noted oilseed experts at the Donald Danforth Plant Science Center, a leading not-for-profit research institute in St. Louis. Metabolix will assemble a team of scientists to establish a research and development presence in St. Louis. The team will work closely with Danforth’s Principal Investigators Drs. Jan Jaworski, Edgar Cahoon and Joseph Jez. This collaboration is supported financially by a 2-year, $1.14 million grant from the Missouri Life Sciences Trust Fund to the Danforth Center. “The Danforth Center has extensive experience in oilseed technology. Combining their experience with Metabolix’s patented technologies could expedite the commercialization of multiple products in oilseed crops. This technology is expected to play an important role in reducing our reliance on fossil fuels,” said Dr. Oliver Peoples, co-founder and Chief Scientific Officer of Metabolix. “This initiative aims to create another biobased route to economically produce bioplastics and biofuels in high yields directly in non food crops. “ Industrial oilseeds represent the third crop system to which Metabolix is applying its patented technology. The company is a leader in developing enhanced switchgrass, and is also developing sugarcane crops to coproduce biobased and biodegradable plastic within the leaves and stems of these crops to more economically meet clean energy and bioplastic needs globally. www.metabolix.com

First-Ever Biodegradable PHBV Plastic Homegoods Products The average plastic container purchased today will live more than 10,000 times longer than its original owner, but consumers who today purchase the latest bath accessories from design experts Design Ideas®, Springfield, Illinois, USA, can take comfort that these plastic goods, with proper disposal, will safely decompose within a matter of months. “Design Ideas is the first design company to utilize EcoGenTM plastic in the production of decorative home goods,” said Andy Van Meter, Design Ideas president. “We’ve listened to our consumers and, more and more, they are conscious of their purchase decisions’ impact on the environment. We are happy to provide them a new choice they can feel good about.” EcoGen plastic is a PHBV (poly-3-hydroxy butyrate-co-valerate) “one of the five molecules that will change the world,” according to Forbes Magazine. To create practical household applications using this biodegradable material, Design Ideas enlisted the expertise of Professor Hans Maier-Aichen, a design teacher at the Karlsruhe University of Arts and Design in Germany and an award winning plastics designer. Professor Maier-Aichen leads a team of engineers in Europe, China and America. EcoGen can withstand temperatures of 110°C and will last indefinitely under normal conditions,” said Dr. Jim Lunt, vice president of Sales and Marketing at Tianan, the enterprise partnering with Design Ideas to produce the raw PHBV material. Design Ideas will be launching its first EcoGen line of bath products in April 2008. The bath items feature a bath cup, pump bottle, soap dish, toothbrush holder and waste can. www.ecogenlife.com

bioplastics MAGAZINE [02/08] Vol. 3


(left to right) David Beeby, Chief Executive Officer and Andy Sweetman, Market Development Manager, Sustainable Technologies plant the final tree at Sand Martin Wood,

News

‘Bioplastics in Packaging’ special theme at interpack 2008 The offerings highlighting the special theme ‘Bioplastics in Packaging’ at interpack PROCESSES AND PACKAGING Düsseldorf, Germany, which opens its doors between 24 to 30 April 2008, will form the biggest exhibition of its kind in the world. Roughly 10,000 trade visitors came to the ‚Innovationparc Bioplastics in packaging‘ at interpack 2005. With 1,000 m² of booth space for the ‘Bioplastics in Packaging‘ show at interpack 2008, co-organizer European Bioplastics is now proud to offer twice as much space for this special group exhibition as in 2005. About 40 International exhibitors active in sectors including raw materials, additives, finishing, plastics processing and packaging production will ensure that the topic bioplastics packaging is covered thoroughly. The showcase will feature all material classes (synthetic material/biodegradable, materials based on renewable primary products/biodegradable and materials based on renewable primary products/non-biodegradable). Visitors will be able to investigate the special theme in Hall 7a throughout interpack’s run. An ancillary programme including talks on current industry issues will round out the showcase. In the next issue bioplastics MAGAZINE will feature a comprehensive show preview. www.bioplastics-in-packaging.com

Cover-photo Our Covergirl Nicole says: „Interesting, that in today‘s cars natural fibres are being used. But that the old ‚Trabi‘ was made with Cotton Fibres is absolutely fascinating“.

NatureFlex goes carbonzero Innovia Films has achieved CarbonZero status on its full range of NatureFlex™ coated biodegradable and compostable packaging films through the implementation of carbon-reduction schemes. NatureFlex is one of the few packaging materials that has been tested to and complies with the specification required for soil, home composting and waste water applications at ambient temperatures, as well as for industrial composting. It has now built on its environmental credentials with its new CarbonZero status. Following a comprehensive Life Cycle Assessment (LCA) on its NatureFlex products during 2007, which was conducted to allow the company to quantify the environmental impact of the product on a ‘cradle to gate’ basis; Innovia Films were able to determine the carbon footprint of coated NatureFlex biodegradable and compostable packaging films in 2008. “Reducing a company’s carbon-footprint should principally be achieved through improvements in energy efficiency and reduced energy consumption, enhanced process technology and waste reduction. We have already made significant cuts in this way and are committed to continuing this in the future. Any manufacturing process will inevitably have an environmental impact and our involvement in these initiatives allows us to offset the overall effect of NatureFlex production and reassure our customers it is actually CarbonZero at the point of despatch from Innovia’s premises.” said David Beeby, Innovia Films Chief Executive. The fact that Innovia Films uses renewable raw materials to manufacture NatureFlex is an excellent start-point; NatureFlex films are typically around 95% renewable as measured by ASTM D6866. Working with a leading carbon services company, co2balance, who provide carbon reduction schemes both locally and globally, Innovia Films decided to plant 3,000 trees at Sand Martin Wood, Faugh, Cumbria. The planting of this new forest with a mix of British broad leafed trees within 30 km of their Wigton site was selected because NatureFlex is manufactured in Cumbria. The forest is directly owned and managed by co2balance, which will ensure that it is properly maintained into the future. www.innoviafilms.com, www.co2balance.com

bioplastics MAGAZINE [02/08] Vol. 3


Automotive

Toyota’s use of Bioplastics in Automotive Applications:

A

s consumers, we are all becoming increasingly aware of our impact that our decisions and actions have on the global environment. That is why, as a corporate citizen, Toyota is working on their own transition from the era of large-scale production and large volume consumption toward a recycle-oriented society that promotes conservation, reuse, and recycling. Within Toyota, this is called ‘Monozukuri in harmony with the Earth’.

This kind of thinking is growing globally within the Toyota company. It should be noted however, that this sustainable mentality does not apply only to their vehicles. For example, at the Canadian sales headquarters, Toyota has introduced containers, cutlery, and plates made from corn, sugarcane and potatoes. As a result, almost all of the building’s cafeteria waste can now be sent to compost, instead of to a landfill.

In 2003, Toyota made public its ‘Toyota Recycling Vision’ which aimed at achieving a 95% vehicle recovery rate by 2015. Today, many people associated with the bioplastics industry are aware of Toyota’s use of PLA and kenaf fibers that started with the 2003 Raum. However, these original applications were only a first step toward Toyota’s current bioplastics goal: ‘Development of technology allowing 20% use of resin parts by 2015 (combining bio plastic and recycled materials)’.

Moving forward, Toyota will continue their ongoing efforts to achieve their ‘Monozukuri in harmony with the earth’. Monozukuri literally translates to ‘product creation’-- but to Toyota, it is more than a literal translation-it is a way of thinking that incorporates activities and processes from material development through vehicle sales and service. Within this general idea, Toyota is aggressively pursuing biotechnology and bio-resource distribution through the establishment of novel biotechnologies, new bioplastics, and new ways to achieve a cycle of harmony with nature. As a result, in both the short term, and in the decades to come, one will see Toyota continue to work diligently to stay on the leading edge of automotive use of bioplastics.

In the summer of 2007, Toyota made another large step toward their corporate goal, implementing polyurethane seats that contain an average of slightly more than 5% soy polyol for the North American Toyota Corolla and Lexus RX (see photo above). Due to Toyota’s high material performance requirements, it was determined that the 5% soy level was appropriate based on the currently available technology. Toyota is now working closely with threir suppliers to expand the number of vehicle applications and to increase the level of soy being used in our flexible polyurethanes.

www.toyota.co.jp

Late in 2007, Toyota published its Seventh Annual North American Environmental Report. Each year, this public document outlines Toyota’s progress towards a sustainable society. In the section titled ‘Recycling and Improved Resource Use’, Toyota prints: “Along with soybeans in seats, Toyota is aggressively developing a North American vision that incorporates all aspects of biorenewable materials in future vehicles.”

bioplastics MAGAZINE [02/08] Vol. 3


Automotive

Interior component made of Mazda Biotechmaterial

Mazda introduced ‘Biotechmaterial’ for interior applications

T Mazda Premacy Hydrogen RE Hybrid

he world’s first biofabric made with completely plant-derived fibers, suitable for use in vehicle interiors, has been developed by Mazda Motor Corporation in collaboration with Teijin Limited and Teijin Fibers Limited. This newly developed biofabric does not contain any oil-based materials, yet it possesses the quality and durability required for use in vehicle seat covers. Resistant to abrasion and damage from sunlight, in addition to being flame retardant, the new biofabric meets the highest quality standards. This newly developed biofabric has harnessed the latest technologies to control the entire molecular architecture of raw resins to improve fiber strength until the fabric attained sufficient resistance to abrasion and light damage for practical use in vehicle seat covers. The biofabric is made of 100% PLA. Mazda developed this new biofabric in collaboration with Teijin Limited and Teijin Fibers Limited, companies with R&D and manufacturing sites in the region near Mazda’s headquarters in Hiroshima. Other crucial qualities necessary for the highest perform-

bioplastics MAGAZINE [02/08] Vol. 3


Automotive

ing fabrics, such as fire retardant properties, were achieved through Mazda’s accumulated experience in surface technologies built up through years of cooperation with several local companies. Seita Kanai, Mazda’s director and senior executive officer in charge of R&D, said, “Mazda succeeded in developing this 100% plant-derived biofabric for use in vehicle interiors by leveraging the technical expertise we have amassed in the Hiroshima area. We are convinced that our new technology, which enables the manufacture of this material without any oil-based resources, will become a cornerstone for future biotechnologies aimed at reducing the burden on the environment. Mazda, working together with our locally-based partners, will continue its research and development programs aimed at achieving a future car society that is eco-friendly.” Based on this biotechnology, Mazda will strengthen its future research and development on non-food-based materials in consideration of the impact such technologies have on food supplies. Mazda plans to use the biofabric for the seat covers and door trim in the all-new Premacy Hydrogen RE Hybrid that was exhibited in October at the Tokyo Motor Show 2007. The all-new Premacy Hydrogen RE Hybrid will also feature a bioplastic, which Mazda developed in 2006, in the vehicle’s instrument panel and other interior fittings. It is planned to start commercial leasing of this vehicle in Japan in 2008. “We have been trying to overcome technical challenges such as ensuring the bioplastic is strong enough to protect occupants in the event that an occupant is thrown against it in a collision, “ said a Mazda spokesperson. “We have achieved the highest quality standards for vehicle interior parts and their dimensions; and improved durability after repeated testing for heat, cold and dampness in various test conditions. In addition, we have been preparing the necessary design requirements for mass production of parts as well as building a large, reliable database of information.” All of Mazda’s biomaterials fall under the “Mazda Biotechmaterial” brand name. Mazda is dedicated to continuing its research and development efforts for these environmentally friendly technologies which will help to realize a sustainable society in the future. www.mazda.com

bioplastics MAGAZINE [02/08] Vol. 3


Automotive

Cereplast’s Biopropylene™ and its application in automobiles Article contributed by Frederic Scheer President and CEO Cereplast Inc. Hawthorne, California, USA

Biopropylene: Application examples

T

he automotive industry has been on the cutting edge of many technological breakthroughs. Today’s vehicles integrate state-ofthe-art entertainment systems, convenience features like rainsensing windshield wipers and proximity keys, and safety advancements that can help drivers avoid accidents. And many automakers are applying their engineering sophistication to advanced powertrain options that may lead to a more sustainable form of transportation in the future. But environmentally friendly powertrains are only one part of the sustainability equation in building vehicles of the future. To truly reduce the environmental footprint of automobiles, automakers must also consider both the manufacturing process and the raw materials they select to build their products. Consider that a typical automobile uses about 114 kg of plastic , which requires petroleum as a building block and significant energy to mold. Automakers must use virgin plastic because the cost of recycled material is simply too high. Suddenly the hybrids on the road today and tomorrow’s hydrogen-powered fuel cell vehicles only offer an incremental improvement in sustainability. But new bioplastic alternatives are bringing the vision of a truly sustainable automobile closer to reality. Developing vehicles that replace traditional petroleum-based plastic parts with bioplastics is an exciting new area of development in the auto industry and many others. Cereplast Inc., a Hawthorne, Calif.-based maker of proprietary, bio-based, renewable plastics which are used as substitutes for petroleum-based plastics, recently announced a new plastic resin product that may be the next step in automotive sustainability. Cereplast’s “Hybrid Resins,” also commercialized as Biopolyolefins™, offer properties of traditional petroleum-based plastics but require only half the oil content. The result is a cost-competitive bioplastic that can be processed on traditional converting equipment with significantly less energy consumption. Biopolyolefins replace a large portion of the petroleum content in traditional plastic products with biobased materials to answer the growing demand for sustainability in industries that also demand the structural integrity and durability of traditional plastics. In October 2007, Cereplast introduced the first product from this family, Biopropylene™, a 50 percent bio-based thermoplastic resin containing starch, polypropylene, plasticizers, and compatibilizer that can replace traditional polypropylene in many durable applications, including automobiles.

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Automotive

The potential size of the market opportunity for Biopropylene is quite large and could have a serious impact on the carbon dioxide offset of automobile companies. The automotive industry is a large user of polypropylene. Traditional components include interior panels, air conditioning equipment, etc. A reduction in both fossil fuels feedstock and processing temperature for these items could allow automakers to claim some CO2 offsets for their industrial activities.

New facility in Indiana

Currently, automaker PSA Peugeot Citroën is exploring Biopropylene in the development of sustainable automobiles. The car has an influence on the environment at each stage in its life cycle. In its approach to eco-design, the PSA Peugeot Citroën Group aims to take environmental requirements into account at each phase in the vehicle life cycle, by limiting the resources necessary to production, through the responsible management of industrial sites, and by limiting the impacts of vehicle use and end of life. Consumers today are first concerned with the reduction of CO2 emissions, second the consumption and the price of fuel and third the design and materials used. PSA Peugeot Citroën is developing automobiles using sustainable materials as this has recently become more important the European auto market. Sandrine Raphanaud manager of the MAATEO project said, “Biopropylene is a very interesting and promising material that could assist PSA in reducing the carbon footprint of our automobiles.”

a contact angle of 99°. The contact angle of a non-polar solvent, benzene, is 27° for Biopropylene and 37.8° for PP. The higher surface energy of Biopropylene renders it more amenable to painting with less surface treatment than PP, an important differentiator for automobile usage. Biopropylene should be processed at temperatures below 200°C, thus requiring significant less energy consumption than PP processing, where temperatures in excess of 200°C are typically used. In summary, Biopropylene, with a bio-based content of 50% or more, offers a balance of properties and performance that makes it very attractive in various applications in the automobile industry demanding an improved environmental footprint. Biopropylene reduces our dependence on fossil fuels, namely, petroleum and offers much more stable pricing fluctuations than petroleum based products.

Biopropylene is manufactured via twin-screw extrusion process and the physical properties shown in Table1 demonstrate the effectiveness of its use in automobile manufacturing.

This target market explains the strategic location of Cereplast’s new manufacturing facility in Indiana which will reach half billion pounds by year 2010. Indiana is a state well known for its automotive activity and is about 4 hours from Detroit, Michigan.

Biopropylene has higher tensile strength, modulus, and heat distortion temperature than homopolymer polypropylene (PP). Furthermore, it also has higher surface energy than PP. The contact angle of water, a polar solvent, on Biopropylene resin film is 85° whereas PP has

www.cereplast.com

Physical Property

ASTM Method

Units

Bio-PP* Homo PP

Tensile Strength @ break

D 638

MPa

16.61

11,37

Elongation @ break

D 638

%

9.5

130.1

Young‘s Modulus

D 638

MPa

2,063

824

Flexural Modulus

D 790

MPa

965

701

Notched Izod Impact

D 256

lb-ft/in

0.57

1.81

HDT @ 264 psi (1.82 MPa)

D 648

°C

60

54.4

MFI 190°C @ 2.16 Kg

D 1238

g/10 min

3-6

3

Density

Calculated

g/cm³

1.04

0.9

*BioPP is compared to the same PP homopolymer used in its composition

Table 1: Physical Properties of Biopropylene vs Polypropylene (values recalculated)

End of last year Cereplast won the inaugural AUTOPLAST SPEICON award for the Highest Contribution in Plastic Material Development Used in the Auto Industry. The award was presented by the Society of Plastics Engineers (SPE) at AUTOPLAST 2007 in Mumbai, India. It recognizes outstanding achievements in the development of new plastics technology for automotive applications. Cereplast earned the honor for its recently launched Biopropylene™ product from the Cereplast Hybrid Resins™ family.

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Natural Fibres

Natural Fibre and Biocomposites for Technical Applications Article contributed by: Andrzej K. Bledzki, Adam Jaszkiewicz, Institut für Werkstofftechnik, Kunststoff- und Recyclingtechnik, University of Kassel, Germany Dietrich Scherzer, BASF SE, Global Polymer Research – Biopolymers, Ludwigshafen, Germany

A

new group of materials, consisting of bioplastics reinforced with natural fibres, offers a broad and very interesting field of applications because of their highly promising properties. For years fibres, such as jute, hemp, sisal, kenaf or cotton, have continuously gained more and more importance (see article on page 18). In spite of their many advantages, natural fibres also have some drawbacks. Lack of reproduction consistency and insufficient impact strength limit their use. Thus these material properties will have to be further researched and improved. In 2003 Daimler and Rieter Automotive together with the Philippine company Manila Cordage started a project with the aim of developing a natural-fibre-reinforced plastic component for the automobile body and to introduce it into mass production. The motivation for this project was the potential for weight and cost reduction compared with common glass-fibre-reinforced composites (GFC). Parts made of PP/abaca are now installed in Mercedes A-Class automobiles as sub-floor coverings (fig. 1).

Figure 1: Rear cover in the Mercedes A-Class, produced by Rieter Automotive AG, Switzerland

Figure 2: Abaca fibre cord as delivered from Rieter Automotive AG, Switzerland.

Abaca (banana fibre, ‘musa textilis’ or Manila hemp, see fig. 2) was chosen as a suitable reinforcement fibre. The reason was the precise growth and preparation control of the fibres (cooperation with fibre manufacturer Manila Cordage) as well as very good mechanical properties when compared with other natural fibres. Cellulose is a base component of plants and thus is an almost inexhaustible source of raw material. The raw material for man-made cellulose fibres (fig. 3) is mainly the cellulose that is obtained from wood. In recent years the possibilities for reinforcing with cellulose spun fibres (man-made cellulose, e.g. Cordenka, Lenzing) have been intensively researched, especially with regard to injection moulding. Produced using a variant of the viscose process in a method geared to technical fibres of cellulose it becomes a filament yarn, similar to glass fibre roving. Also biocomposites, with both biogenous matrix and natural fibres, are slowly establishing themselves in market place. Parts made of biocomposites can be found predominantly on the Japanese market. Companies like

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Natural Fibres Toyota, Mazda, NEC (Nippon Electric Company), and Sony have already started production of some applications. For example a PLA/Kenaf spare tyre cover (Toyota Raum and Prius, see bM 01/2007), a PLA-based Walkman housing (Sony) and a PLA/Kenaf cell-phone housing (NEC, see bM 01/2006). Other applications are under examination.

Research project of Kassel University

The composites that were tested consist of a biogenous matrix (70% by weight) and Abaca or man-made cellulose fibres (30% by weight). PHAs were blended with Ecoflex® (biodegradable synthetic polymer from BASF) and additives. The blend properties were adopted to be similar to common PP. The content of PHAs in the blend is over 65% by weight.

Figure 3: Man-made cellulose fibre ‘roving’.

E Modulus 10000 8000 [MPa]

Biocomposites on a technical scale are mostly thermoplastics, which allows processing methods such as injection moulding or extrusion. For this reason research at the University of Kassel in Germany is focused on thermoplastic biopolymers. They are established on the market, have good mechanical properties and are available with guaranteed reproducibility of properties on a technical scale. Materials chosen for the project described here are PLA (4042D from NatureWorks) and polyhydroxyalkanoates (PHA from Tianan Biologic Material).

Abaca fibres from Manila Cordage (with the kind assistance of Rieter Automotive) were added as continuous fibres (filament yarn). The man-made cellulose fibres used here were made by Cordenka (Cordenka® 700 Super 3). All compounds were pre-processed by extrusion, using a coating technique. In a first step the polymers, together with the fibres, were extruded via a coating nozzle (like cable-coating), cooled to ambient temperature with water and cut into long pellets. In a second step these pellets were melted and homogenised on a single-screw extruder and then injection-moulded into ‘dog bone’ specimen in line with DIN EN ISO 294-1 (specimen type 1A).

Figures 4 and 5 show the results of tensile tests for biocomposites in comparison with PP composites. PP composites were reinforced with the same fibres and produced by the same processing techniques. The main difference is the use of a coupling agent (maleic anhydride; MAH-PP) for PP/natural fibres; for the biocomposites no coupling agent was used.

4000 2000 0

PP Composites

PHA Composites

PLA Composites

Figure 4: E-Modulus of tested biocomposites in comparison to PP composites.

Tensile Strength 120

80 [MPa]

The processing temperatures during extrusion were in the range of 150-200°C (depending on the biopolymer); during homogenisation approx. 150-180°C. The temperature profile during injection moulding was about 170190°C. Virgin granulate and fibre-filled pellets were dried each time before further processing. The moisture content was about 0.02% for the virgin polymers and about 0.20% for the compounds. All tests were performed according to DIN standards.

6000

40

0

PP Composites

PHA Composites

PLA Composites

Figure 5: Tensile strength of tested composites.

unreinforced polymer abaca composite cellulose composite

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Natural Fibres Charpy A-notched impact strength +23°C 40

[kJ/m2]

30 20 10 0

PP Composites

PHA Composites

PLA Composites

Figure 6: Charpy A-notched impact strength at 23°C. Charpy A-notched impact strength -30°C 40

[kJ/m2]

30 20

O O

10 0

CHR PP Composites

PHA Composites

unreinforced polymer abaca composite cellulose composite

All of the latest news will be presented during the upcoming 7th Global WPC and Natural Fibre Composites Congress to be held in Kassel on June 18th 2008. Besides Wood Plastic Composites (WPC), the Congress focus will be on biofibres and biocomposites. Specialists from all over the world (approx. 45 lectures) will cover a wide scope, from material development to the newest applications in the field of Natural Fibre Composites (NFC). Besides the lecture programme, an interactive poster presentation and an exhibition will take place in the historical location of the ‘Stadthalle Kassel’. For more details please visit www.wpcnfk.de. Proceedings from previous conferences can also be ordered at www.kutech-kassel.de.

bioplastics MAGAZINE [02/08] Vol. 3

O

PLA Composites

Figure 7: Charpy A-notched impact strength at -30°C.

14

With the addition of abaca fibres the stiffness of all composites increased significantly. The level is much higher for stiff PLA than for PHA and PP. PHAs have similar stiffness to PP. It can also be seen that the fibres significantly increase the tensile strength. Especially with man-made cellulose fibres a significant improvement can be achieved. The PHA blends and composites, however, did not meet the researcher’s expectations. Probably, the polymer decomposed during processing, along the lines of the following formula:

H CH2

CR

O

T>180° O CHR

O OH H2C

CR

O

This is due to poor thermal stability at higher temperatures. This effect can be avoided by using multifunctional polymers as chain extenders and compatibilisers. For example by the addition of the reactive chain extender Joncryl® (BASF), a significant increase in strength and stiffness can be achieved. For instance the addition of 1% by weight of Joncryl 4368 S raises the strength from 27.3 to 34.6 MPa. Other properties can be similarly enhanced. Thanks to the use of a coupling agent in PP composites, a higher tensile strength could be achieved. The major improvement in mechanical properties is noticeable in the impact properties (Charpy A - notched impact test, figs. 6 and 7). Because of its special fibre structure, reinforcing with man-made cellulose leads to the best effect: an enhancement up to factor 6 (for PHA composites, fig. 6). This is due to favourable fibre geometry and roughness. A pull-out mechanism occurs more often with man-made cellulose composites then with abaca. The pull-out of fibres absorbs a high amount of fracture energy and therefore an improvement of impact strength can be observed. It is obvious that


PHA/cellulose composite shows the highest impact strength of all the materials tested. Reinforcing with abaca improves the impact strength only for biocomposites, whereas using man-made cellulose the overall results are much better compared with unreinforced virgin polymers. Probably this is due to the fracture mechanics at the fibre/matrix interface, which has been mentioned. The abaca fibres that were used are low priced natural fibres with relatively good mechanical properties. Reinforcing with manmade cellulose showed a significant improvement in all tested values, but the fibre price is not competitive with abaca. This means that the choice of fibres should be made with regard to the fibre cost and the requirements of the endproduct properties. In the tests described here it was shown that some mechanical properties of the analysed biocomposites are very similar to ‘common’ PP composites. The PP used here was impactmodified. For that reason some results, where the ductility is the major factor, are better, for example compared to stiff PLA composites. However, by modifying (blending) biopolymers like PHAs it is possible to achieve a comparable level of toughness. Biocomposites based on PLA can be applied where the stiffness and strength are the ‘key factors’. Further research should be focused on compatibilisation of highly hydrophilic and polar natural fibres with non-polar polymer chains. Also a study of functional additives (e.g. the chain extender Joncryl) should be undertaken with a view to melt stabilisation and molecular weight improvement.

Acknowledgements: The authors are grateful to Rieter Automotive AG (Mr. B. Scherübl) for the supply of abaca fibres. www.kutech-kassel.de

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Natural Fibres

Go, Trabi Go! „Back to the future?“ Article contributed by Rosemarie Karner

It started about 50 years ago The Zwickau motor factory (AWZ) produced its first pilot series of small cars in 1957. In total 50 of the so-called P50‘s were built. Because the spirit of the times was still one of optimism and a bright future, a simple name like the P50 for such a ‘modern example of ingenious socialist engineering’ was hardly in keeping with the mood. It was therefore fortuitous that in October 1957 the Soviet Union launched the first „Sputnik“ earth satellite. This led to the adoption of the name „Trabant“, which, like „Sputnik“, means „travelling companion“. In 1964 the 601 model was introduced, with one of the main features being new bodywork. The car no longer looked quite so rotund, and there were small changes to the rear „fins“ that were popular at the time, especially in the USA. After 1964 nothing on the Trabant really changed. Between 1957 and 1991 a total of 3,051,385 Trabants were built (source: www.sueddeutsche.de)

An old Trabant is also shown on this issue’s cover photo and you can see the original 601 commercial at http://www.teamburg.de/bioplastics/misc/trabi.php

T

he Trabant - it still to be seen on German roads (and not only German roads). A mass-produced car from the former DDR (German Democratic Republic). Fans of the Trabant call it the ‘Trabi’, others call it ‘Rennpappe’ (‘cardboard racer’). But as well as being a nostalgic icon the Trabant has some interesting features, particularly with regard to the material used for the bodywork. Let’s go back to the 1950‘s, where we can take a closer look.

History At that time the automotive engineers at the VEB Sachsenring car factory in Zwickau were faced with a serious problem. The situation regarding automobile mass production was far from good. There was a serious lack of machines and materials. During the Cold War there was an embargo on sheet steel, and a regular supply from the USSR was also subject to limitations. Something had to be done. A solution had to be found, and the East Germans started experimenting with different kinds of materials. After initial trials with a fibre mixture based on PVC with wood chip and cotton fibres the search was on to find a better solution. The need to find a material that could withstand substantial temperature variations, both heat and cold, with better mechanical properties, and that would be reasonably easy to process led researchers down various routes until they finally developed a thermosetting material whose properties they were able to improve as time went by and the manufacturing process was perfected.

Cotton fibres and phenolic resin In the early trials a carding machine was used to produce a fibrous mat from cotton, which was then wound onto a drum. As it was wound onto the drum the cotton mat was impregnated, by a sprinkler device, with a synthetic resin powder until the resin content reached 52%. The impregnated mat was then compressed by passing it between calendar rollers. The next step was to produce two more resin-impregnated mats with modified resin levels. The aim of the three layer process was to achieve a particularly weatherproof outer surface with a high level of Photo: Th. Kraft / Wikipedia 16

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(Photo: Daimler)

Natural Fibres

rigidity, and to avoid delamination of the pressed parts if they became distorted or warped. For the series production of what was finally a 5-layer resin mat the following process was developed. Five carding machines processed the loose cotton fibre flock on a conveyor belt, converting it into a cohesive mat. Before the continuous mat was laid in the press it was sprinkled with a specially produced synthetic resin. Because each machine fed a slightly different thickness and mixture of material onto the conveyor the final layered mat was given the desired characteristics. The compressed cotton and phenolic resin mat finally consisted of five layers with different resin contents and different fibre orientation. The weatherproof outer layer had to be made only of fibres that were totally free of components which could swell. The fibres were chemically pre-treated by the so-called bucking process, designed to remove fats and waxes.

Criss-cross layers to improve performance With the other layers care was taken to place them on top of each other with the fibres in a criss-cross pattern. One reason was the fact that shrinkage across the fibres was greater than the linear shrinkage, so that placing the layers at 90 degrees to each other compensated for the difference in shrinkage, thus largely avoiding any warpage. In addition the oriented fibres made a significant contribution to the rigidity of the finished sheet. Using randomly scattered fibres would have produced no more than conventional moulded mass properties. In a subsequent step the multilayer resin mat was cut into rectangular pieces. The dimensions of the individual pieces could be adjusted, and later the mat could even be cut, and the sizes altered, as it passed down the production line. The scrap material that was trimmed off during cutting was reclaimed, separating the cotton and the resin using a beating opener and fed back into the middle layers at the material preparation stage. The parts taken out of the press-tool still had loosely compacted edges which were not trimmed off during

pressing but were removed later by various methods. To finish the edges they were partially die-cut and then milled smooth in a special fixture. At times a band saw was used. Made in this way the production of a roof panel took only a few seconds. The curved cut-outs in the front wing panels were done by hand on the finished pressing using electric rotary cutters.

Final assembly looked just like sheet metal The process for manufacture and assembly of the Trabant thermoset parts had to be appropriate to the material being used (draft angles). The final bodywork design even fooled experts in sheet metal bodywork, who assumed that it was made of metal-clad parts. Fixing the parts to the steel framework was done by baking on a heat-hardening resin adhesive, using screws and rivets, and crimping. The picture above shows the basic skeleton with the pressed parts that are to be mounted onto it. When repairs were required the individually mounted parts could be removed without damaging the framework. The material research carried out included investigating, for example, flexural strength, elasticity, heat resistance and moisture absorption. Material testing was carried out not only in Germany but in Hainan in the Chinese tropics, in African deserts and in the Arctic Circle. Ongoing tests and modifications were necessary for various reasons, including the variations in the price, quality and availability of cotton and resin, with different fibres resulting in different levels of shrinkage. The pressings themselves, even over an extended period of time and with no painting, proved to be almost indestructible. The Trabant is „history on the move“, at least as long as a few examples keep running. On the other hand, cotton fibres, are enjoying a new lease of life in modern automobile manufacture, with applications in moulded parts. Is this a case of „back to the future“? Source: Sonntag W./Barthel W.: „Kunststoffe für Karosserieverkleidungen“ (Plastics for bodywork panels), 2002, 4th International Wood and Natural Fibre Composites Symposium

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Natural Fibres

Natural Fibres in Automotive Applications Article contributed by Andrzej K. Bledzki, Adam Jaszkiewicz, Markus Murr and Volker E. Sperber Institut fĂźr Werkstofftechnik, Kunststoff- und Recyclingtechnik, University of Kassel, Germany Omar Faruk, Department of Forestry, Michigan State University Michigan, USA

Automotive exterior components made from flax fibre reinforced composites (Photo: DBU)

A

utomotive components made with materials from renewable resources have moved successfully from pipe dreams long ago to the state-of-the-art applications of today: Natural fibres are enjoying a comeback in high-tech development. The related research has experienced an explosion of interest, particularly with regard to natural fibre‘s comparable properties to glass fibres within composites materials. Above all, the automotive industry is interested because cars have been required to be partially decomposable or recyclable since 2006. The main area of increased usage is in interior applications, because the need is the greatest here. A DEFRA report from 2002 projected the growth rates for bio-fibres in automotive components at 54% per year. In the last decade bio-fibre reinforced polymer composites have been embraced by European car makers for door panels, seat backs, headliners, package trays, dashboards, and trunk liners. Recently the trend has reached North America where bio-fibre composites are gaining widespread acceptance. Nowadays, in the USA more than 1.5 million vehicles include applications for bio-fibres such as kenaf, jute, flax, hemp and sisal in combination with thermoplastic polymers such as polypropylene and polyester. Bio-fibres have benefited from being eco-friendly, and even more by providing enhanced stiffness and sound damping at lower cost and density than glass fibres and mineral fillers. Furthermore, those composites contribute to the automotive manufacturer‘s final goal by delivering a 30% weight reduction and a cost reduction of 20%.

Lightweight and recyclable Increased social awareness of environmental problems posed by the non-degradable, non-recyclable contents of salvaged automobiles is forcing automotive manufacturers to enhance the biodegradable content by switching to bio-fibres. To accelerate this process legislators in the USA and Europe have issued a specific directive on end-oflife vehicles that promotes the use of environmentally safe products and reduces landfill. The directive, which came into effect at the turn of this century, predetermined the

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Natural Fibres (Photo: Daimler AG)

Under-floor protection trim of a Mercedes „A“ class made from banana fibre reinforced composites (Photo: Rieter Automotive)

deposition fraction of a vehicle to 15% for the year 2005, and then gradually reduces it to 5% for the year 2015. Bio-fibre composites in the automotive industry both reduce material waste and increase fuel efficiency. On the one hand a major problem is the waste disposal of glass fibre from composite materials after their life cycle. This leads to a clear advantage for bio-fibre composites. On the other hand, the second environmental benefit is the reduction of fuel emissions. Europe is committed to the Kyoto protocol. If lighter materials are used in the automotive industry, fuel efficiencies rise, making it easier to meet the goals. In the current situation, it is estimated that no more than 50 kg of natural fibres can be used in a car. This corresponds to a reduction of about 10 kg if glass fibre composites are replaced with bio-fibre composites in an automobile. If the weight of a car can be reduced by 10 to 20 kg, the effect on the environment will be significant.

Processing bio-fibre reinforced composites In principle, the production techniques for natural fibre composites can be similar to those with glass fibres. Exceptions to this are techniques where continuous fibres are used, such as pultrusion (a yarn has to be made first), or where fibres are chopped up, as in spray-up or SMCprepreg preparation. The most important technology is undoubtedly compression moulding. Different variations of this process (details depending on the company adopting the process) are suitable for the processing of plant fibres. Such compression moulding of resinated natural fibre mats, natural fibre/PP hybrid mats and NMT (natural fibre mat reinforced thermoplastics), was developed by BASF in Germany about 15 years ago. A specific improvement of NMT made it closely equivalent to the performance of GMT (glass fibre mat reinforced thermoplastics). In general, the differences lie in the way that fibres and binding polymers are combined and brought into the mould. Some processes use a pre-melted polymer (e.g. the EXPRESS technology), some use a fibrous polymer that is combined with the plant fibres into hybrid mats before compression moulding, and others use polymer

powder that is introduced into the fibre mats before compression moulding. As almost all processes use the fibres in the form of mats, decortication of the fibres and the processing of the mats are key issues for the technology. The extrusion press processing (express-processing) was developed for the production of flax fibre reinforced polypropylene at the research centre of DaimlerChrysler, Ulm, Germany. A short overview of the current main technologies is given in the following:

FIBRIT Process The FIBRIT process is the first process based on renewable raw materials. Chips of pine are washed, ground to wood-like fibres and silted with the addition of water, phenolic resin (as a binder) and cellulose, thereby giving a wood fibre pulp. This is applied as slurry to a contoured part of the interior door panel, eliminating any water surplus. Through compression moulding at 230 to 250°C, a blank is obtained with only 50% of the former thickness. Following this the blank undergoes vacuum forming in a pre-heated mould. Once specific holes have been stamped out, the finished support is obtained.

Wood Fibre/Phenolic Resin (Lignotock Process) This process uses wood chips (preferentially red pine) as the base material. The chips are shredded in two stages and mixed into a fibre mass under the action of steam. After mixing in phenolic resin (as binder) hot thermoplastic and an adhesive cross-linking agent, the basic compound thus obtained is processed on a needle-punching unit into mat nearly 6 mm thick. From this the finished support is finally formed in a heated mould.

Polywood Process In this process a compound made up of 50% wood flour and 50% polypropylene is extruded into a Polywood sheet that is the support material of the trim panel. The sheet is heated in an infrared oven, making it easy to form. The finished trim panel is then obtained through compression moulding.

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Natural Fibres

Automotive door in-liner, instrument panel made from bio-fibre reinforced composites (Photo: Dräxlmaier Group)

Natural Fibre/PP (LoPreFin, Fibroflax) Natural fibre/PP is made of two different types of fibres. These are natural fibres (flax, sisal or similar) on the one hand and thermoplastic fibres (PP or similar) on the other hand. The two types of fibre are mixed in a closed tank to a homogeneous mixture. The non-woven mat obtained can be formed by placing in a heated mould and forming under pressure. The synthetic fibres are melted and given the shape of the finished part.

Fibropur A needle-punched vegetable fibre mat is sprayed into a mould together with a two component PU system. The sprayed mat is then heated to 125°C and compression moulded to realize a light structural carrier.

COIXIL

Fibre Resources The principal fibres being used for automotive components come from flax and hemp, grown in the temperate climates of Western Europe, the sub-tropical fibres, jute and kenaf, mainly imported from Bangladesh and India, banana fibre from the Philippines, sisal from the USA (Florida), South Africa and Brazil, and wood fibre from all over the world. The table shows the commercially important fibre sources of agricultural bio-fibres that could be utilized for composites. The traditional source of agro-based composites has been wood, and for many countries this will continue to be the major source.

Commercially important fibre sources [Suddell, Evans, 2005]

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Fibre

Species

World Origin production [103 t]

Wood

>10,000 species

Bamboo

>1,250 species

10,000 Stem

Cotton lint Gossypium sp

18,450 Fruit

1,750,000 Stem

Jute

Corchorus sp

Kenaf

Hibiscus cannadbinus

970 Stem

Flax

Linum usitatissimum

830 Stem

Sisal

Agave sisilana

378 Leaf

Hemp

Cannabis sativa

214 Stem

Coir

Cocos nucifera

100 Fruit

Ramie

Boehmeria nivea

100 Stem

Abaca

Musa textiles

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2,300 Stem

70 Leaf

COIXIL is a Johnson Controls Automotive co-injection technology with sequential injection of two different materials in the melted state from the same point - first a soft TPO skin (A) and then a more rigid core material (B) which is a short bio-fibre reinforced polyolefin to give shape and resistance to the component. The final structure is a sandwich (A-B-A).

Exterior parts are on the way The automotive industry requires composite materials that meet performance criteria as determined in a wide range of tests. A typical market specification includes criteria such as ultimate breaking force and elongation, flexural properties, impact strength, flammability and fogging characteristics, acoustic absorption, processing characteristics, dimensional stability, water absorption or crash behaviour. Most of the composites currently used are designed with long-term durability in mind. Generally, bio-fibres can be used as both filler and reinforcement for interior components and are now generally accepted for those applications. Furthermore they can be expected to increase steadily with increased model penetration. But today more and more bio-fibre composites are also used in the exterior components of an automobile. DaimlerChrysler‘s innovative application of abaca fibre (banana) in exterior underfloor protection for passenger cars has been recently recognized. Exterior parts such as front bumpers or under-floor trim for buses made from flax fibre reinforced composites are other examples. A full list of references for further reading can be obtained from the publisher. www.kutech-kassel.de


Materials

Improving heat-resistance of PLA using poly(D-lactide) by Sicco de Vos Sr. Polymer Product Development Engineer PURAC Innovation Center Market Unit Chemical & Pharma

Introduction In 1987, Tsuji & Ikada were the first to publish about the handshake of mirrored polylactides: the stereocomplexation between poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) that produces crystals with a melting temperature beyond 200°C. Many scientific papers on stereocomplex-PLA followed, but its commercial utilization had to wait until the 21st century. A decisive development for commercialization of PDLA is the start-up of a dedicated plant for D-lactic acid in 2008 by Purac. In addition, Purac plans to expand its product portfolio with L- and D-Lactide. These cyclic monomers can be polymerized in one-step to PLA, thereby eliminating several time- and cost-intensive technologies for the PLA producer. Purac PDLA is a bio-based additive for blending with PLA with the following benefits:  More efficient nucleating agent in injection molded PLA than talc at lower loading  Semi-crystalline PLA plastics with HDT B values of 100 - 150°C possible  PLA plastics with better heat resistance enable new applications, e.g. automotive parts  Reduced shrinkage of film and fiber  Bulk density of PLA unchanged

Purac’s roots in PLA PLA was already developed in the 1960s for use in medical applications. Purac is a significant player in that market with its medicalgrade lactides, PLLA, and other resorbable lactide copolyesters. Fermentation is the core expertise of Purac and is used to produce lactic acid, the key ingredient for lactide. Lactide is the cyclic dimer of lactic acid that is basically obtained by dewatering lactic acid. Subsequent ring-opening polymerization of lactide is the simplest route to PLA.

PLA Material Properties: Strengths and Weaknesses PLA for technical applications has conquered a promising market volume and is the strongest growing bioplastic with a favorable environmental footprint. The added value of PLA originates primarily from its unique combination of properties, such as high optical clarity, rigidity and strength, and favorable gas and water barrier properties for food packaging. These properties can be modified by value added

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Materials polymer technologies, such as co-polymerization, blending, modification with additives, and combining materials or films with different properties. Further recognition of PLA in specific high-end applications is currently limited by a number of material properties that need improvement to meet the material requirements in these markets: 1. weak structural integrity at elevated temperatures, expressed as the heat deflection temperature (low HDT), 2. brittleness, i.e., low impact strength, Figure 1: PLA cup collapsed with hot coffee

3. gas barrier performance, in particular for bottle applications. The biggest issue is the low heat resistance of PLA. The material becomes soft and weak upon heating beyond temperatures of 50-60°C, which causes practical problems during storage, transportation and use of pellets and finished articles. When hot coffee is poured into a PLA cup, if collapses (Fig. 1). Clearly, amorphous – glassy – PLA loses its structural integrity completely when subjected to temperatures above its glass transition temperature. Due to the chiral (see box) nature of lactic acid, several distinct forms of polylactide exist: poly(L-lactide) (PLLA) is the product based on L(+) lactic acid or L-lactide, the major product of Purac. Likewise, polymerization of D-lactide produces PDLA. Today commercially available PLA grades are random copolymers of D- and L-lactic acid isomers with relatively slow nucleation and crystallization rates. As a result, most PLA materials will be amorphous – i.e., glassy and not crystalline – after melt processing. These materials become sticky and soft at temperatures above 60°C. Purac allows polymer producers to add value in a new way by offering L-lactide and D-lactide as solid flakes, available in bulk quantities from 2009. By combining these lactides smartly, new PLA grades with tailored physical properties – like improved heat-stability – can be made by polymer industry.  If lactides are combined in the same polymer chain by a one-pot polymerization of L- and D-lactides, polylactides with melting temperatures ranging from about 130-180°C can be made. At very low D-isomer content, semi-crystalline PLLA is obtained, while amorphous, optically clear PLA is made with D-contents higher than 10-15%.  Polymerization of only the D-lactide monomer produces PDLA. This PLA type is the mirror reflection of PLLA and can be mixed with PLA (co)polymer to improve the material’s heat resistance according to the stereocomplexation concept.

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Materials A solution for the low heat-resistance while maintaining transparency would accelerate the acceptance of PLA and widen the application window. The use of PDLA results in the formation of PLA stereocomplex crystallites (sc-PLA) that act as a so-called nucleating agent and crystallization enhancer for PLA. Six years of innovative research and development at Purac have resulted in the commercial availability of D(-)-lactic acid and D-lactide, the monomer that enables large-scale utilization of PDLA.

Concept of Stereocomplexation PLA stereocomplex crystals (sc-PLA) are formed by mixing polymers resulting from separately polymerized L-lactide and D-lactide. Melt-blending PLLA and PDLA produces crystals, by association of the polymers in a 1:1 ratio, with a melting temperature of about 230°C, i.e., at least 50°C higher than common PLA. This semi-crystalline sc-PLA is a suitable polyester for melt-spun fibers and biaxially stretched film.

Figure 2: Large PLLA crystals formed slowly upon cooling from the melt at 140°C.

Melt-blending of PLA (copolymer) with a few percent of PDLA as an additive, produces sc-PLA crystallites in the PLA melt by racemic crystallization of the PDLA with an equivalent amount of PLA. Upon cooling the melt, e.g. during injection molding, the presence of the sc-PLA crystals promotes crystallization. Thus, the sc-PLA crystals act as heterogeneous nucleation sites for PLA crystallization and are nucleating agents. The nucleation efficiency of PDLA is superior to that of talc, a common filler and nucleating agent. PLA can crystallize 20-30 times faster by blending with only 1-5% (w/w) of PDLA. The resulting material will exhibit a higher degree of crystallinity, which will translate macroscopically into structural integrity up to higher temperatures and will be opaque.

Unique features of Stereocomplex PLA Apart from the mixing ratio, key parameters that control stereocomplexation in PLA/PDLA blends are the molecular weight and stereochemical purity (L/D ratio) of the constituents. Homopolymers of either L- or D-lactide are stereochemically pure, while all intermediate compositions have reduced stereochemical purity. PDLA of relatively low molecular weight (<20kg/mol) has demonstrated excellent performance as a nucleating agent in injection molded commercial PLA of high stereochemical purity. As explained above, the true nucleating agents are the scPLA crystals with their high melting temperature of 205250°C, depending on their size and the stereochemical purity of the constituent polymers.

Figure 3: PDLA increases the number of PLLA crystals upon cooling from the melt at 140°C, resulting in faster crystallization and higher crystallinity

The crystal growth rate of sc-PLA was reported to be comparable to that of well-known commodity polymers like PA-6 and PE. It can be as high as several thousand na-

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Materials

nometers per second, while the maximum crystallization rate of PLLA is 600nm/s. Commercial PLAs of reduced stereochemical purity exhibit even slower crystallization. The ability to act as nucleating agent for PLA homocrystallization can be seen from fig 2 and 3. The pictures show few crystals (white) and a lot of molten PLA (black) in the absence of PDLA (fig 2). Under the same conditions, PLA blended with 5% PDLA, exhibits much higher nucleation density as illustrated by the abundantly present white spots (crystallites) (fig. 3). The end result is faster crystallization in the PLA/PDLA blend compared to homogenously nucleated PLA.

Improving heat resistance of PLA using poly(D-lactide) The heat deflection temperature of PLA can be increased from approximately 60°C to up to HDT values beyond 130°C by incorporating PDLA. Bioplastics with even higher values are possible upon stretching the material into oriented film or fiber, or upon incorporation of mineral fillers or natural fibers. The maximum effect in temperature stability is found in compositions with a 1:1 ratio of PLA and PDLA, as shown by Dutch company Hycail (2005). They demonstrated that potatoes can be fried in boiling oil in a transparent, heat resistant tray prepared from a 50/50

Mirror, mirror on the wall … the stereochemistry of lactic acid and PLA The person in the mirror looks just like you – same height, same eyes, yet there is a crucial difference: the left and right sides are switched around. Your hands are another good example of a mirrored pair. Similarly, certain molecules also exist in mirrored pairs, lactic acid being a famous example. The molecules exhibit chirality and the pairs are called enantiomers. Chiral substances are able to rotate polarized light. This phenomenon is called optical rotation. In a chiral substance with one chiral center, like lactic acid. both enantiomers (the two molecules of which the structure is the mirror image of the other) will give opposite optical rotations. This means that one enantiomer will give a rotation clockwise (positive) and the other a rotation of the same magnitude, but counter clockwise. Thus, the two enantiomers of lactic acid (2 hydroxypropionicacid) are:

O H3C

O OH

OH

H3C

OH OH

Lactic acid enantiomers: L(+)-lactic acid (or S-lactic acid), and D(-)-lactic acid (R-lactic acid)

A 1:1 mixture of both enantiomers is called a racemic mixture. It does not rotate polarized light and is optically not active. Over the last few years, Purac has successfully developed a fermentation process for the so-called ‘mirror image’ of traditional L(+)-lactic acid: D(-)-lactic acid. A unique feature of the Purac fermentation processes for lactic acids

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is that they yield the lactic acid enantiomers with high stereochemical purity. The concept of racemic crystallization, called stereocomplexation for polymers, is not unique for polymers or PLA. An equimolar mixture of D- and L-lactide, the cyclic monomers of PDLA and PLLA, is a physical blend with a melting point of 125°C called DL-lactide. The melting point of the pure lactides is only 98°C. When the interaction between enantiomeric polymers existing as D and L-configurations prevails over that between polymers of identical configuration, association between polymer chains of opposite configuration can take place. Such association is described as stereocomplexation. Other polymers, like polypeptides, specific types of PMMA, polyesters and polyethers, also have the ability to stereocomplexation. Polymerization of D-lactic acid produces PDLA, a completely bio-based polyester like PLA. PDLA can be used as an additive to improve one of PLA’s main weaknesses – the low heat resistance. PLA already deforms at temperatures below 50°C. This creates major problems for the storage, transportation and usage of both granular and finished articles. A solution for the low heat stability while maintaining transparency would drive further acceptance of PLA and widen its application window. PLA’s heat stability can be increased from less than 60 to more than 130°C by combining it with Purac PDLA. The mirror molecules fit to each other, almost like hands in a handshake, to increase crystallinity and temperature resistance. 50/50 mixtures of PLLA and PDLA have the highest potential for applications where high temperature stability is a must. At lower PDLA loadings, PDLA allows for modifications of the physical properties of PLA, resulting in bioplastics that can be used for apparel with improved ironing qualities, microwaveable trays, hot-fill bottles and even engineering plastics for automotive applications.


PLLA/PDLA composition. At lower loadings (<10%), PDLA will also form stereocomplex crystals that accelerate crystallization resulting in faster production and better temperature resistance of PLA. Ultimately, it is the combination of ingredients and processing that produces the set of material properties. Mixtures of PDLA and PLA can be used to widen the application window and include applications such as woven shirts (ironability), microwavable trays, hot-fill bottles and even engineering plastics for automotive applications. A future challenge is fine-tuning polymer structure and processing of PDLA with PLA to produce heat-resistant PLA without sacrificing optical transparency. Finally, PDLA is completely bio-based, does not affect PLA bulk density and contains no heavy metals, so there is an outlook on compliance with EN 13432. Due to limited space, this article had to be shortened. The full text will be in the online archive at the bioplastic MAGAZINE website.

Acknowledgement Special thanks for contributions to this paper to Hans van der Pol, Jan van Breugel and Jan van Krieken (all Purac). Gerald Schennink of Wageningen University (Agrotechnology and Food Sciences group) is gratefully acknowledged for valuable discussions and for performing compounding and injection molding work. www.purac.com, www.csm.nl

References  H. Tsuji et al, Macromolecules 24, 2719-2724 (1991);  H. Tsuji, Macromol. Biosci. 5, 569-597 (2005)  K.S. Anderson and M.A. Hillmyer, Polymer 47, 2030-2035 (2006);  H. Tsuji and Y. Tezuka, Biomacromolecules, 5, 1181-1186 (2004);  D.W. Grijpma and A.J. Pennings, Macromol. Chem. Phys., 195, 1649-1663 (1994);  Natureworks paper on “Crystallization and drying of PLA”, website Natureworks LLC  S. de Vos, Presentation PLA bottle conference, Hamburg, Sept. 2007;  S. de Vos, Presentation Bioplastics conference, Cologne, Dec. 2007.

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Processing

REItruder corotating twin-screw extruder

Extrusion Lines of Biodegradable Article contributed by

Frank Steinbrecher, Processing Engineer Reifenhäuser Extrusion GmbH & Co. KG Troisdorf, Germany

3-layer Filmtec blown film line

T

he focus of Reifenhäuser, a leading manufacturer of high-performance extrusion lines, is on consistent research and further development of line concepts. The resulting innovations maintain the company’s competitive edge worldwide. Especially the use of new raw materials and the involved changes in processing requirements call constantly for new technical solutions. For this reason, biodegradable raw materials (biopolymers), form essential parts of Reifenhäuser’s future strategy. Not least because Reifenhäuser has recognized the importance of the biopolymer market very early already, the company became one of the first members of the European Bioplastics Association. Reifenhäuser is the only extruder manufacturer in this association supporting its ideology as a machine building company. Today, biopolymers are increasingly used in thermoforming sheet and blown film extrusion. In thermoforming sheet extrusion, Reifenhäuser is laying emphasis on a further development of singlescrew extruders and corotating twin-screw extruders for processing biopolymers. The first successes could be presented by the Troisdorf, Germany based company to the expert visitors during its inhouse exhibition held concurrently with ‘K 2007’. PLA was successfully processed by NatureWorks on a 5-layer thermoforming sheet line using a single-screw extruder and a pre-drying stage. A ‘REItruder’ corotating twin-screw extruder without pre-drying operation could also be recommended for the mentioned application. Excellent results were achieved on the pilot line installed in the Reifenhäuser Technology Centre. Trials conducted with thermoform-

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Processing

Thermoforming sheet line

for Processing Raw Materials ing PLA sheets by end customers and manufacturers of automatic vaccum forming units were successful without excemption. PLA polymer which has shorter drying times and lower processing temperatures shows the highest resemblance with PET in extrusion processes. Since the presentation of this development project, if not already before, the market has recognized that PLA, in addition to PP, PS and PET is a polymer suitable to be processed into polished sheets on Reifenhäuser extrusion lines.

for the production of bio-packagings without the need for modification. Newly developed low-temperature screws and three REItorque single-screw extruders are special features of the versatile line concept. REIcoflow gauge control system ensuring the most exacting tolerances and REIcofly turner bars providing highquality films are part of the standard line equipment. For achieving optimum results in the complex winding process of biopolymers an SFA II tandem winder highly recommended.

The constantly rising oil price and the resulting price situation of raw materials, such as PP, PS and PET, make PLA an alternative polymer for the production of thermoforming sheets in the future. For this reason, Reifenhäuser expands its proven standard program by targeted further developments in screw geometry, flow channel optimisation and in many other areas - perfectly matched to biopolymers.

At Reifenhäuser, processing of biopolymers does not end with the compounding of the raw material, mostly available as pellets, but the company’s Extrusion Center offers solutions for the very production of the finished compound. Especially the twin-screw extruder with corotating screws of modular design is ideally suitable to meet the requirements of the sensitive natural materials. Segmented screws and barrels developed and designed by the Technology Centre for specific raw material formulations, enable the processing of materials sensitive to shear stress and heat. Multi-venting and lateral feeding possibilities extend the application range for bio-fabrics, starch and liquids.

A further interesting application can be found in the blown film area. Reifenhäuser was able to achieve almost identical performance rates with starch-based polymers and with polyolefins processed on a standard 3-layer blown film line. High throughputs and good mechanical properties of the extruded film can be obtained with a two-third reduction of energy consumption. Special properties of the film are an excellent barrier behaviour, in particular against oxygen and gases, and its biodegradability according to DIN 13432. The international expert public could witness the excellent film quality during the Open House in Troisdorf. The 3-layer blown film line of the Filmtec 3-1700IBC-RHS type is ideal for the production of laminating film, deep freeze packaging film, stand-up pouches, stretch film and stretch wrapping film. It is also suitable

The commonly used under-water pelletizing or dieface pelletizing is replaced by Reifenhäuser more and more by direct extrusion. Since there is no need for an intermediate compounding step, up to 30 % of the total production costs can be saved by direct operation. Upon request, blown and cast film lines are available to customers and interested parties for trials in the Reifenhäuser Technology Center. It is also possible to use pelletizing lines, depending on the application. www.reifenhauser.com

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Politics

Responsible Innovation: Impact with NatureWorks Article contributed by Erwin Vink Environmental Affairs Manager, NatureWorks LLC

N

atureWorks LLC is committed to producing polymers from annually renewable resources, which meet the world‘s needs of today without compromising the earth‘s ability to meet the needs of tomorrow. Within this philosophy NatureWorks LLC defined their environmental objectives and concrete plans including: 1. Sourcing raw materials from renewable feedstock 2. Reducing fossil or non-renewable energy use 3. Reducing greenhouse gas emissions 4. Minimizing water use 5. Eliminating waste and byproducts and

On October 1, 2007, NatureWorks LLC became a 50/50 joint venture (JV) between Cargill of USA and Teijin of Japan. The company applies its proprietary technology to process natural plant sugars into a family of NatureWorks® biopolymers, which are then used to make and market finished products under the IngeoTM brand name. The new JV provides an elegant combination of the ‘front end’ feedstock technology of Cargill with the ‘back end’ applications and polymer expertise of Teijin. This new investment allows NatureWorks LLC to continue the expansion of the Blair, Nebraska, facility to maximize its 140,000 metric ton name-plate capacity. This capacity is on plan to be available late 2008/early 2009. In addition, the new JV is expected to increase NatureWorks reach into key market areas such as the Asia Pacific.

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6. In a vision of zero waste, providing the greatest number of end-of-life options. A key world concern today is the availability and price of petroleum resources and the increasing levels of greenhouse gases in the atmosphere leading to global climate change. These concerns are concentrated around carbon and how to manage carbon in a more sustainable and environmentally responsible manner. Carbon is the major building block of biobased and petroleum-based products, biotech products, fuels and even life itself. The value proposition of bio/renewable feedstock is to replace ‘old’ (fossil) carbon with ‘new’ (biobased) carbon.

Carbon is the key The sequestration of carbon from biomass has been a process taking place for millions of years and leading to the huge resources of petroleum, natural gas and coal. These raw materials have been used by modern society for the last hundred plus years to produce polymers, chemicals and fuels meaning that much of the carbon that has been sequestered during these millions of years has been released into the atmosphere within a time frame of 100-200 years. It is assumed that this increase of carbon dioxide (and other greenhouse gases) has been a significant contributor to climate change on a global scale. The bio-chemical industry can help remedy this imbalance by closing the short-cycle carbon dioxide loop by converting the carbon sequestered in biomass and crops during the growing season directly into polymers, chemicals and fuels. In theory it is a carbon-neutral system. Of course the bio-chemical industry also needs fuels to drive its processes. The key to success is to minimize this fossil energy use or to replace it with renewable energy sources such as biomass and wind energy.


Politics

Reducing Environmental Biopolymer Bioplastics vs. food ?  For polymers like polylactide (PLA), fermentable sugars are required as the basic raw material. Today sugars can come from e.g. corn, wheat, potatoes, sugar cane, sugar beets, or rice. In the near future the bio-chemical industry will use alternatives like straw, corn stover or bagasse. There are various drivers for this change including:  Avoiding competition with food. It is expected that the world population will grow from 6.7 billion people today to 10 billion people around 2035, so industry has to look for non-food feedstock.  Lowering the costs so more people can afford these bioplastic-based consumer good products, man-made fiber articles and packaging materials.  Improving the life cycle of these biopolymers (less fossil resource use, less greenhouse gas emissions).  More efficient use of land.  More outlets for agricultural waste streams will lead to additional revenues for farmers.  Locally grown crops helping developing local economies which so also become less dependent on the few oilproducing countries today. It is not expected that bio-materials will replace all fossil-based materials, but by replacing a part of them, the fossil resources will remain available for future generations. Today there is some tension on the world food market especially due to increasing prices of agricultural products. This is caused by several factors. A key factor are the growing economies in South East Asia where people are eating more meat and therefore creating the need to produce more feed for agricultural feedstock. Another factor is the policy of having lower stocks in place and increased reliance on the world market. In the past these stocks were used to balance lower local or regional harvests. And finally, to a lesser extent, the increased production of biofuels. All these factors are leading to higher demands and so higher prices. The effect of producing NatureWorks biopolymer in this mix is very limited. Assuming a name-plate capacity of 140,000 metric tons, about 0.12% of US corn is used. Even if the capacity triples in the next 10 years, the impact remains below 0.5%. Short term, the

increased demand on agricultural feedstock can be balanced by taking more land into production and increasing the yield per hectare. In many countries the yields are still rather low. Longer term, the increased use could be balanced by switching to the use of agricultural waste streams in combination with the development of other more efficient / higher yield crops. Genetically modified crops are not required to produce NatureWorks biopolymer. Due to the current plant location – Blair, Nebraska, - a mixed stream of conventional and genetically modified corn is used. To meet the needs of the market NatureWorks LLC has developed a three tiered program consisting of Certification, Feedstock Sourcing and Identity Preservation. Certification confirms the absence of genetically modified material in NatureWorks bio-polymer by lot, order, and run. This is conducted periodically through the year by GeneScan, Inc., an internationally recognized certification organization. With the Feedstock Sourcing program, our commercial partners are offered the option to support the production and delivery of conventional corn in relation to their NatureWorks biopolymer purchase. For every kilo of NatureWorks biopolymer purchased, NatureWorks LLC will purchase, verify and deliver 2.7 kilos of conventional corn to the corn mill at a slightly higher price. The last program is called Identity Preservation (IP). For the last two years, large-volume customers with multiple-year supply contracts are given the opportunity to purchase NatureWorks biopolymer sourced and produced from 100% conventional corn. This program requires a minimum volume commitment of 20 million pounds (approx. 10,000 metric tons). NatureWorks LLC is finalizing an alternative IP option, in which customers are given the opportunity to purchase for specific applications NatureWorks biopolymer produced from lactic acid which is derived from a 100% GM free feedstock. This route has the advantage that it can start with lower volume commitments (approximately 5 million pounds or 3,000 metric tons). The volumes mentioned can be shared among various customers. Both options have significant lead time in order to insure execution.

End of life options NatureWorks biopolymer (polylactide, or PLA) offers more disposal options than any other plastic. In addition to the traditional disposal options for petrochemical-based polymers (landfill, incineration and mechanical recycling)

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Politics tics. Since NatureWorks biopolymer is often compared in Life Cycle Assessment (Appendices 2 and 3) studies with these traditional plastics, the eco-profiles for current and near future NatureWorks biopolymer were calculated using the same methodology as developed by PlasticsEurope. Dr. Ian Boustead, the consultant of PlasticsEurope was contracted to guide and review the development of the NatureWorks eco-profiles. The NatureWorks eco-profiles were published in the peer reviewed journal Industrial Biotechnology in March 2007. This publication can be downloaded from the NatureWorks website. PLA offers the additional options of industrial composting and chemical recycling. The end-of-life vision in the long term is to maintain a journey to zero waste – keeping the biopolymer, regardless of form, out of the landfill and being able to recycle into the same use or higher valued use if possible. NatureWorks biopolymer – marketed as Ingeo - is today predominantly used in food packaging, food serviceware and fiber-based products. Therefore the end products will be handled in current infrastructures, similar to the handling of PET, HDPE and other traditional polymers. Through innovation, technology and education NatureWorks LLC is looking to build a bridge to a better end-of-life. Today, there is immense value in increasing the use of PLA for food packaging and food serviceware especially where industrial composting has the potential to remove a large portion of the organic food waste stream from landfill disposal. So, where food composting infrastructure exists, PLA packaging and serviceware which is heavily contaminated with food waste can be composted assisting food waste diversion from landfill. These package/food waste streams are generated at many different places within the modern society such as quick-service restaurants, canteens, retailers, music festivals, sport arenas and households. To do this right, clear material identification and separation in the waste stream is required. However, it does not make environmental sense to stop here. While composting is superior to landfill – the fate of most food waste and packaging – it is still not a high form of recycling the carbon and the energy content present in the package. The real cradle-to-cradle potential for PLA is in higher-value applications via recycling. Besides applying mechanical recycling, PLA plastic can also be recycled back into lactic acid through chemical hydrolysis. In the future, as use increases significantly in multiple PLA applications, the demand for recycled PLA should contribute to the emergence of an economically sustainable recycled PLA (rPLA) market. Large-scale PLA recovery and conversion to lactic acid will fulfill the biopolymer’s promise of a closed-loop self-sustaining feedstock model.

Summary of the results of the NatureWorks biopolymer eco-profiles Since the early nineties, PlasticsEurope has published the eco-profiles (see Appendix 1) for the traditional plas-

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Two important NatureWorks’ objectives are the reduction of fossil energy consumption and greenhouse gas (GHG) emissions. Before executing the second objective, it is important to know where and in which quantities greenhouse gases are emitted in the production chain. This basic data was collected during the construction of the NatureWorks biopolymer eco-profiles drawing two conclusions:  41% of the GHG were linked to electricity production used in the cradle-to-pellet production system and  the vast majority of the GHG were emitted during the lactic acid production phase, including the upstream contributions from the direct inputs such as electricity, natural gas, steam and raw material use. Therefore, NatureWorks LLC is following two tracks to reduce the GHG emissions and fossil energy use. The first track consists of the optimization of lactic acid process technology. Within the current technology used one could achieve further reductions using more energy efficient equipment, with changes in raw materials and in energy carriers and looking for on/off-site waste heat stream. Longer term, (2010+) it is the intention to implement major changes in lactic acid production and purification. These first track options are specifically related to those processes under the direct control of Cargill/NatureWorks and require additional technological development, a process which is underway and which will deliver future improvements.

Optimized electricity production The second track consists of the optimization of electricity production. There are various methods to replace the electricity from the public grid, including:  On-site renewable generation such as solar photovoltaic systems, wind mills, and bio fueled heat/power installation;  Green power: purchasing both electricity + environmental attributes from a local supplier; and  Renewable energy certificates (RECs) (implemented since January 2006). The first options within the second track are not applicable today from a practical/economical point of view, but that does not mean they are not useful future options.


Politics Concerning the second option, NatureWorks made the decision that beginning in 2006 it would purchase renewable based electricity to cover all electricity needs in the cradle-to-polymer-pellet production system. The preference is for the local utility to supply the Green Power directly. During 2006 limited volumes were available, but during 2007 already about 1/3 of the electricity required came from Green Power generated by the local utility. Since this was/is still not sufficient, NatureWorks LLC purchases so called Renewable Energy Certificates (RECs). In this case the renewable energy is not produced by the local supplier, but in a neighboring state which shares the same power grid. However, for the environment itself it does not make a difference where the renewable energy is being produced, as long as it is being produced in increasing quantities. NatureWorks LLC is purchasing RECs since the beginning of 2006 to cover all it electricity needs in its cradle-to-pellet NatureWorks biopolymer production system. NatureWorks LLC has calculated four eco-profiles (see box 1-3 for some explanation) for NatureWorks biopolymer (PLA) production:  PLA5: Represents the 2005 cradle-to-pellet NatureWorks biopolymer production system.  PLA6: Represents the current, 2006/2008, cradle-topellet NatureWorks biopolymer production system. In this eco-profile the fossil fuel-based electricity has been replaced by renewable energy-based electricity through investments in Green Power and RECs.  PLA/NG no WP: Represents the next generation (NG) cradle-to-pellet NatureWorks biopolymer production system. It includes the implementation of major changes in the lactic acid production and purification. This new technology will reduce energy and raw material use and co-product creation and is expected within 3-5 years. Electricity is imported from the public grid and is mainly fossil fuel-based. (‘no WP’ means that no wind or renewable power is used in this eco-profile).  PLA/NG: The same as PLA/NG no WP, but now Green Power is used to supply electricity in the Cargill / NatureWorks controlled production processes. This combination will make the cradle-to-pellet NatureWorks biopolymer a greenhouse gas sink.

Renewable Energy Certificates - REC A REC represents the environmental attributes – for example the avoided CO2 emissions – that are created when electricity is generated using renewable resources instead of using fossil fuel sources. NatureWorks purchases Green-e certified RECs. The Center for Resource Solutions operates this certification and auditing program. A certified REC assures that the green energy is being produced and delivered, and that the attributes are being claimed only once. Green-e certified RECs also assure that they are from qualifying ‘new facilities’ (up to several years),

PLA Plant East Green Grass

Appendix: 1) Eco-profile gives the total energy use, the total raw material use, the total air and water emissions and the total solid waste produced from the cradle to a factory gate. An eco-profile always starts with the extraction of the raw materials from the earth and ends with the production of the product of interest. Eco-profiles are not limited to a particular product. In addition to the eco-profile for NatureWorks biopolymer, eco-profiles can also be calculated for products like lactic acid, dextrose, corn, electricity and steam production. An eco-profile is the same as what is often referred to as ‘cradle-topellet’ or ‘cradle-to-polymer-factory gate’ data. 2) Life cycle inventory (LCI) gives the total energy use, the total raw material use, the total air and water emissions and the total solid waste produced from the cradle to the grave ( = the ultimate disposal). An LCI is basically the same as an eco-profile, but it covers the complete life cycle. So, the LCI of NatureWorks biopolymer ‘pellets’ does not exist, one can only have an LCI of a Ingeo product. For an LCI one has to define among others the application, the production location and technology, the use phase and waste collection and processing. 3) Life Cycle Assessment is a systems analysis tool to account for all the environmental impacts associated with a product or service, covering all stages in a product’s life, from the extraction of resources to ultimate disposal. The basic data set for an LCA is an LCI. In the life cycle assessment the inventory data is converted into a limited series of impact categories, such as fossil energy use, climate change and acidification, followed by an assessment of how relevant these impacts are.

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Politics

Figure 1. Results of the utilization of renewable energy and new technology on energy use.

Figure 2. The results of the utilization of renewable energy and new technology on the net greenhouse gas emissions.

not facilities running for ‘years and years’. For 2006 and 2007, NatureWorks purchased RECs and also for 2008 contracts are in place. The wind energy is being generated by wind farms located within the MAPP region (= the power pool region where NatureWorks’ facilities are located). RECs are only applicable on additional wind power initiatives, not on mandatory wind energy.

the new technology in combination with Green Power is implemented in 2010+ the production systems becomes a GHG sink (-0.67 kg CO2 eq./kg PLA). It may be clear that all numbers are only valid for NatureWorks biopolymer and not for PLA in general.

Figure 1 gives the results of the utilization of renewable energy and new technology on cradle-to-pellet energy use per kg NatureWorks biopolymer. PLA5 is the benchmark. In this production system, 50.2 MJ non renewable energy is required to drive all the processes. If NatureWorks LLC switches to the new technology, a reduction of non-renewable energy can be achieved of 30% (second bar). This new technology is foreseen for 2010+. Since January 2006, we replaced the grid electricity by renewable-based electricity via the purchase of Green Power and RECs. PLA6 shows a reduction of non renewable energy of 46%. When the utilization of the new technology in combination with Green Power is implemented in 2010+, a reduction of 67% in non renewable energy is predicted. Figure 2 gives the results of the utilization of renewable energy and new technology on the net greenhouse gas emissions from the cradle-to-pellet per kg NatureWorks biopolymer. The net GHG emissions in the PLA5 production system is 2.02 kg CO2 eq./kg PLA. When NatureWorks LLC implements the new technology a reduction of 1.27 kg CO2 eq./kg PLA can be achieved (second bar). Since January 2006 NatureWorks is replacing the grid electricity by renewable-based electricity via the purchase of Green Power and RECs (PLA6). Since beginning 2006 the net GHG emissions are 0.27 kg CO2 eq./kg PLA. If the utilization of

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The published eco-profiles are the basic data to perform Life Cycle Assessment studies (see Appendix). In this context this article shall be closed with the following remarks. Quite often new materials, which are in their early stage of development, produced in small scale or singular facilities and for which conversion and final disposal are not optimized, are directly compared with mature materials for which the life cycle has been optimized over several decades. This often leads to a biased comparison. In these cases the ‘performance’ of an ‘adult’ is compared with that one of a ‘child’. LCA practitioners should always include possible optimization steps for immature materials. By not including future outlooks for immature materials, the tool of LCA is becoming a tool that intends to kill innovation at its early stage and that, of course, was never the intention of this tool. It is the key responsibility of the LCA practitioner to give a balanced view. Also for the final reader of an LCA this is important to keep in mind when evaluating an LCA. As people around the globe are working to make mankind less dependent on fossil raw materials, the use of bioplastics contributes to this change in a meaningful way and bio-plastics solutions are a valuable way to demonstrate this important evolution. More details about the Feedstock program, the Ecoprofiles, LCA studies and the Waste Management Options can be downloaded from: www.natureworkspla.com


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Politics

Towards a bioplastics boom in Australia

A

ustralians are among the world’s best in plastics recycling and retailers are becoming more and more focused on a sustainable future. Yet the world’s non-renewable energy sources are depleting at an amazing speed and further steps need to be taken towards adopting more ecosensitive packaging technologies.

The Recycling Revolution

Article contributed by Fleur Wilkins, Marketing & Communications, Plantic Technologies Limited

Australians are concerned about the environment and being environmentally responsible is now more important to Australian consumers than ever before. This became evident in an independent national survey that found the recycling rate for plastics packaging in Australia has equaled last year’s record result and continues to meet environmental improvement commitments. The Plastics and Chemicals Industries Association (PACIA) 2007 National Plastics Recycling Survey found that during 2006, Australian industry and consumers recycled a record 30.5% of plastics packaging for the second consecutive year. The overall plastics recycling rate (for plastics used in all applications) was 15.9%. Whilst this is an excellent result, there is still more we can do for the environment.

Agricultural film made of Mater-Bi, Photo: Novamont

The Role of Retailers The two major supermarket retailers in Australia, Woolworths Limited and Coles Group Limited, are aware that the adoption of sustainable practices is increasingly recognized as a demonstration of sound business operation and corporate management. There is no denying that packaging is necessary to protect goods from damage throughout the supply chain, enable more efficient transport, and increase the shelf-life of perishable products. Both retailers are actively working towards a more sustainable future, but are they doing as much as their European counterparts in terms of tackling the effects of packaging on the environment? Coles Group Limited was the first Australian retailer to sign the National Packaging Covenant in July 2000, a policy framework for corporate environmental responsibility aiming to provide more effective management of packaging. Coles were also involved in the development of the voluntary Code of Practice for Plastic Supermarket Carry Bags, in conjunction with Eco Recycle Australia and the Australian Retailers Association, ensuring that participating companies will minimize the use of plastic carry bags and provide efficient in-store recycling means for these bags. Yet plastic bags

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Politics

Lemons packed with NatureFlex film (Photo: Innovia)

water soluble plantic tray, Photo: Plantic

make up less than 2% of litter, and this is a minor step towards the overall problem of over-packaging and excessive packaging waste. Woolworths have stepped up to the plate by issuing a Sustainability Strategy 2007-2015, outlining the key sustainability challenges faced by Woolworths in the areas of climate change, water, packaging, sourcing, waste and store design. One priority outlined by Woolworths in this report is packaging, including consumer packaging in their private label products and distribution packaging. Woolworths have commissioned the Sustainable Packaging Alliance to undertake a review of the packaging of private brand products, however, they claim that there are cost implications for sustainable packaging choices which need to be considered to ensure their products remain competitive in the market. Is this enough for Australian consumers?

The Inconvenient Truth Whilst major Australian retailers are moving forward with sustainability in packaging, 99% of all traditional plastics are produced or derived from the major nonrenewable energy sources – crude oil, natural gas, coal and naptha – and these resources are depleting at a rapid speed. Less than 3% of all waste plastic worldwide gets recycled. Not to mention the havoc caused by plastics on marine life and our environment. The need for more widespread use of packaging that is biodegradable and made from renewable resources is fast becoming necessary in Australia. Australian retailers must look to their UK equivalents and be led by their examples. Marks & Spencer and Sainsbury’s have adopted compostable packaging materials for their private labels, and in particular materials known to be suitable for home composting. Plantic®, Innovia’s NatureFlex™ film, Novamont’s Mater-bi starch-based material or PLA are being used by these retailers as part of their corporate social responsibility initiatives.

www.plantic.com.au

The Bioplastics Situation in Australia The Australasian Bioplastics Association and the National Packaging Covenant are working hard at putting in place a series of industry standards for bioplastics packaging and, as the environment becomes an increasing concern and as prices for fossil fuels soar, bioplastics are becoming more competitive. Founding members of the Australasian Bioplastics Association are Plantic Technologies Ltd, AusAsia Pty Ltd, Innovia Film Pty Ltd, Natureworks LLC, PCC Packaging, Plastral Pty Ltd and SIGNUM Specialties Pty Ltd. These companies make available a variety of bioplastics applications in Australia, including:  Rigid packaging (thermoformed trays for food packaging, secondary packaging)  Films (overwrapping, hygiene, twist-wrapping, flowwrapping and agricultural mulch films)  Fibres  Beverage containers  Carrier bags and bin liners  Catering products (cutlery, plates and cups) It is Australian brand owners such as Cadbury Schweppes who are actively leading the way in sustainable-driven innovation and product development, making good use of the bioplastics products available. As part of Cadbury Schweppes’ recent bid to halve its total carbon footprint by 2020, the company is currently using Plantic packaging for various products, with the eventual aim of implementing biodegradable wrapping across 60% of its products. Warwick Hall, inaugural President of the Australasian Bioplastics Association said, “Bioplastics are seen as a remarkable advance in technology with many benefits, including the promotion of a sustainable future.” Whilst there is currently no infrastructure in place in Australia for disposing of bioplastics materials, the development of the market should not be postponed…

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Opinion

Be careful what you wish for...

L

ife Cycle Assessment (LCA) can be a useful tool for evaluating a product’s net environmental impact. But don’t assume it’s going to be easy, or that you will get the answer that you want. Life Cycle Assessment is a method for quantifying the net environmental impact of a product or process. The life cycle of bioplastic stretches from the growing of plants to final disposal, with manufacture, use and transportation in between. Most bioplastics aren’t 100% bio-based so the extraction and manufacture of petrochemicals has to be added to the life cycle too. With the growing awareness amongst industry, consumers and policy makers of the effects that human activity can have on the environment, and mounting pressure to make products more sustainable, LCA seems like a simple way for bioplastics to get all the kudos for being ‘eco-friendly’– isn’t it just putting a load of numbers into a spreadsheet? Actually, LCA is simple to say, but not simple to do. For an LCA to be any use, the data that goes into it must be of good quality. This means finding relevant, precise, complete and up-to-date information. However, these criteria aren’t easy to satisfy. Changes in technology mean that data can rapidly become obsolete. An LCA is just a reflection of the data at the time it was performed so they must be revisited to keep them relevant. This also means that comparing LCAs done at different times can be fruitless as you probably won’t be comparing like-with-like. Further complications come from the proliferation of LCA software available, each one using different assumptions and calculations. These assumptions must be analysed in depth to understand individual LCAs and to make accurate comparisons between similar LCAs. Whilst LCA might seem a great way of comparing your bioplastics to other products on the market, are your competitors really going to let you get hold of commercially sensitive information, particularly if it could make their environmental policy look undistinguished? If you’re relying on secondary sources of information, the LCA conclusions could be invalid. It is better to view LCA as a tool that can be used internally to improve the life cycle of your own products. It is also important to remember that LCA is not the culmination of environmental management, but is actually the beginning of the process. LCA identifies the environmental ‘hotspots’ in your production process where making changes will really have an impact. By exploring the options through an LCA, manufacturers can ensure they are not simply transferring environmental burdens from one stage to another, or, importantly in our globalised economy, from one country to another. As an example of the application of LCA to bioplastics we can look at the results of an LCA on single-use carrier bags. UK government and supermarkets have expressed a commitment to abandon HDPE bags and replace them with something more ‘environmentally friendly’. Before any rash

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Opinion decisions are made, assumptions should be set aside and the life cycle of each alternative choice should be evaluated. Defra funded a study, commissioned by the NNFCC and carried out by Imperial College London, to examine the issues. The study looked at the life cycles of four different bags: a typical HDPE carrier bag, used as the reference product; an oxo-degradable lightweight bag made from HDPE with an added catalyst that makes it breakdown in sunlight; a biodegradable MaterBi bag; and a prototype biodegradable bag made from formulations of NatureWorks PLA and BASF Ecoflex. The results showed that waste management scenarios considered in an LCA greatly influence the outcome. The option with the least environmental impacts in the investigation was actually HDPE carrier bags disposed of via an efficient recycling process with 90% avoided product. However, such efficient recycling is currently not a realistic scenario. The next best option is the use of Mater-Bi bags, preferably disposed of by incineration which gives a slightly better environmental profile than composting or landfill. Oxo-degradable bags disposed of via incineration or landfill are the next best options followed by the heavier HDPE bags disposed of via incineration or landfill. The prototype biodegradable bag initially presented the worst environmental profile, but a ‘bad’ LCA result doesn’t mean the product is ‘bad’; it just shows where there is room for improvement. These bags are relatively heavy, but the LCA demonstrates the environmental benefits of reducing their mass. A lighter bag improves the environmental profile down to a level at which they perform better than HDPE bags and only slightly worse than the Mater-Bi bags, indicating that further development of these bags offers much potential for environmental improvement. So which is the best bag? There isn’t a clear ‘winner’, so the answer depends on how you view the alternative waste disposal methods. The takehome message is that the LCA has provided useful information, but hasn’t relieved us from making difficult decisions. LCAs can be worth the time and effort that is put into them as long as you bear in mind these key points:  (1) It’s just a tool!  (2) It is a snapshot of constantly changing reality.  (3 ) LCA is not the end of a process but the beginning.  (4) LCA can help to identify the environmental hotspots in your production process.  (5) Comparing products can be very difficult. LCAs have shown that bioplastics can have significantly lower environmental impacts than petrochemical-based plastics; however, the issues of scale-up, functionality and evolving waste streams must be considered to maximise market penetration of sustainable products. Bioplastics manufacturers should accept that LCA is part of your toolkit, rather than the definitive solution. www.nnfcc.co.uk

Article contributed by Dr. John Williams, Technology Transfer Manager, and Dr. Louise Dommett, Science and Technology Writer The National Non-Food Crops Centre, York, UK

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Basics

Biobased bottle-label

‘BiomassPla’ logo of the Japan BioPlastics Association(JBPA) BiomassPla Logo and Identification System

T

he Japan BioPlastics Association (JBPA) has been managing the ‘BiomassPla Logo and Identification System’ since July 2006.

BiomassPla, as described here, means a product consisting of at least 25% biomass-based plastics as defined by the JBPA .

Logos Part 7 Over the last two years bioplastics MAGAZINE has introduced different logos that inform consumers about the biodegradability or compostability of packaging or other products made from bioplastics. Now we are starting a new series, where we will introduce logos that provide information about the bio-based origin of bioplastics products

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bioplastics MAGAZINE [02/08] Vol. 3

The utilisation of biomass-based plastics is one of today‘s major issues, because using biomass-based plastics can reduce the consumption of fossil resources, which is a major factor in the Earth‘s climate change. JBPA has been making various efforts to promote the popularisation and business development of biomass-based plastics and plastic products since 2003. JBPA has been operating ‘The BiomassPla Identification System’ and authorises the use of the BiomassPla logo in order to ensure that general consumers can easily identify biomass plastics products. The term BiomassPla as used here refers to plastic products that contain at least a specified quantity of substances derived from renewable organic resources as a constituent part of the plastic material. The JBPA’s identification system has as its objective the creation of a greater understanding of biomass-based plastics among the general public, and promoting the popularisation of biomass plastics.


Basics

The definition of Biomass-based Plastics by JBPA High-polymer materials produced from raw materials which can be obtained by chemical or biological synthesis and that contain substances derived from renewable organic resources. (Excludes chemically unmodified nonthermoplastic natural organic high-polymer materials.) The BiomassPla Identification and labelling system is based on the standard as follows: 1. None of the components of BiomassPla shall be substances on the list of prohibited substances. 2. Biomass plastics must satisfy the JBPA’s standards for inclusion on the Positive List. 3. All of the components of BiomassPla must be disclosed to the JBPA Identification Committee. 4. BiomassPla must be plastic products that contain at least 25.0% (by weight) of components derived from biomass. 5. The use of compounds that contain lead, cadmium, mercury or hexavalent chromium is prohibited. Even if these are not used intentionally, the content of these specified toxic substances in the product must not exceed the given values. 6. Even if the overall product does not satisfy the conditions for accreditation as BiomassPla, use of the logo on the part of BiomassPla may be permitted, if it satisfies Item 5 ‘Standards for Acceptance of Use of the Symbol on Limited Parts’. 7. The registration number must, as a general rule, be quoted on BiomassPla.

Registered products for BiomassPla logo More than 40 products have been registered as Biomass-based Plastics Products (BiomassPla). The registered products are mainly packaging for food and clothes but also include cards, stationery, labels, cap seals, shrink sleeve label and parts or housings for consumer electronics and office equipment. One example is the registration of kids‘ shoes, which use a PLA mixed woven textile for the uppers and a soft PLA compound for the sole. This product will be launched in the Spring. www.jbpa.co.jp

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Suppliers Guide

Simply contact:

Tel.: +49-2359-2996-0 or suppguide@bioplasticsmagazine.com

Stay permanently listed in the Suppliers Guide with your company logo and contact information. For only 6,– EUR per mm, per issue you can be present among top suppliers in the field of bioplastics. 1. Raw Materials

1.4 starch-based bioplastics

1.1 bio based monomers

2. Additives / Secondary raw materials

Wiedmer AG - PLASTIC SOLUTIONS 8752 Näfels - Am Linthli 2 Du Pont de Nemours International S.A. SWITZERLAND Du Pont de Nemours International S.A. 2, Chemin du Pavillon, PO Box 50 Phone: +41(0) 55 618 44 99 2, Chemin du Pavillon, PO Box 50 BIOTEC Biologische CH 1218 Le Grand Saconnex, Fax: +41(0) 55 618 44 98 CH 1218 Le Grand Saconnex, Naturverpackungen GmbH & Co. KG Geneva, Switzerland www.wiedmer-plastic.com Geneva, Switzerland Werner-Heisenberg-Straße 32 Phone: + 41(0) 22 717 5428 Phone: + 41(0) 22 717 5428 46446 Emmerich Fax: + 41(0) 22 717 5500 Fax: + 41(0) 22 717 5500 Germany jonathan.v.cohen@che.dupont.com 4.1 trays jonathan.v.cohen@che.dupont.com Phone: +49 2822 92510 www.packaging.dupont.com www.packaging.dupont.com Fax: +49 2822 51840 5. Traders info@biotec.de 3. Semi finished products 1.2 compounds www.biotec.de 5.1 wholesale 3.1 films 6. Machinery & Molds

BIOTEC Biologische Naturverpackungen GmbH & Co. KG Werner-Heisenberg-Straße 32 46446 Emmerich Germany Phone: +49 2822 92510 Fax: +49 2822 51840 info@biotec.de www.biotec.de

Plantic Technologies GmbH Heinrich-Busold-Straße 50 D-61169 Friedberg Germany Tel: +49 6031 6842 650 Tel: +44 794 096 4681 (UK) Fax: +49 6031 6842 656 info@plantic.eu www.plantic.eu 1.5 PHA 1.6 masterbatches

FKuR Kunststoff GmbH Siemensring 79 D - 47 877 Willich Tel.: +49 (0) 2154 9251-26 Tel.: +49 (0) 2154 9251-51 patrick.zimmermann@fkur.de www.fkur.de

Transmare Compounding B.V. Ringweg 7, 6045 JL Roermond, The Netherlands Phone: +31 (0)475 345 900 Fax: +31 (0)475 345 910 info@transmare.nl www.compounding.nl 1.3 PLA

bioplastics MAGAZINE [02/08] Vol. 3

www.earthfirstpla.com www.sidaplax.com www.plasticsuppliers.com Sidaplax UK : +44 (1) 604 76 66 99 Sidaplax Belgium: +32 9 210 80 10 Plastic Suppliers: +1 866 378 4178 3.1.1 cellulose based films

PolyOne Avenue Melville Wilson, 2 Zoning de la Fagne 5330 Assesse Belgium Tel.: + 32 83 660 211 info.color@polyone.com www.polyone.com

Sukano Products Ltd. Chaltenbodenstrasse 23 CH-8834 Schindellegi Phone +41 44 787 57 77 Fax +41 44 787 57 78 www.sukano.com 1.7 reinforcing fibres/fillers made from RRM

40

Maag GmbH Leckingser Straße 12 58640 Iserlohn Germany Tel.: + 49 2371 9779-30 Fax: + 49 2371 9779-97 shonke@maag.de www.maag.de

INNOVIA FILMS LTD Wigton Cumbria CA7 9BG England Contact: Andy Sweetman Tel.: +44 16973 41549 Fax: +44 16973 41452 andy.sweetman@innoviafilms.com www.innoviafilms.com 4. Bioplastics products

natura Verpackungs GmbH Industriestr. 55 - 57 48432 Rheine Tel.: +49 5975 303-57 Fax: +49 5975 303-42 info@naturapackaging.com www.naturapackagign.com

FAS Converting Machinery AB O Zinkgatan 1/ Box 1503 27100 Ystad, Sweden Tel.: +46 411 69260 www.fasconverting.com

Molds, Change Parts and Turnkey Solutions for the PET/Bioplastic Container Industry 284 Pinebush Road Cambridge Ontario Canada N1T 1Z6 Tel.: +1 519 624 9720 Fax: +1 519 624 9721 info@hallink.com www.hallink.com

SIG Corpoplast GmbH & CO. KG Meiendorfer Str. 203 22145 Hamburg, Germany Tel. +49-40-679-070 Fax +49-40-679-07270 sigcorpoplast@sig.biz www.sigcorpoplast.com 7. Plant engineering

Uhde Inventa-Fischer GmbH Holzhauser Str. 157 - 159 13509 Berlin Germany Tel.: +49 (0)30 43567 5 fax: +49 (0)30 43567 699 sales.de@thyssenkrupp.com www.uhde-inventa-fischer.com 8. Ancillary equipment 9. Services 10. Research institutes / Universities


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bioplastics MAGAZINE [02/08] Vol. 3

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Companies in this issue Company BASF Beutsche Bundesstiftung Umwelt (DB) Biotec Cadbury-Schweppes Cargill Cereplast Coles Group Cordenka Daimler Design Ideas Donald Danforth Plant Science Center DuPont European Bioplastics Fairnomenal FAS Converting FkUR GeneScan Hallink Innovia JBPA JEC Johnson Controls Automotive Maag Manila Cordage Marks & Spencer Mazda Messe Düsseldorf Metabolix Michigan State University Natura NatureWorks NEC Novamont PCC Packaging Plantic Plastics Suppliers Plastral PolyOne PSA Peugeot Citroën Purac Reiffenhäuser Rieter Automotive Sainsbury‘s Sidaplax SIG Corpoplast Signum Specialties Sony Sukano Teijin The National Non-Food Crops Centre Tianan Biologic Material Toyota Transmare Uhde Inventa Fischer Universität Kassel Wiedmer Woolworth

Editorial 12,19 18 35 28 10 34 12 19 5 5 6

29 6,35 38 20 12 35 8,13 6 5 18 13, 25, 26, 28 13 35 35 34 35 11 21 24 12,19 35 35 13 28 36 5,13 7,13 12,18 34

Events Advert 40

40 41 2 40 40 40 40 41 40

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44 40 22, 40 40

Rigid packaging

03/08 04/08 05/08 06/08

Trays

Basics: Masterbatches, Additives 42

bioplastics MAGAZINE [02/08] Vol. 3

March 12-14, 2008 8th International Automobile Recycling Congress The Westin Grand Munich, Arabellapark, Munich, Germany April 1-2, 2008 Third World Congress, Wood Plastic Composites Crowne Plaza, San Diego California, USA www.executive-conference.com

April 1-3, 2008 JEC Composites Paris including biobasesd polymers and natural fibers Paris, France www.jeccomposites.com

22, 40 40 40

April 16-17, 2008 2nd Bioplastics Markets Intercontinental Shanghai Pudong, Shanghai www.cmtevents.com

April 22-23, 2008 „Connecting comPETence“: PETnology Europe 2008 Düsseldorf/Neuss , Germany, prior to Interpack http://www.petnology.com

40 40 40

For the next issue of bioplastics MAGAZINE (among others) the following subjects are scheduled:

Next issues:

www.greenpowerconferences.com

www.icm.ch 40,43

Next Issue Topics:

March, 12, 2008 Bioplastics & Biochemicals Alternative Bioproduct Uses for Biomass Feedstocks in the Biorefinery Process 10% discount for readers of bioplastics MAGAZINE see banner on the right for details Brussels Expo, Brussels, Belgium

April 2008 July 2008 September 2008 November 2008

April 24-30, 2008 Interpack - 2008 and here: Bioplastics in Packaging The interpack 2008 Group Exhibition Düsseldorf, Germany www.european-bioplastics.org www.interpack.com

meet bioplastics MAGAZINE June 18-19, 2008 7th Global WPC and Natural Fibre Composites Congress and Exhibition Kongress Palais, Stadthalle, Kassel, Germany www.wpc-nfk.de


natura means business

natura packaging develops and markets innovative, 100% biodegradable packaging solutions. Our Europewide activities can be divided into three main categories; Industriestraße 55 - 57

• Fruit and vegetable packaging • Waste management (including the MaxAir system) • Shopping bags (including our popular ‘happy bag’)

48432 Rheine

Te l . : + 4 9 ( 0 ) 5 9 7 5 / 3 0 3 - 5 7

Let natura help you get the most out of your business. Call +49 (0)5975 30357 or send an e-mail to info@naturapackaging.com. Fax. : +49 (0)5975/303-42

www.naturapackaging.com

Email : info@naturapackaging.com


A real sign of sustainable development.

There is such a thing as genuinely sustainable development. Since 1989, Novamont researchers have been working on an ambitious project that combines the chemical industry, agriculture and the environment: "Living Chemistry for Quality of Life". Its objective has been to create products with a low environmental impact. The result of Novamont's innovative research is the new bioplastic Mater-Bi 速. Mater-Bi 速 is a family of materials, completely biodegradable and compostable which contain renewable raw materials such as starch and vegetable oil derivates. Mater-Bi 速 performs like traditional plastics but it saves energy, contributes to reducing the greenhouse effect and at the end of its life cycle, it closes the loop by changing into fertile humus. Everyone's dream has become a reality.

Living Chemistry for Quality of Life. www.novamont.com

Inventor of the year 2007

Mater-Bi速: certified biodegradable and compostable.

Meet us at Interpack 2008 - Hall 7a Stand E05


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