bioplastics MAGAZINE 01-2012 by bioplastics MAGAZINE

01 | 2012

ISSN 1862-5258

January/February

Highlights Automotive | 10 Basics

bioplastics

magazine

Vol. 6

Basics of PLA | 54

1 countries

... is read in 9

FKuR plastics – made by nature!®

Transparent cups made from Biograde®

Enjoy a cold drink at our NPE booth!

FKuR Kunststoff GmbH Siemensring 79 D - 47877 Willich Phone: +49 2154 92 51-0 Fax: +49 2154 92 51-51 sales@fkur.com

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Editorial

dear readers It was quite a shock last week, to read about ADM ending the Telles joint venture. I cross my fingers and hope that Metabolix soon find a new partner (or partners), and a new business model. Meanwhile, let’s have a look into this latest issue. ‘Automotive’ is in first place, as usual for the beginning of a year. In addition to a new episode in the life of my favourite racing car we present a number of interesting articles about automotive applications and other developments related to the automotive industry.

‘Foam’ was also promised, but we are getting a bit short of news for this issue. Initially planned just for the ‘Basics’ article, PLA has become another real highlight in this issue. Here you will also find our NPE’2012 preview. After 40 years in Chicago this big North American trade show has moved to the Orange County Convention Center in Orlando, Florida. Besides a preview, with brief notes about some of the exhibiting companies, we offer a detachable centrefold with a floor plan of the exhibition as a special service to all NPE visitors. If you are coming to the show be sure to drop in to the bioplastics MAGAZINE booth and say hello (booth # 58047). If you prefer Europe as the place to pick up the latest news and information on the innovations in our business, then please take a look at the recently published programme (page 6) for our 2nd PLA World Congress on May 15th and 16th, 2012, in Munich, Germany. I sincerely hope to see you, either here or there …

Be our friend on Facebook: www.facebook.com/bioplasticsmagazine

… and until then, we hope you enjoy reading bioplastics MAGAZINE

Sincerely yours Michael Thielen

2nd PLA World

C o n g r e s s

15 + 16 MAY 2012 * Munich * Germany

bioplastics MAGAZINE [01/12] Vol. 7

Content Materials New biobased plastic for technical applications. . . . . . . 24 Transparent packing material from birch . . . . . . . . . . . 31 Four-unit process technology for PLA manufacturing. . 50

Application The biological bearing material . . . . . . . . . . . . . . . . . . . . 27

Foam Editorial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

PHBV foams and its engineered composites. . . . . . . . . . 28

News. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

Report

Application News. . . . . . . . . . . . . . . . . . . . . . . . . . . 40

BIOCORE – a biorefinery concept. . . . . . . . . . . . . . . . . . . 42

Suppliers Guide. . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

Successful start in Thailand. . . . . . . . . . . . . . . . . . . . . . . 52

Event Calendar. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

From Science & Research

Companies in this issue . . . . . . . . . . . . . . . . . . . . . 66

PLA nanocomposites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

Basics

NPE

Basics of PLA. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

Show Preview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

Did you know ?

Show Guide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

Photovoltaic vs biofuels. . . . . . . . . . . . . . . . . . . . . . . . . . . 58

01|2012

Interview Pilar Echezarreta. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

January/February

Automotive BioConcept-Car . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Fuel line made of bio-PA 1010 . . . . . . . . . . . . . . . . 13 Bioplastics in automotive applications. . . . . . . . . . 14 PLA and carbon nanotubes. . . . . . . . . . . . . . . . . . . 18 Automotive parts must be predictable. . . . . . . . . . 20 Rubber from dandelions for tyres. . . . . . . . . . . . . . 22

bioplastics MAGAZINE [01/12] Vol. 7

Cover: Michael Thielen

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News

Telles JV is ending – Mirel shall go on … Metabolix announced on Jan. 12, 2012 that ADM has given notice of termination of the Telles, LLC joint venture for PHA bioplastics. Metabolix however, will remain committed to successfully commercializing PHA bioplastics, as Richard Eno, Chief Executive Officer of Metabolix points out. The effective date of the termination will be February 8, 2012. Telles was established as a joint venture between Metabolix, Cambridge, Massachussetts, USA, and ADM, Decatur, Illinois, USA in July 2006. The joint venture sold PHA-based bioplastics, including Mirel and Mvera, in the USA, Europe and other countries. All Metabolix technology concerning PHA bioplastics that was used in the joint venture, including intellectual property rights, will revert solely to Metabolix. “Clearly, we are disappointed by ADM’s decision to withdraw from Telles. While this is a setback, we remain committed to successfully commercializing PHA bioplastics. Over the past few years, we now have proven the technology at industrial scale and believe that we now have the opportunity to launch this business with a different business model,” said Richard Eno. He continued, “We sincerely thank our customers, distributors, and partners for their interest in developing PHA-based solutions to address a growing market need for bioplastics. We will be evaluating alternate plans for commercialization and clearly wish to supply this growing market in the future.” Being asked by bioplastics MAGAZINE how such alternate plans could look like, Richard Eno responded:” Given Metabolix’s PHA intellectual property technology portfolio and longtime experience within the industry, we’re confident that we’ll be successful in finding a new option for manufacturing

and commercialization. The Company has been in contact with potential partners who expressed interest – these include raw materials suppliers, manufacturers, industry players and customers. Metabolix will continue to engage in new partnering discussions and evaluate options to launch its PHA bioplastics business with a new model.” And he added: “The bioplastics market is growing at 20 percent per year, and based on our experience, we can see where a PHA offering can participate in this growth – as is evidenced by the strong customer validation we’ve had for the product. Metabolix’s PHA technology platform is a valuable contribution to the industry, and as such, the Company plans to continue to focus on the development of PHA bioplastics. Metabolix is also developing biosourced industrial chemicals and a proprietary platform technology for co-producing plastics, chemicals and energy, from crops. We believe that Metabolix is positioned for growth, as the demand for biobased technologies continues to rise.” And finally, Eno is keen to: “... express my appreciation for the efforts put forth by the Telles and ADM Polymer teams, who have demonstrated the commercialization of PHA bioplastics at world scale. MT www.metabolix.com

Richard Eno, CEO, Metabolix

Rodenburg acquired Optimum Rodenburg Biopolymers BV, Oosterhout, the Netherlands, manufacturer of potato starch based Solanyl bioplastic compounds, has purchased Optimum BV, Rotterdam, the Netherlands, producer of FlourPlast biodegradable biopolymers. Details about the financial terms of the deal were not disclosed. Both products, Solanyl and FlourPlast, were developed with the German company Wacker Chemie from Munich. The acquisition enables Rodenburg to serve both the converter and the compounder markets with biopolymers. The raw materials for their Solanyl compound are based on reclaimed side stream starch from the potato processing industry. This is now complemented by Optimum’s proprietary FlourPlast biopolymer, based on grain-derived products, which can be directly compounded with existing biopolyesters. In addition, FlourPlast allows processors to fine-tune bioplastic or polyolefin formulations to achieve desired properties and reduce costs. Solanyl, available since 2004 can be used in injection moulding, sheet extrusion, thermoforming and blow moulding. It is sold as a compound, where as FlourPlast is sold as a pre-compound system. MT www.biopolymers.nl www.optimumbioplastics.com

bioplastics MAGAZINE [01/12] Vol. 7

News

bioplastics MAGAZINE presents: The 2nd PLA World Congress in Munich/Germany is the must-attend conference for everyone interested in PLA, its benefits, and challenges. The conference offers high class presentations from top individuals in the industry and also offers excellent networkung opportunities. Please find below the preliminary programme. Find more details and register at the conference website

2nd PLA World

C o n g r e s s

15 + 16 MAY 2012 * Munich * Germany

www.pla-world-congress.com

2nd PLA World Congress, Preliminary Program Tuesday, May 15, 2012 08:00 - 09:00

Registration, Welcome-Coffee

09:00 - 09:15

Michael Thielen, Polymedia Publisher

Welcome

09:15 - 09:45

Harald Kaeb, narocon

Keynote Speech: Bioplastics - Future or Hype ?

09:50 - 10:15

Udo Mühlbauer, Uhde Inventa-Fischer

Latest developments in production of PLA

10:15 - 10:40

Chae Hwan Hong, Hyundai-Kia Motors

Development of Four Unit Process Technologies for PLA Manufacturing

10:40 - 10:55

Q&A

10:55 - 11:20

Coffeebreak

11:20 - 11:45

Mark Vergauwen, NatureWorks

The Latest in Ingeo Performance Developments

11:45 - 12:10

Francois de Bie, Purac

High Heat PLA for use in high performance fibers and other durable appl.

12:10 - 12:35

Kevin Yang, Shenzhen Brightchina

ESUN PLA

12:35 - 12:50

Q&A

12:50 - 14:00

Lunch

14:00 - 14:35

Patrick Zimmermann, FkUR

Modifying PLA to the next level

14:35 - 14:50

Karin Molenveld, Wageningen (WUR)

Strain induced crystallisation as a method to optimize PLA properties

14:50 - 15:15

Daniel Ganz, Sukano

PLA Masterbatch Technology – State of the art and latest trends

15.15 - 15:40

Marcel Dartee, Polyone

Additives / Masterbatches for PLA

15:40 - 15:55

Q&A

15:55 - 16:30

Coffeebreak

16:35 - 17:00

Jan Noordegraaf, Synbra

PLA particle foam

17:00 - 17:25

N.N., Toray International

Toray‘s modified PLA materials

17:25 - 17:50

Mr. Shim, SK Chemicals

title t.b.c.

Wednesday, May 16, 2012 09:00 - 09:25

Karl Zimmermann, Brückner

Latest Technology in Film Stretching

09:25 - 09:50

Frank Ernst, Taghleef

NATIVIATM – The BoPLA film for packaging and labelling applications

09:50 - 10:15

Larissa Zirkel, Huhtamaki

Innovative Concepts of Functional PLA Films

10:15 - 10:40

Shankara Prasad, SPC Biotech

Bio conversion of agriwaste to polylactic acid

10:40 - 10:55

Q&A

10.55 - 11:20

Coffeebreak

11:20 - 11:45

Johann Zimmermann, NaKu

Processing PLA (title t.b.c.)

11:45 - 12:10

N.N., Ireland, t.b.c.

Processing PLA (title t.b.c.)

12:10 - 12:35

Mathias Hahn, Fraunhofer IAP

Modification of PLA with view to enhanced barrier and thermal properties

12:35 - 12:50

Q&A

12:50 - 14:00

Lunch

14:00 - 14:35

Steve Dejonghe, Galactic

Building the recycling scheme for PLA

14:35 - 14:50

Gerold Breuer, Erema

Closing the loop on bioplastics by mechanical recycling

14:50 - 15:15

Sebastian Schippers, (IKV)

Recycling of polylactic acid and utilization of recycled polylactic acid

15.15 - 15:40

Ramani Narayan, Michigan State University

Positioning and branding PLA products from carbon footprint and end-of-life

15:40 - 15:55

Q&A

16:00 - 16:30

Panel discussion: End of life options

(subject to changes, visit www.pla-world-congress for updates)

bioplastics MAGAZINE [01/12] Vol. 7

News

New plants to produce succinic acid and BDO BioAmber Inc. from Minneapolis, Minnesota, USA, a next generation chemicals company, and Mitsui & Co., Chiyodaku, Tokyo, Japan, a leading global trading company, have partnered to build and operate the previously announced manufacturing facility in Sarnia, Ontario, Canada. The initial phase of the facility is expected to have production capacity of 17,000 tonnes of biosuccinic acid and commence commercial production in 2013. The partners intend to subsequently expand capacity and produce 35,000 tonnes of succinic acid and 23,000 tonnes of 1,4 butanediol (BDO) on the site. Bioamber and Mitsui also intend to jointly build and operate two additional facilities that, together with Sarnia, will have a total cumulative capacity of 165,000 tonnes of succinic acid and 123,000 tonnes of BDO. BioAmber will be the majority shareholder in the plants. Succinic acid and 1,4-BDO are used to make polybutylene succinate biopolymer (PBS), a biodegradable polymer that until now is made from petroleum. “The use of BioAmber Biosuccinic Acid enables the PBS biopolymer to be not only biodegradable, but also partially renewable and — more cost effective”, as Babette Pettersen, Senior VP Marketing & Sales of BioAmber explained to bioplastics MAGAZINE, “in addition, BioAmber also has a low-cost route to Bio-1,4-BDO, based on technology licensed from DuPont, that enables us to tranform biosuccinic acid into Bio 1,4-BDO. This will enable a 100% renewable biopolymer (Bio-Succinic Acid + Bio-BDO).” One of the key issues with biopolymers to date has been lack of performance. PBS takes this to another level, and BioAmber‘s mPBS (modified PBS) enhances these properties further. Designed and formulated using BioAmber’s proprietary technology, their mPBS meets end-user requirements for higher performing, biodegradable plastics. The uniformity, performance and processability of mPBS in existing equipment has been confirmed by a number of end

users, with applications ranging from foodservice cutlery and coffee cup lids to plates, bowls, straws and stirrers, through to durable applications in Automotive, Building & Construction... BioAmber and Mitsui plan to build and operate a second plant in Thailand, which is projected to come on line in 2014. The partners are currently undertaking a feasibility study for the Thailand plant with PTT MCC Biochem Company Limited, a joint venture established between Mitsubishi Chemical Corporation and PTT Public Company Limited. BioAmber and Mitsui & Co. also plan to build and operate a third plant, located in either North America or Brazil, which will be similar in size to the Thailand project. “Our goal is to play a leading role in the growth of renewable chemicals, as evidenced by our recent joint ventures with BioAmber in North America for biosuccinic acid and The Dow Chemical Company in Brazil for biochemicals,” said Masanori Ikebe, General Manager of Mitsui’s Specialty Chemicals Division. “We believe that biosuccinic acid and bio‐BDO will experience rapid growth over the next decade, and BioAmber’s technology leadership is an excellent fit with Mitsui’s strength across the supply chain,” he added. “BioAmber’s partnership with Mitsui & Co. is a strong endorsement of our technology platform,” said Jean‐ Francois Huc, CEO of BioAmber. “Mitsui is an ideal partner thanks to its long term commitment to renewable chemistry, its extensive reach into chemical markets and its strategic access to sustainable feedstocks. Mitsui also has the financial strength to support our expansion and help us compete internationally,” he added. MT www.bio-amber.com www.mitsui.com

CHINAPLAS 2012 Grand Returns to Shanghai CHINAPLAS 2012 (The 26th International Exhibition on Plastics and Rubber Industries), which is dedicated to showcasing the world-class cutting-edge plastics and rubber technologies, will grandly return to Shanghai and held at Shanghai New International Expo Centre on April 18-21, 2012. One of 11 theme zones the organizer has set up in order to highlight the development of each specialized area comprehensively by displaying their cutting-edge technologies, techniques and applications for various industries is dedicated to bioplastics. The Bioplastics Zone will be the second year established in CHINAPLAS 2012, expecting more than 40% increase in the area. With the growing global concern on green manufacturing, bioplastics is inevitably the focus in the plastics industry, with enormous potential in the market. As the international platform for advanced technology in the plastics and rubber industries, CHINAPLAS 2012 will introduce the world’s leading bioplastics suppliers and their products like PLA, PHA, PBS, PPC, PCL, PVA, TPS, PA and PTT. The renowned exhibitors include Cardia, Danisco, Ecomann, Esun, Hisun, Kingfa, Mirel Plastics, NatureWorks, Nuvia, etc. Highlighting advanced technology and latest development on bioplastics, the 4th International Conference on Bioplastics and the Applications will be held concurrently with CHINAPLAS 2012. Like the last edition held in 2011, speakers from the leading bioplastics suppliers will be invited. Overseas and Chinese plastics associations will continue to support the conference. www.chinapasOnline.com

bioplastics MAGAZINE [01/12] Vol. 7

News

Congress unveiled two-figure growth in WPC production With nearly 300 participants from 21 countries and 30 exhibitors, the 4th German WPC Congress, Cologne (13th-14th December 2011) organised by nova-Institute once more lived up to its reputation as the industry’s leading European event. The European market for Wood Plastic Composites (WPCs) has been growing at an average annual rate of 35% since 2005. Given the current levels of investment in expanding production and growing interest from both trade and consumers, the industry is optimistic about the future and expects continued growth in every sector in the coming years over the next few years. WPCs are predominantly used in applications that emphasise product characteristics such as great rigidity and low shrinkage (compared to pure plastics) and better durability and mouldability (than pure wood products). However, as prices for plastics rise, it is only a matter of a few years before WPC pellets are cheaper than pure plastic pellets (they are presently 20-30% more expensive) and can then conquer mass markets.

Winners of the WPC Innovation Prize – Evonik, Möller and Werzalit The presentation of the ‘WPC Innovation Prize’, which was sponsored this year by BASF Color Solution Germany was awarded to three companies. The audience of the congress voted for their favourites out of a short list of six innovations.

1st place: Evonik Industries, Essen, Germany - PLEXIGLAS® Wood PMMA-wood composite Together with Reifenhäuser, Evonik developed a pure PMMA-wood composite that could be used to produce directly extruded profiles. Evonik says that the new material ‘takes WPCs to a whole new level in terms of weather resistance, colour stability, dimensional stability and technical strength’. The 2nd place went to Möller, Meschede, Germany for a new WPC noise protection profile and the 3rd place was awarded to Werzalit, Oberstenfeld, Germany for their process technology for in-mould coating of injection-moulded WPC parts. MT www.wpc-kongress.de

Coca-Cola signed agreements to develop 100% plant based bottles In Mid December 2011 the Dutch company Avantium, Amsterdam, The Netherlands announced an agreement with The Coca-Cola Company to further co-develop their YXY technology for producing PEF bottles. First milestones include the start-up of an Avantium PEF pilot plant last December. Avantium plans to initiate commercial production of PEF in about three to four years. The Coca-Cola Company at the same time announced multi-million dollar partnership agreements with two other leading biotechnology companies to accelerate development of the first commercial solutions for next-generation PlantBottle™ packaging made 100% from plant based materials. The Coca-Cola Company‘s first generation PlantBottle packaging is the only fully recyclable PET bottle made with up to 30% plant-based material available today. PlantBottle packaging is made up of two components: MEG (monoethylene glycol), which makes up 30% of the PET, and is already made from plant materials, and PTA (purified terephthalic acid), which makes up the other 70%. In the next step, PTA will be replaced with plant-based materials, too.

bioplastics MAGAZINE [01/12] Vol. 7

Therfore, Coca-Cola signed agreements with Virent and Gevo, also industry leaders in developing plant-based alternatives to materials traditionally made from fossil fuels and other non-renewable resources. Virent, Madison, Wisconsin, USA, has a patented technology that features catalytic chemistry to convert plantbased sugars into — among others — bio-based paraxylene, a key component needed to deliver plant-based terephthalic acid. Gevo, Englewood, Colorado, USA is going develop and commercialize technology to produce paraxylene from biobased isobutanol. Since introduced in 2009, the Coca-Cola Company has already distributed more than 10 billion partly biobased PlantBottle packages in 20 countries worldwide. MT www.thecoca-colacompany.com www.yxy.com www.gevo.com www.virent.com

News

New crystal clear bioplastic for injection moulding End of last year FKuR from Willich, Germany presented its further developments of the cellulose acetate based Biograde速 products. The highlight of this development is Biograde速 V 2091 which is a completely transparent injection mouldable grade that has been developed for thin wall parts with long flow paths. Along with its high transparency, Biograde V 2091 stands out due to its smooth and shiny surface. Moreover, especially for thin walled parts, it outperforms standard polystyrene (PS) as to flexibility and heat distortion temperature. With these extended properties, the product line Biograde sets new standards and allows for the realization of diverse applications within the electronic and household appliances sector.

Plate and cup made from transparent Biograde V 2091 (Photos FKuR Kunststoff GmbH)

FKuR will present more details on their PLA activities at the

www.fkur.com

2nd PLA World

C o n g r e s s

15 + 16 MAY 2012 * Munich * Germany

Contact sales@fkur.com, to get a 15% discount on the conference fee. organized by bM

A truly globally diverse conference addressing the entire value chain.

Experience networking and interactive events for real-time collaboration unlike any other.

w w w. b i o p o l y m e r w o r l d . c o m Mestre-Venice, Italy, 23-24 April

+1 858.592.6951 Early Bird Discount Ends 24 February

Latest technology, future directions, & emergent trends that will leave you inspired.

bioplastics MAGAZINE [01/12] Vol. 7

Automotive

BioConcept-Car – New approaches into biomaterials By Michael Thielen

The rear hatch made of flax and hemp

he BioConcept-Car has become a true and faithful companion of bioplastics MAGAZINE. In our first ‚automotive issue‘ in early 2007 we introduced the Ford Mustang racing car with bodywork made of flax fibre reinforced linseed acrylate. In 2009, during the Composites Europe trade show the next generation BioConcept-Car, a green Renault Mégane Trophy was shown and bioplastics MAGAZINE reported in issue 01/2010. Last autumn the current BioConcept-Car, in this case a Volkswagen Scirocco, was introduced on the famous German race track, the Nürburgring, and during this event I was invited to experience a lap in the passenger seat of the car. I must admit: “What an experience !” Thomas (Tom) von Löwis of Menar, head of the Four Motors racing team, drove me around the legendary Nordschleife (‘The green hell’) at up to 240 km/h (150 mph) — up and down the ‘Eifel’ hills and through one hairpin bend after another …. It was a great day. And after this experience I spoke with Tom von Löwis as well as with Prof. Hans-Josef Endres1, who consults for Four Motors with regard to the future use of bioplastics in the BioConcept-Car.

On automanager.tv (an Internet platform) the editor and presenter Guido Marschall conducted an interview2 with these two gentlemen. This article comprises parts of both these interviews. The Volkswagen Scirocco BioConcept-Car — in short the ‘BioRocco’ — is a biodiesel driven racing car like its predecessors, but fuelled with a new generation of biodiesel, the so-called ‘NExBTL’. And it is becoming more and more sustainable. As a first step, the car was equipped with a rear hatch made of hemp and flax fibres. MT: What were the main reasons to convert the rear hatch to this special material?

The new ‘Bio-Rocco’ (Michael Thielen as passenger)

TvL: Besides the fact that we are trying to use as much biobased material as possible, lightweighting is an important issue. HJE: The topic of lightweighting is certainly important not only in order to win races, but also with a view to the fuel consumption and the exhaust emissions. But another very important fact here is the topic of resource conservation in terms of the materials used. We want to build highly efficient cars, however, not simply by using the resources that are available today. We also want to do this in 50 years from now. We want to apply plastics, with their fantastic properties, in the future, and also for demanding technical applications. Thus we need materials that do not depend on limited resources but are available even in the long term — and with the technical properties we need.

bioplastics MAGAZINE [01/12] Vol. 7

Automotive

The â&#x20AC;&#x2DC;Bio-Roccoâ&#x20AC;&#x2DC; (Photo: Four-Motors)

GM: Now, these new materials are not being developed in the first place with the aim of achieving new records in car racing, but motor sport offers the possibility of testing these new materials to the limit, and then to take advantage of these experiences for series production vehicles. Besides the fun that motor sport offers, this has been common practice for years, even in Formula 1. Which new insights are being collected with biomaterials used in motor sport today? TvL: One example is lightweighting, which we just mentioned. Let us compare this new version with a component in the first Mustang in 2006. The natural fibre reinforced material at that time was slightly heavier than a fibreglass material. Today, for example with the support of Professor Endres, the new hemp/flax version is almost as light as carbon fibre. HJE: We have learned a lot. Natural fibres in fact show similar, although different, properties from those of glass or carbon fibres. And subsequently the processing is similar but also different. Here questions had to be resolved, for example concerning the draping of a fabric. How does the weaving technology have to be adopted in order to optimise the draping behaviour? What is the optimum weight per area of a fabric so that the fabric can absorb enough resin and lead to an optimum final density? What about the compatibility (fibre/matrix adhesion) of the natural fibres and the resins? What are the resulting material properties of the composite? We are at the very beginning of an exciting learning process.

looking at different technical bioplastics like bio-PA or new biopolyesters, and in future also at biobased polypropylene. GM: Which components in the racing car can be replaced by components made from biobased materials? TvL: I would not venture to say all, but most probably all those body parts that can be replaced in a racing car, such as the hood, left, and right doors, the rear hatch, the front and back bumpers, fenders etc. can all be made from these new natural fibre composites. MT: Are these natural fibre composites as stable as conventional ones? HJE: They can withstand the same loads as body parts made from fibreglass or carbon fibre, and one additional advantage is that they do not splinter in crashes. GM: And this is most especially desirable if we think about converting the material to series production vehicles. HJE: Yes, and they are lighter today than fibreglass parts, and only 30 percent of the weight of a steel version. In a small production series they can even be manufactured at a lower cost. Tom von LĂświs, Hans-Josef Endres and Guido Marschall on automonager.tv (photo: automanager.tv)

GM: What kind of biomaterials are we talking about here? HJE: The natural fibres we are using are flax and hemp. For the time being we are combining these with petroleum based castable crosslinked resin systems because we wanted to concentrate first on the optimisation that we mentioned in terms of fibres and weaving. But in future steps we also want to look into resin systems based on vegetable oils, such as linseed or sunflower. For the thermoplastic materials we are

bioplastics MAGAZINE [01/12] Vol. 7

GM: For example in the field of electromobility consumers set great store on showing that they are doing good for the environment. Shouldn’t biomaterials offer the possibility of showing this particular property, i.e. of being ‘green’? Or is it still a ‘no-go’ to leave natural fibres openly visible in a car? TvL: For carbon fibre parts it is sexy to see the black fabric through the resin in an unpainted part. People want to see and show what high tech parts they have. We should take a similar approach. Make it visibly clear that we are using biobased materials — and be proud of it. Hans-Josef Endres and Tom von Löwis

MT: And what comes next? HJE: In addition to the doors, fenders etc, we will look into three-dimensional parts such as mirror housings or parts of the dashboard. But here completely different thermoplastic processable bioplastics are needed. And even here we want to compete with petroleum-based materials in terms of quality, durability and cost. GM: Will all this also be suitable for mass production? We know from carbon fibre applications that it was not possible to convert the manufacturing processes easily to series production. Now we are getting there slowly, and step by step. HJE: Of course we see a chance here and this is a challenge. But we are only at the beginning of the development. In fact there are already quite a number of bioplastics in automotive applications today. These are parts in the interior such as hatracks, spare-wheel covers or parts of the instrument panel. All these can be manufactured with existing mass production techniques. However, most of these parts are invisible or covered. One of the next steps is to make exterior parts and visible parts.

GM: Let’s talk about money. The OEMs and sub-suppliers are always interested in the cost factor. I assume these new materials are not cheaper than the conventional ones, otherwise the automotive industry would be applying them already. HJE: Well, you should not only look at the raw material cost but at the complete system. If we consider for example the ‘end of life’, we know that in waste incineration glass fibres would create ash. Natural fibres, however, don’t leave behind so much ash but contribute to what we call ‘renewable energy’. If we look at the processing we see that glass fibres are more abrasive, whereas natural fibres are not abrasive. Thus the life-time of tools and dies is much longer. MT: In addition it can be observed that the cost of traditional plastics is rising with the increasing price of oil. So biobased plastics will become competitive in the mid to long term, and not only via economies of scale with larger production capacities. But after all this talking about materials and renewable resources, there is one more important target for Tom von Löwis and his team: They want to drive and win races with their BioConcept Car. Good luck for the coming season! www.fourmotors.com www.ifbb-hannover.de www.fnr.de

1: Prof. Dr.-Ing. Hans Josef Endres, IfBB, Institute for Bioplastics and Biocomposites, University Hanover, Germany. Supported by the FNR (Agency for Renewable Resources within the German Federal Ministry of Food, Agriculture and Consumer Protection) the IfBB will assist Four Motors to develop more and more components made from biobased materials (natural fibres and bioplastics) for the BioConcept Car. 2: We are grateful to Guido Marschall and autmomanager.tv for the permission to publish parts of their ‘auto-talk’ interview of Dec. 13th 2011. www.automanager.tv

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Covergirl Christine also took a ride in the Bio-Rocco. She said: “Amazing, a ‘green car’ in the’green hell’ and with more biobased plastic parts it becomes even greener.”

Automotive Photo: DuPont

Fuel line made of bio-PA 1010

he fluid transfer system supplier Hutchinson SRL, of Rivoli, Italy, has specified a DuPont™ Zytel® RS polyamide grade based on PA 1010 for the production of fuel lines used with both diesel and biodiesel. The renewably-sourced long-chain nylon was chosen in preference to competitive grades of PA12 on the basis of its superior temperature resistance and long-term aging performance in biodiesel. The extruded, monolayer fuel line from Hutchinson is already in use on commercial new turbo and multijet diesel engines used on several Fiat vehicles, including the Fiat 500, Panda, Punto, Lancia Delta, Alfa Romeo MiTo and Giulietta. As well as seeking to increase the use of renewablysourced polymers to reduce dependence on fossil fuels, automotive manufacturers, OEMs and materials suppliers are modifying engine and fuel systems to run efficiently on the latest generation of biofuels, including biodiesel. Components for such systems must resist the chemicallyaggressive biofuels, temperature extremes and mechanical stresses for the lifetime of the vehicle. This specific Zytel RS grade based on PA1010, which contains more than 60% renewably sourced ingredient by weight, offers properties typical of flexible polyamides with additional benefits such as superior high temperature resistance when compared to materials such as PA 12, high chemical resistance and low permeability to fuel and gases. It is suitable for a range of extrusion applications including fuel lines, hydraulic hoses, corrugated tubes, transmission oil cooler hoses and pneumatic tubes. “We were seeking a polymer for our fuel line application that was preferably renewably-sourced, for a more sustainable

solution, and was able to provide the best aging stability in biodiesel,” explains Katia Rossi, development manager at Hutchinson. “We considered a number of flexible polyamides, including PA12 as they had previously been specified for similar fuel line systems, but material testing showed Zytel RS PA1010 to meet our requirements. It combines, for example, superior temperature resistance to PA12 with the best resistance to biodiesel at high temperatures.” Data on aging performance in biodiesel was obtained by immersing the materials in the most common biodiesel – rapeseed methyl ester (RME) – at 125 °C (257 °F) for 1,000 hours and measuring retained mechanical properties. The B30 biodiesel used for testing is made up of 30% biofuel from rapeseed and recycled vegetable oil and 70% standard diesel and is suitable for many diesel cars. By specifying the DuPont material for its fuel line for diesel engines, Hutchinson gains a longer-lasting solution that is also market leading in terms of its renewably-sourced content. “With more than 60% by weight, this Zytel RS grade based on PA1010 has one of the highest levels of renewablysourced content currently available for a high performance nylon,” confirms Mario Delbosco, development programs manager at DuPont Performance Polymers. The renewable carbon in PA1010 comes from sebacic acid, which in turn is derived from castor oil. The successful adoption of renewably-sourced Zytel nylon for the fuel line, which is already in commercial use on diesel-engined cars, has encouraged Hutchinson to extend the application to other automotive manufacturers in Europe and beyond as well as other fuel system applications. www.dupont.com

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Automotive

Bioplastics in automotive applications By Daniela Rusu, SĂŠverine A.E. Boyer Marie-France Lacrampe, Patricia Krawczak Ecole des Mines de Douai, Department of Polymers and Composites Technology & Mechanical Engineering, Douai, France

owadays, polymeric materials represent approximately 20 % of the total weight of an automobile, in other words 100 to 150 kg/car. This substantial need in plastics, and recent economical and ecological issues such as the increasing crude oil price, accelerated depletion of fossil resources, together with the new regulations for controlling greenhouse gas emissions and management of the end-of-life of vehicles, has encouraged the automotive industry to develop, adapt or revive some long existing more eco-friendly plastic materials and biocomposites for their modern cars. Currently bioplastics cover a wide range of materials, from commodity thermoplastics up to engineering materials and thermosetting resins. Within these bio-based polymeric materials, some are already validated for different automotive applications: it is the case for some bio-based polyamides and bio-based polyurethane foams, but also for polylactic acid formulations and fabrics. Other bioplastics with potential/validated use in automotive industry are belonging to the class of bio-based polyesters and copolyesters, starch plastics, bio-based polyolefins and bio-based thermosetting polymers such as unsaturated polyester resins or bio-based epoxies (for more details see [1]). And even if some of their present features are not yet optimal for durable automotive applications, they could offer in future real alternatives for petrochemical plastics in modern cars.

Taken from Handbook of Bioplastics and Biocomposites Engineering Applications edited by Srikanth Pilla â&#x20AC;&#x201C; Wiley-Scrivener 2011 (http://www.wiley.com/WileyCDA/WileyTitle/ productCd-0470626070.html).

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Automotive The following shows three examples of bioplastics and vegetal fibre reinforced bioplastics to have an idea about the potential of these types of materials for automotive applications.

Biopolyamides (Bio-PA) Polyamides (PA) are engineering thermoplastics that combine excellent mechanical properties, such as high mechanical strength and stiffness, wear properties, good heat resistance, together with chemical resistance to oils and solvents, dielectric properties, fire resistance, good appearance, and good processability. All these interesting features design them for high-end automotive applications, especially for under-the-hood car compartment. In fact, PA and PA composites represent about 10% of the plastics parts in modern cars. Until recently, the polyamides for car applications were petro-based, except the Rilsan®PA 11 from Arkema, derived from castor oil, and already used for flexible tubing, mono-wall fuel lines and Rilperm® multi-layer fuel lines, such as in ESD-Flex conductive fuel-pump module for General Motor car models, and for friction parts, quick connectors, pneumatic brake noses. Today, several other new bio-based polyamides appeared on the market, derived (at least partly) from renewable feedstocks such as castor beans and sugar cane. A recent example of an under-the-hood application of a biopolyamide, the DuPont™ Zytel® RS, PA 6.10 (with 62.5% biobased carbon content), is the new automotive radiator end tank proposed by Toyota, Denso and DuPont Automotive consortium, and used in some 2009 Toyota Camrys vehicles.

Castor plant

In appears that current and emerging bio-PA are promising new solutions for replacing the petrochemical polyamides, but also for extending the metal substitution in car applications, improving automotive comfort, design and insulation, and enriching the performances with fuel economy and reduced CO2 emissions.

PLA and PLA-based composites While the biopolyamides already represent themselves as engineering polymers for high-end automotive applications, PLA is a rather new polymer in automotive applications and from some aspects, still in development. For long time, this aliphatic biodegradable polyester was intended only for biomedical and packaging uses, but in the last years, new PLA-improved materials were proposed for durable applications, such as transportation, electrical applications and electronics. Up to now, PLA fibers and fabrics were proposed for floor mats, in Toyota Raum and Prius cars (2003), and for canvas roof and carpet mats in Ford Model U (2003). The more recent Biofront™ stereocomplex PLA codeveloped Teijin & Mazda, is intended for automotive applications such as car seat fabric, as for Mazda Premacy Hydrogen RE Hybrid vehicle, but also floor mats, pillar cover, door trim, front panel and ceiling material.

Accelerator pedal made from bio-PA 6.10 (prototype)

Vegetal fibre reinforced PLA is another class of green materials, with current and potential car applications. For instance, Toyota is already proposing automotive applications for PLA/kenaf biocomposites, such as the cover spare wheel on Toyota Prius and Toyota Raum (2003) or the translucent roof PLA/kenaf and ramie biocomposites on Toyota 1/X plug-in hybrid concept vehicle.

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However, the long-term properties of PLA-based materials intended for durable applications are to be validated over different time periods and aggressive environment conditions, before thinking to extend their automotive applications.

Bio-based polypropylene (bio-PP) Petrochemical polypropylene (PP) is largely used in modern cars, and this is an important motivation for developing alternative greener materials with similar features, able to substitute it. Several attempts were made for obtaining bio-PP via bio-ethanol from different renewably feedstocks. For instance, Braskem and Novozymes announced a research partnership to develop large-scale production of green PP from sugarcane, a resin already obtained on laboratory scale (Braskem) and certified as 100% renewable. In the same time, Mazda is actively developing a bio-route for obtaining various PP and ethylenepropylene copolymers from cellulosic biomass. These new bio-based materials are intended in future to replace their petrochemical counterparts automotive applications such as (i) car bumpers and bumper spoilers, lateral siding, roof/boot spoilers, rocker panels, body panels; (ii) dashboards and dashboard carriers, door pockets and panels, consoles; (iii) heating ventilation air conditioning, battery covers, air ducts, pressure vessels, splash shields.

parts applications in dashboards, door panels, parcel shelves, seat cushions, backrests and cabin linings, car disk brakes and even for exterior applications, such as the engine/transmission covers in Mercedes-Benz Travego Coach.

In future, the new bio-based PP could also gradually shift the petrochemical PP from its biocomposites with natural fibers, in trim

General Conclusions

conference on sustainable packaging

2012

SusPack

www.suspa c k.e u For the second time at the Anuga FoodTec, the conference „Sustainable Packaging - SusPack 2012“ is taking place from March 29th - 30th 2012. At the two-day conference (at Koelnmesse, Cologne) current issues and solutions for sustainability in the packaging industry will be presented and discussed. The focus is on bio-based packaging: Where and in what form have they been able to establish? What benefits do they bring? What has to be considered in the use? And finally, what innovations, trends and potentials are becoming evident? Topics SusPack 2012: booking now on new developments in bio-packaging w w w. s u s p a c k . e u End-of-life options overview over packaging market how to reduce food decay through new packaging solutions packaging from bio-based Polyethylen Call for papers & SusPack Award Take part and send your application to Ms. Lena Scholz, phone: +49 (0)2233 48 1448, e-mail: lena.scholz@nova-institut.de, by January 27th, 2012.

Organiser

Partner

Do you have any questions concerning SusPack 2012? We are happy to help you! Mr. Dominik Vogt Tel.: +49 (0) 22 33 – 48 14 49

www.nova-institut.eu

www.anugafoodtec.de

dominik.vogt@nova-institut.de

bioplastics MAGAZINE [01/12] Vol. 7

PLA based car seat fabric (photo: Mazda)

Recent economical and ecological increasing concerns are offering strong motivations for substituting the well-known polymeric materials derived from fossil feedstocks and, in some cases, some metal materials with more ecofriendly materials from renewable resources, for a wide range of durable applications. More particularly, the green high-end polymeric materials are presenting a large potential for car applications and this trend is expected to grow over the next decades, knowing that the next-generation of vehicles will need to show enhanced efficiency in material use and increased technical and functional performances, while providing improved ecological footprint and less dependence on fossil feedstock costs. www.mines-douai.fr [1] Handbook of Bioplastics and Biocomposites Engineering Applications, chapter “Bioplastics and Bioplastics and Vegetal Fibre Reinforced Bioplastics in Automotive Applications”, edited by Srikanth Pilla

BIOADIMIDETM IN BIOPLASTICS. EXPANDING THE PERFORMANCE OF BIO-POLYESTER.

AILABLE: CT LINE AV EXPAND U D O R P W NE IVES E™ ADDIT TER BIOADIMID IO-POLYES B F O E C N MA THE PERFO

BioAdimide™ additives are specially suited to improve the hydrolysis resistance and the processing stability of bio-based polyester, specifically polylactide (PLA), and to expand its range of applications. Currently, there are two BioAdimide™ grades available. The BioAdimide™ 100 grade improves the hydrolytic stability up to seven times that of an unstabilized grade, thereby helping to increase the service life of the polymer. In addition to providing hydrolytic stability, BioAdimide™ 500 XT acts as a chain extender that can increase the melt viscosity of an extruded PLA 20 to 30 percent compared to an unstabilized grade, allowing for consistent and easier processing. The two grades can also be combined, offering both hydrolysis stabilization and improved processing, for an even broader range of applications.

Focusing on performance for the plastics industries. Whatever requirements move your world: We will move them with you. www.rheinchemie.com

Automotive

PLA and carbon nanotubes Nanotechnology for automotive applications By A. Tielas, V. Ventosinos, M. de Dios Plastic Product / Process Area Engineering & Development Department Galician Automotive Technological Centre (CTAG) PorriĂąo, Spain

he continuous development of science is making possible the design of new materials with properties that were unthinkable a few years ago. The constant searching for lighter compounds, durable and compatible with the environment, has become one of the main goals of many researches today. In this sense, nanotechnology has quickly revolutionized the whole picture of current design of high added value materials due to the unique properties that those composites exhibit in fields as diverse as electronics, mechanics, optics or magnetism. Carbon nanotubes (CNTs) perfectly illustrate all the benefits that nanotechnology can bring, especially in the manufacture of polymer based nanocomposites. This is due to, among other reasons, their high electrical and thermal conductivity, which are transferred to the polymer, even using relatively small loads of CNTs. Many studies are being carried out to optimize the fabrication of polymer/CNT compounds, especially to improve the dispersion of CNTs within the polymer matrix. The Galician Automotive Technology Centre (CTAG), through its Engineering and Development department in the area of plastic products, seeks to explore and exploit all the inherent advantages of joining together polymer science and nanotechnology. Committed to the need to preserve respect for the environment by using, as far as possible, renewable sourced materials, CTAG currently develops compounds based on polylactic acid (PLA) and CNTs intended for diverse applications.

1,4 1,2

Conductivity (S/cm)

1 0,8 0,6 0,4 0,2 0

PLA/CNT (7%)

PLA/CNT (7%) Talc (10%)

PP/CNT (7%)

PP/CNT (7%) Talc (10%)

Fig. 1. Conductivity measured by the Van der Pauw method of 15x15x2 mm polylactic acid (PLA) and polypropylene (PP) pieces filled with the same content of CNT. PLA pieces exhibit more than five times the conductivity of PP samples.

Rimpact Rt=â&#x2C6;&#x17E; Impact Fig. 2. Resistance profile in a polymer/CNT sample during an impact.

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Indeed, one of the most interesting properties of PLA/CNT composites from the standpoint of the practical applicability is their electrical conductivity. It is known that internal CNT networks are formed beyond a given threshold concentration of filler, the point at which a great increase of the electrical conductivity of the material appears. The electrical behaviour of the polymer also largely depends on the degree of alignment and dispersion of CNTs within the polymer matrix. PLA favours the dispersion of CNTs due to its polar character, and, in fact, PLA/CNT compounds exhibit in the order of five times the conductivity of PP/CNT composites (Figure 1). It has been shown that an external factor that can alter the disposition of CNTs, further produces conductivity changes in the sample. This behaviour allows, for example, the detection of impacts, by conductivity measurements, on pieces made of this material. The potential applications are vast, from the dynamic monitoring of structural damage of key parts of a car, to the localizing and counting of impacts on the surface of an airplane fuselage (Figure 2). Based on the same principle, we have developed prototypes of smart pedals that can detect emergency braking situations and activate adequate safety measures in case of an imminent

Automotive

collision. Drivers react instinctively by contracting their bodies under impact danger situations, and this fact can reduce the braking efficiency just at the very moment prior to a possible collision. The conductivity of a pedal made of polymer/CNT composite depends on the pressure exerted over its surface, thus it is possible to predict risky braking scenarios and enhance the security profile of the entire car (Figure 3). An added advantage of PLA/CNT composites relies on their ability to act as electromagnetic shields. As many parts of an automobile, and generally many everyday electronic devices, have electronic circuits susceptible to emitting radiation, it is necessary to make use of materials of capable EM shielding in order to avoid interferences between them, and also for the provision of a radiation free environment that meets the current electromagnetic emissions legislation for health (e.g. UNE-EN 50083-212007). First results show the suitability of this kind of material for electromagnetic shielding purposes, to a certain extent due to their high conductivity, in the order of 1 S/cm (S=Siemens), which is in the range of semiconductors.

Fig. 3. Fully functional prototype of a brake pedal sensitive to the pressure exerted

Although the use of PLA offers many advantages, this material still does not meet the requirements of durability and resistance needed in the automotive industry. It remains a challenge to clearly understand the biodegradation mechanisms of PLA/CNT composites. Although there are numerous studies on the influence of the incorporation of CNTs over the degradation kinetics of the material, the role of nano-fillers over the structural stability of the composite is still unclear. Several factors, such as concentration and functionalization of CNTs, or the surface to volume ratio of the sample, have to be taken into account in order to minimize the degradation and maintain the added value of the nano-filled materials; nevertheless, much more effort should be made with the aim of better understanding PLA/CNT interactions. Nanotechnology offers a great variety of compounds allowing not only the enhancement of electric properties of the polymer, but also the optical, magnetic and mechanical ones. In the near future, and even at present, two important challenges must be faced. First, to try to better comprehend the behaviour of nanometric composites in order to control a large range of amazing new properties, and the most important, to take advantage of those properties, keeping in mind the necessity of producing environmental and health friendly materials for a sustainable progress. Although there remains much hard work to find the best way to combine renewably sourced polymers such as PLA with nanoscale structures, is a foregone conclusion that the partnership between polymer science and nanotechnology opens a new era of intelligent materials with astounding properties. www.ctag.com

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Automotive

Automotive parts must be predictable Material and flow models for natural fiber reinforced injection molding materials for practical use in the automotive industry By Erwin Baur M-Base Engineering + Software GmbH Aachen, Germany

or many years natural fibers (NF) have been considered for reinforcement of plastics. They show good mechanical properties and the principle qualification has been demonstrated in many projects. However, natural fibers are a relatively new type of material, unknown to the classical plastics industry. The producers of natural fiber reinforced plastics and even more the producers of fibers have a hard time to match all expectations of potential users concerning product information, support in design and processing, and predictability of products. Very interesting high volume application fields, like in the automotive industry, can not be served due to this lack. Natural fibers can be processed in many different ways, but considering the actual use of plastics in the automotive industry, injection molding applications seem to be most promising. Polyproylene would be the most likely matrix material, because it is already broadly used in relevant applications and its thermal properties allow the compounding with natural fibers.

Fig. 1: Automotive part made from natural fiber reinforced PP with 30% Sisal (Source Ford)

Today the automotive producers are strongly interested in the use of materials from renewable sources and a reduction of the carbon footprint of their products. The willingness to use bio materials has increased, even against well established concerns towards unstable qualities, challenging processing and small processing windows. In one point, however, the automotive designers do not like to compromise: every part needs to be predictable, which means the material must allow simulation of performance during processing/manufacturing and in the final use. All components must show complete theoretical proof that they meet product safety requirements and are fit for purpose through using digital simulation. This is a fixed, established procedure in the automotive industry to meet todayâ&#x20AC;&#x2122;s development times. So far injection moldable natural fiber reinforced thermoplastics could not offer the requested predictability. A new project, coordinated by M-Base Engineering + Software GmbH, Aachen, Germany has been started in order to bridge this gap. During a phase of three years relevant models for the simulation of natural fiber reinforced materials shall be developed, material parameters shall be measured and the validity of the new models shall be proofed with a realistic serial part. At the same time the basic simulation parameters shall be identified for as many different natural fibers as possible, so the results can be used for future projects. This project aims to open the way to enable natural fiber reinforced plastics to be designed theoretically and simulated in the automotive

bioplastics MAGAZINE [01/12] Vol. 7

Automotive

i 



Ti-1,i

Fig. 3: First results of flow simulation using specific mechanical properties of a natural fiber in a fountain flow. These patterns allow prediction of the most important effects during injection molding (Source: Tim Osswald, University of Wisconsin, Madison).

FHi 

THi



Fi-1,i

Fig. 2: Mechanistic model for a single fiber (Source: Tim Osswald, University of Wisconsin, Madison)

industry and subsequently in other industries. This will give natural fiber reinforced plastics the same status as established conventional plastics when selecting materials and in the long term their use in the industry will grow. The project will consider all aspects of simulation, the mechanical calculations will focus on simulating crash response (including in total vehicle simulation), which is vital for most automotive applications. Meeting these aims means considering the process as a whole, especially the anisotropic mechanical properties have to be considered, which follow completely different laws, compared to classical glass fibers. The following tasks are necessary, in order to find an integrative solution, covering the complete process: Establishing the micro-mechanical characteristics of natural fibers before and after processing Deriving a suitable fiber orientation model



Fck,i 

Fi+1,i



Ti+1,i

compounded and analyzed. The elementary mechanical properties of the fibers will be measured and incorporated into the flow models. Using special mechanistic models the flow behavior of the fibers during processing will be evaluated, including orientation, fiber damage and fiber matrix separation. Based on these first steps, new flow and orientation models will be incorporated into commercial injection molding simulation software, allowing prediction of the orientation in real parts. The orientation information will be used to determine the anisotropic mechanical properties of the parts. In addition to the fiber properties, the characteristic rheological and thermal properties for process simulation will also be measured for all compounds. Especially the viscosities curves will be challenging, due to fiber jamming in conventional capillary rheometers. The project partners offer a unique combination of expertise and equipment that is needed to fulfill these tasks efficiently:

Modeling typical side-effects when using NF plastics (fiber damage, separation etc.)

Ford Research & Advanced Engineering, Aachen

Produce NF compounds and test pieces

LyondellBasell, Frankfurt

Describing the rheological and thermal characteristics of NF compounds completely

Kunststoffwerk Voerde Hueck & Schade GmbH & Co. KG, Ennepetal

Determining quasi-static and dynamic mechanical properties

Simcon Kunststofftechnische Software GmbH, Würselen

Integrating the fiber orientation model with commercial flow simulation software

University of Wisconsin-Madison, Madison

IAC (International Automotive Components), Krefeld

M-Base Engineering + Software GmbH, Aachen

Scaling up compound production for selected materials to near-series level

Hannover Technical College, Institute of bioplastics and biocomposites, Hannover

Integrating material models with commercial CAE software, especially for processing and crash simulation purposes

Hochschule Bremen, Bremen

Simulating a serial component

Deutsches Kunststoff Institut (DKI), Darmstadt

Producing the serial component and conducting extensive mechanical testing, including crash response

The project is funded by the Federal Ministry of Food, Agriculture and Consumer Protection (BMELV) via the Agency for Renewable Resources (FNR).

During the project numerous combinations of several different PP matrix materials with natural fibers (Flax, Hamp, Sisal, Wood, Straw, Cellulose Regenerate) will be

Technical University Clausthal, Institute of polymer materials and plastics, Clausthal

www.m-base.de

bioplastics MAGAZINE [01/12] Vol. 7

Automotive

ven the rubber industry has felt the impact of a shortage of raw material and so is seeking alternatives to the supply of natural rubber from the Hevea brasiliensis tree.

This tree grows very slowly and needs about 20 years before it yields its harvest. “Natural rubber is gaining in interest because of the price of oil”, says Dirk Prüfer, professor and head of department at the Institute for Plant Biochemistry and Biotechnology at the Wilhelms University in Münster. The amount produced today will hardly be enough to cover demand. As an alternative dandelions are possibly a solution. During World War II the Americans, Soviets and Germans were looking at such alternatives. The idea of using dandelions as a natural source of raw materials was initiated by the Soviets in the early 1930s. When the Japanese occupied South-East Asia the Russians and Americans started to look seriously at producing a natural product from dandelions. On the occupation of the region by the Americans the Germans were using the technology

Rubber from dandelions Could Taraxacum koksaghyz be a future source of rubber for the tyre industry?

Taraxacum koksaghyz (photos: Christian Schulze Gronover)

Dandelion produces in its root, amongst other things, natural rubber, and can be successfully grown in wide areas of Europe which in other respects are not particularly fertile. If this were to be done on a commercial scale then the numerous existing wild species would have to be grown under agricultural conditions. In particular it will be a case of increasing the yield. A German group of six research partners have been working since spring 2011 on the methodical basis of a cultivation programme for Caucasian or Russian dandelion (Taraxacum koksaghyz). The project is being promoted by the German Federal Ministry of Food, Agriculture and Consumer Protection (BMELV) via the Agency for Renewable Resources (FNR). The first step in the research programme is the adaptation of existing biotechnical cultivation methods to dandelion cultivation. Alongside this the researchers want to obtain seeds in kilogram quantities. The Continental Tyre Company (Continental Reifen AG), an industrial partner of the group, is planning tests of the first natural rubber samples. In terms of cultivation the researchers, unlike in other European R&D projects on the same topic, are focussing on two year old plants. They expect to obtain, among other things, a higher potential yield in the second year. The disadvantage of a 2-year cycle is that the cultivation takes longer because only in the second year do the plants produce seed. For this reason the scientists want to use methods such as special analysis techniques to accelerate the process as much as possible. In February of this year, a new project, supported by the German Federal Ministry of Education and Research (BMBF) will be launched. The project partners are: Continental Reifen Deutschland GmbH, Synthomer, Südzucker AG, Fraunhofer IME & ICB, Aeskulap GmbH, University Stuttgart, Max-PlackInstitute for Plant Breeding, Julius Kühn Institut, LipoFIT Analytic GmbH. The goal is the sustainable development of dandelion as an alternative source to replace natural rubber, latex and inulin. Stay tuned - bioplastics MAGAZINE will keep you updated on this project. MT

bioplastics MAGAZINE [01/12] Vol. 7

Automotive

80% Bioplastic ‘Ecological Plastic’ covers 80% of new Toyota ‘Sai’ interior

oyota Motor Corporation has successfully used ‘Ecological Plastic’ to cover approximately 80% of the total interior surface area in the partially redesigned Japan-market ‘Sai’ gasoline-electric hybrid sedan. ‘Ecological Plastic’ is Toyota’s collective name of plastics developed by the company for automobiles and that use plant-derived material and are more heat- and shock-resistant, etc., than conventional bio-plastics.

www.toyota.com

Toyota announced that they achieved 80% coverage through the use of a new bio-PET-based Ecological Plastic in the seat trim, floor carpets, and other interior surfaces that require a higher abrasion-resistance than could be achieved with an earlier Ecological Plastic used in other parts of the interior. Bio-PET means that 30% by wt. (the monoethylenegykol component) is derived from renewable resources, here sugar cane. Toyota’s new material dramatically outperforms other general bioplastics in terms of heat-resistance, durability, and shrink-resistance, and performs on par with petroleum-derived plastics, with cost of parts included. Ecological Plastic is considered by TMC to be instrumental to cutting CO2 emissions and to using less petroleum resources over the lifecycle of a vehicle, from manufacturing through to disposal. This is because the plastic uses plants, which absorb CO2 from the atmosphere as they grow, as a raw material instead of petroleum-derived plastics. Furthermore, the benefits of an environmental technology like Ecological Plastic are increased when used in mass-produced products such as automobiles.

Total Ecological Plastic coverage approx. 80% of interior surface

Toyota has been working on applying Ecological Plastic to automobiles since 2000. In May 2003, TMC became the first in the world to use bioplastic made from polylactic acid in a mass-produced vehicle when it introduced the material in the spare-tire cover and floor mats of the Japan-market ‘Raum’ compact car. They achieved another world-first when it used its bioPET Ecological Plastic in the trunk lining of the Lexus CT 200h released in January 2011. bioplastics MAGAZINE reported about these developments. The Japanese car manufacturer continues its proactive push in the development of new technologies and practical applications to further expand the use of Ecological Plastic in vehicle parts. MT New Ecologial Plastic coverage

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Materials

New biobased plastic for technical applications By Masaya Ikuno Design for Environment Group Fuji Xerox CO. Kanagawa; Japan

Ratio of Plant-based content

High The new plastic

Alloy PLA plastics in the market The former plastic ABS plastic HB V-2 V-1 V-0 5V Flame retardance level (UL94)

Fig. 1: The new bio-based plastic’s position in the Japanese market of flame-retardant polylactic-acid-based plastics.

The former plastic The new plastic Ratio of plant-based content 5 4 3 2

Impact resistance

1 0

Flame retardance

Flexibility

Heat resistance

Fig. 2: Comparison of characteristics between Fuji Xerox’s new biomass plastic, the former biomass plastic, and conventional ABS plastic

bioplastics MAGAZINE [01/12] Vol. 7

As the issue of climate change was discussed as one of the main agendas in the G8 summit and in the United Nations Framework Convention on Climate Change, the subject is now attracting attention around the world. Under these circumstances, the Japanese government promotes the use of the renewable resource ‘biomass’ through the ‘Biotechnology Strategic Scheme’ and the ‘Biomass Nippon Strategy’ policies. This is because the government focuses on the ‘carbon neutrality’ of biomass to prevent climate change and also aims to reduce the use of fossil resources by using biomass as a renewable resource. In response to the above two policies, the size of the Japanese market for biobased plastic is expanding gradually, although the speed is still far slower than expected by the government. In 2007, to be more environmentally friendly, Fuji Xerox developed a plantbased plastic (hereinafter referred to as former plastic) that represented an alternative to petroleum-based flame-retardant acrylonitrile butadiene styrene (ABS). This plastic was introduced for movable sections inside multifunctional machines and printers. Parts made of the former plastic were the first to acquire the Japanese BiomassPla logo (BP logo see Fig. 3) for multifunctional machines and printers. A BP logo is a certification provided to plastic products with a plant-based content of more than 25 percent by weight by the Japan BioPlastics Association (JBPA) (see bM 02/02008). After that, this plant-based plastic has been progressively introduced for parts in new Fuji Xerox products. The former plastic, however, was a material with a biomass ratio (by weight) that is comparatively low for biobased materials because it consisted of a polymer alloy of polylactic-acid (PLA) and a ‘petroleumbased resin blend’. In recent years, to have customers use multifunctional machines and printers more safely, high flame retardancy (according to UL 94) has been required for some plastic parts. Flame retardancy of the former plastic was not high enough (rated V-2) to be introduced for such parts.

Conventional ABS plastic

Moldability

1. Introduction

Therefore, with a strong design concept to develop a high plant-content plastic without using rapidly depleting resources but by fully utilizing the experiences in developing the former plastic, Fuji Xerox succeeded in establishing the new formulation of biobased plastic that has a high plantbased content and high flame retardancy, and succeeded in introducing the plastic for use in movable sections inside multifunctional machines and printers.

2. Characteristics of the new plastic Fig. 1 shows the position of the new plastic in the Japanese market. The main characteristics of this plastic are a biobased content of approximately 60 % and flame retardancy rated V-1 (UL 94). Since the biobased content is comparably high, the new plastic was the first in the multifunctional machine and printer industry to acquire the BiomassPla 50 logo, which is provided to plastic products with a plant-based content of more than 50% by wt. by the JBPA.

Materials Fig. 2 shows the comparison between the characteristics of the new plastic with those of the former plastic and those of Fuji Xeroxâ&#x20AC;&#x2122;s conventional flame-retardant ABS plastic. Although the new plastic holds the advantage in terms of biobased content and flame retardancy, some of its properties are inferior to those of the former plastic and those of the conventional ABS plastic. Collaboration between the material development department and the engineering design department led to an improved material so that it can now be used for those movable sections in multifunctional machines and printers. Fig. 3 shows the Drum Cover, which is one of the parts for which the new plastic is being used. Since it is a movable section, the evaluation must reflect its actual usage. The static and dynamic loads applied to this movable section, which is opened and closed for cleaning or replacement of parts by customers or service engineers, were closely examined. For example, it was predicted how often the part will be opened and closed, and opening and closing tests for several hundreds of times were conducted. By repeating such tests reflecting the actual usage of each part, it could be confirmed that there are no issues in practical use and Fuji Xerox was confident to introduce the new biobased plastic to products.

Fig. 3: Drum cover of Fuji Xerox copy machine

3. Technology Summary of the New Plastic As is shown in Fig. 1, many of the PLA based materials in the market consist of polymer alloys of PLA and petroleum-based resins. This is because it is difficult to ensure flame retardancy and strength for plastics which only use plant-based resins (PLA) as its base constituent, compared to polymer alloys.

Actually, a material based on the combination of only PLA and flame retardants would result in a plastic material with insufficient properties and it would be impossible to be used in a multifunctional machine. To ensure the strength of the plastic, the additives to increase the adhesion between the base resin and additives (Fig. 4) were optimized, as well as the molecular weight and cross-linkage of the base resin to create a material that is highly resistant to impact (Fig. 5 and Fig. 6). By introducing this technology, eventually a plastic of high biobased content and high flame-retardancy was introduced for movable sections.

Additive

Before adding the new additive

After adding the new additive

Fig. 4: Comparison of adhesion of additives and base resin in plastic before and after adding the new additives

High

Flexibility Elongation at break %

Fuji Xerox overcame this issue by selecting effective phosphorous flame retardants and combining the flame retardants to achieve higher retardancy (rated V-1, UL 94) in the new plastic based on polylactic acid resin compared to that in the former plastic. To achieve high flame retardancy, it is necessary to include higher amounts of flame retardants, which generally have a negative impact on some of the properties of the plastic. Therefore, it was essential to develop a material that delivers high flame retardancy and still maintains the characteristics required for the plastic parts.

Additive

Fivetimes timeshigher higher Five

Low Before adding the new additives

After adding the new additives

Fig. 5: Comparison of flexibility before and after adding the new additives

bioplastics MAGAZINE [01/12] Vol. 7

Materials

Crack

Before adding the new additive

After adding the new additive

Fig. 6 Surface impact test The result after dropping a 500 g iron ball from a certain height

4. Mouldability of new plastic As is shown in Fig. 2, since the viscosity and thus the flow behaviour of the new plastic is improved compared to the former plastic and the conventional ABS plastic, it is possible to create thin plastic parts and reduce the weight of the parts. On the other hand, since polylactic acid resin is a crystalline resin, there are remaining issues such as demoulding and post-shrinkage after demoulding when compared to conventional materials. First successes in solving these issues were reached through collaboration with the manufacturing technology department so that the new plastic could be introduced to manufacture products.

5. Future efforts for new plastic The new plastic was introduced as the improved type of the former plastic to be used for parts inside machines. Research is on-going to further improve its flame retardancy and properties to introduce the plastic to outside parts where flame retardancy rating of 5V (UL 94) is required. Fuji Xerox is also aiming to increase the bio-based resin content in a product. Currently, work is on-going on the environmentallyfriendly design of plant-based plastic parts from the material design phase, the moulding phase, the engineering design phase, and to commercialization by communicating with the related departments. The target is to develop plant-based plastic that is equivalent to conventional plastic in terms of properties, cost, and mouldability through closer collaboration with related members inside and outside Fuji Xerox to expand the use of environmentally-friendly plastic. Fuji Xerox has evolved the new biobased plastic from the materials it developed in 2007 with technical assistance from FUJIFILM Corporation aiming to not use petroleum-based materials. UNITIKA LTD. has also been cooperating in developing the system for mass production. wwwfujixerox.co.jp

bioplastics MAGAZINE [01/12] Vol. 7

Applications

The biological bearing material

Plain bearing made of iglidur N54

olymer researcher and bearings specialist igus GmbH, Cologne, has developed a plain bearing material that is based on 54% renewable raw materials. About 90% of the material for the new ‘iglidur N54’ plain bearing consists of a partly biobased PA 6.10 which is made from 62% vegetable oil rather than finite crude oil. The company’s mechanically and tribologically optimised biological plastic is suitable for universal use in the low-load range: “Not only at K’2010 we observed a distinctive trend towards biopolymers“ said igus product manager René Achnitz, “so we asked ourselves how we could exploit the potential for the benefit of our customers?” igus thought that bioplastics could be an ideal solution to make environmentally friendly products such as the lubricant free plain bearings even ‘greener’. René Achnitz: “The new, lubricant-free ‘iglidur N54’” material joins our broad range of high-performance materials for general purpose, low-load applications and is a first serious step towards ‘green bearings’.” As well as general mechanical engineering applications, igus mainly sees possibilities in consumer goods markets, for example furniture or other items of daily use.

Ecological advantage of polymer bearings The new bio-bearing smoothly fits in with the company’s concept of developing environmentally friendly alternatives for more and more applications that currently work with

lubricated metallic plain and roller bearings. On the one hand, ‘iglidur’ bearings help to protect resources and the environment due to the incorporated solid lubricants. Polymer bearings from igus do not require any oil and grease, are lubricant- and maintenance-free, which means no contaminants are released to the environment. In addition, they have a low weight in comparison with metallic options, leading to lower masses and thus reduced energy consumption. Furthermore, the energy balance for the production of plastics is significantly better than for metals. Whereas the energy from 15 litres of crude oil is necessary to produce 1 litre of aluminium, and 1 litre of steel requires 11 litres of crude oil calculated on the same basis, the production of 1 litre of plastic only needs an average of 1.8 litres of crude oil. According to igus, this value is expected to fall even further on account of the major progress currently being made in the field of vegetable oil based polymers. MT www.igus.de

New ‘basics‘ book on bioplastics This new book, created and published by Polymedia Publisher, maker of bioplastics MAGAZINE will be available from early April 2012 in English and German language. The book is intended to offer a rapid and uncomplicated introduction into the subject of bioplastics, and is aimed at all interested readers, in particular those who have not yet had the opportunity to dig deeply into the subject, such as students, those just joining this industry, and lay readers. It gives an introduction to plastics and bioplastics, explains which renewable resources can be used to produce bioplastics, what types of bioplastic exist, and which ones are already on the market. Further aspects, such as market development, the agricultural land required, and waste disposal, are also examined. An extensive index allows the reader to find specific aspects quickly, and is complemented by a comprehensive literature list and a guide to sources of additional information on the Internet. The author Michael Thielen is editor and publisher bioplastics MAGAZINE. He is a qualified machinery design engineer with a degree in plastics technology from the RWTH University in Aachen. He has written several books on the subject of blowmoulding technology and disseminated his knowledge of plastics in numerous presentations, seminars, guest lectures and teaching assignments.

110 pages full color, paperback ISBN 978-3-9814981-1-0: Bioplastics ISBN 978-3-9814981-0-3: Biokunststoffe

Pre-order now for € 18.65 or US-$ 25.00 (+ VAT where applicable, plus shipping and handling, ask for details) order at www.bioplasticsmagazine.de/books, by phone +49 2161 6884463 or by e-mail books@bioplasticsmagazine.com

bioplastics MAGAZINE [01/12] Vol. 7

Foam A

CO2

Photosynthesis/ carbon fixation

Starch

Figure 2:

Propionic acid

(a) Synthesis of PHBV by bacterial fermentation process;

Harvest & processing

Photosynthesis/ carbon fixation

Threonine  2-ketobutyrate  isoleucine

Glucose Propionyl-CoA Fermentation

(b) Direct synthesis of PHBV in crop plants. Graphic according to Y. Poirier, Nature Biotechnology, Vol. 17, p. 960, 1999

PHBV

Harvest & processing

PHBV

Acetyl-CoA  Fatty acids

PHBV

Harvest & processing

PHBV foams and its By Alireza Javadi , Srikanth Pilla , Lih-Sheng Turng2,3, Shaoqin Gong1,2 1,2

Department of Biomedical Engineering, University of Wisconsin–Madison, WI, USA 1

Wisconsin Institute for Discovery, Madison, WI, USA

Department of Mechanical Engineering, University of Wisconsin–Madison, WI, USA 3

PHBV

3HB

3HV

Figure 2: Schematic chemical structure of Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV).

bioplastics MAGAZINE [01/12] Vol. 7

Introduction In the past few years, extensive research on biobased and biodegradable polymers has led to a better understanding of their properties and morphologies, as well as their structure–property relationship. Poly(hydroxyalkanoates) (PHAs), a family of linear polyesters produced in nature by bacterial fermentation of various renewable sources such as sugars, lipids, and alkanoic acids, are among the most promising biobased and biodegradable materials currently being investigated [1]. Among PHAs, poly(3-hydroxybutyrate) (PHB) and its copolymers Poly(3-hydroxybutyrate-co-3hydroxyvalerate) (PHBV) have attracted a lot of attention in the past two decades due to their unique properties. PHBV is either produced directly from plants or synthesized by microorganisms by consuming sugars in the presence of propionic acid (Figure 1) [2]. PHBV (Figure 2) is available commercially under various names including Tianan Biologic’s ENMAT Y1000P™, Biomer’s Biomer L™, and Metabolix’s Mirel™. In spite of improved mechanical (e.g., toughness) and thermal properties compared to PHB, PHBV still exhibits some disadvantages including low strain-at-break, narrow processing window, slow crystallization rate, and higher cost as compared to petroleum-based synthetic polymers [3]. In order to tailor its properties and decrease its total cost, several approaches have been proposed such as forming blends or composites with biodegradable polymers, natural fillers, or inorganic fillers. PHBV-based polymer blends and composites have been extensively studied in order to reduce their material cost, improve their processability, and engineer their

Foam

Figure 3: Representative scanning electron microscopy (SEM) image of the tensile fractured surface of a component processed by microcellular injection molding.

engineered composites mechanical (e.g., toughness) and thermal properties (e.g., degree of crystallinity) [4]. In order to fully utilize PHBV in diverse applications, improving its thermal and mechanical properties (such as brittleness and low strain-at-break) and employing economic processing techniques (such as microcellular injection molding [5]) is important.

Processing Similar to other thermoplastics, PHBV processing can also be done using conventional polymer processing equipment such as twin-screw extruder, injection-molding machine, etc. However, due to its sensitivity to thermal degradation, it is critical that lower processing temperatures are employed. Since this is practically difficult to implement with conventional processing equipment, a special fabrication technology has been implemented by the authors in all of their work on PHBV. This unique processing method, called microcellular processing technology, is an environmental-friendly polymer processing method capable of mass-producing components with minimally compromised material properties while consuming less energy and materials, as compared to components produced by the conventional processes [6]. The microcellular process uses a supercritical fluid (either CO2 or N2) which acts as a plasticizing agent thereby reducing the processing temperature of PHBV. Some of the most common types of microcellular processes available today are microcellular extrusion, injection molding, and blow molding. The microcellular process encompasses three major steps: gas dissolution, cell nucleation, and cell growth. Due to their unique properties, microcellular components (Figure 3) are particularly attractive for applications such as food packaging, automotive industry, sporting equipments, roof

sheet insulators, microelectronic circuit board insulators, electronic wire insulation, and molecular-grade filters [37].

Properties One of the major drawbacks of PHBV is its poor thermal stability [7]. This co-polyester, similar to other types of polyesters, undergoes thermal degradation and hydrolysis which can lead to a reduction in molecular weight at temperatures above 170Â°C. Several methods such as incorporation of supercritical fluids (discussed above) [8], natural fibers (including kenaf fiber [9], pineapple fiber [10], and bamboo fiber [11]), and inorganic nanofillers [7] (e.g. organically modified nanoclay) into the PHBV matrix have been shown to improve the thermal stability of PHBV. Another significant drawback of PHBV is its brittleness which can be attributed to: (1) low nucleation density and a slow crystallization rate which leads to the formation of large spherulites [12]; (2) a logarithmic increase in the degree of PHBV crystallinity during storage time when more amorphous regions integrate into the crystalline regions, which will result in physical aging and a significant reduction in the impact strength [13]; and (3) circular and radial cracks inside the large spherulites which can act as stress concentration spots and promote the brittleness of PHBV [14]. To improve the mechanical properties of PHBV, several approaches such as blending with tough polymers (including poly(propylene carbonate) (PPC) [4] and poly(butylene adipate-co-terephthalate) (PBAT)) [5], and organic/inorganic nanofillers [7, 15] (including hyperbranched polymers and nanoclay) have been utilized to improve the PHBVâ&#x20AC;&#x2122;s strainat-break and toughness [15].

bioplastics MAGAZINE [01/12] Vol. 7

Foam Applications

References

Owing to the fact that it has similar mechanical and thermal properties to polyolefins, PHBV is considered a promising alternative for fossil resource based polymers in the automotive, construction, agricultural, and packaging industries [16]. PHBV exhibits excellent barrier properties; thus, can be used in packaging and agricultural industries [17,18]. In the agricultural industry, PHBV is also used as a carrier for pesticides in order to achieve the controlled release of pesticides via PHBV biodegradation [18]. Additionally, due to its natural origin and microbial polymerization process, PHBV does not contain any catalytic residues, which makes it suitable for biomedical applications such as bone tissue engineering, cartilage tissue engineering, nerve guidance channels, intestinal patches, wound dressings, surgical sutures, and drug carrier systems [19].

1. K.G. Satyanarayana, G.G.C. Arizaga, F. Wypych, Progress in Polymer Science, Vol. 34, p. 982, 2009. 2. A. K. Mohanty, M. Misra, G. Hinrichsen, Macromolecular Materials and Engineering, Vol. 276, p. 1, 2000. 3. S. F. Wang, C. J. Song, G. X. Chen, T.Y. Guo, J. Liu, B.H. Zhang, S. Takeuchi, Polymer Degradation and Stability, Vol. 87, p. 69, 2005. 4. J. Li, M.F. Lai, J.J. Liu, Journal of Applied Polymer Science, Vol. 98, p. 1427, 2005. 5. A. Javadi, A. J. Kramschuster, S. Pilla, J. Lee, S. Gong, L. S.Turng, Polymer Engineering and Science, Vol. 50, p. 1440, 2010. 6. S. Gong, L.S. Turng, C. Park, L. Liao, â&#x20AC;&#x153;Microcellular Polymer Nanocomposites for Packaging and other Applications,â&#x20AC;? in: A. Mohanty, M. Misra, H.S. Nalwa, eds., Packaging Nanotechnology, American Scientific Publishers, pp.144, 2008. 7. M. Avella, E. Martuscelli, M. Raimo, Journal of Materials Science, Vol. 35, p. 523, 2000. 8. M.J. Jenkins, Y. Cao, L. Howell, G.A. Leeke, Polymer, Vol. 48, p. 6304, 2007. 9. M. Avella, G.B. Gaceva, A. Buzarovska, M.E. Errico, G. Gentile, Journal of Applied Polymer Science, Vol. 104, p. 3192, 2007. 10. S. Luo, A.N. Netravali, Polymer Composites, Vol. 20, p. 367, 1999. 11. S. Singh, A. K. Mohanty, T. Sugie, Y. Takai, H. Hamada, Composites: Part A, Vol. 39, p. 875, 2008. 12. G. J. M. Koning, P. J. Lemstra, Polymer, Vol. 34, p. 4089, 1993. 13. G. J. M. Koning, A. H. C. Scheeren, P. J. Lemstra, M. Peeters, H. Reynaers, Polymer Vol. 35, p. 4598, 1994. 14. J. K. Hobbs, T. J. McMaaster, M. J. Miles, P. J. Barham, Polymer, Vol. 37, p. 3241, 1996. 15. P. J. Barham, A. Keller, Journal of Polymer Science Part B: Polymer Physics, Vol. 24, p. 69, 1986. 16. L. Jiang, E. Morelius, J. Zhang, M. Wolcott, J. Holbery, Journal of Composite Materials, Vol. 42, p. 2629, 2008. 17. C.A. Lauzier, C.J. Monasterios, I. Saracovan, R.H. Marchessault, B.A. Ramsay, Tappi Journal, Vol. 76, p. 71, 1993. 18. P. A. Holmes, UK Patent Application, Great Britain, 2160208, 1985. 19. C.W. Pouton, S. Akhtar, Advanced Drug Delivery Review, Vol. 18, p. 133, 1996. 20. S. Singh, A.K. Mohanty, Composites Science and Technology, Vol. 67, p. 1753, 2007. 21. M. 26, G. Rota, E. Martuscelli, M. Raimo, P. Sadocco, G. Elegir, Journal of Materials Science, Vol. 35, p. 829, 2000. 22. N.M. Barkoula, S.K. Garkhail, T. Peijs, Industrial Crops and Products, Vol. 31, p. 34, 2010. 23. A.K. Bledzki, A. Jaszkiewicz, Composites Science and Technology, Vol. 70, p. 1687, 2010. 24. A. Javadi, Y. Srithep, S. Pilla, J. Lee, S. Gong, L. S. Turng, Materials Science and Engineering: C, Vol. 30, p. 749, 2010. 25. G.X. Chen, G.J. Hao, T.Y. Guo, M.D. Song, B.H. Zhang, Journal of Applied Polymer Science, Vol. 93, p. 655, 2004.

Several research groups have blended PHBV with other biodegradable polymers such as PPC (polypropylene carbonate) [4] and PBAT (polybutylene adipate terephthalate) [5] to modify its mechanical, biodegradation, and morphological properties and to broaden its applicability in various industries. Also, natural fibers such as wood fiber [20], bamboo fiber [11], wheat straw [21], flax [22], abaca [22], jute [23], and coir fiber [24], which are cheap, lightweight, and abundantly available, have been incorporated into the PHBV matrix to tailor its mechanical properties and reduce its weight and production cost. Moreover, inorganic nanofillers such as nanoclays have been incorporated into the PHBV matrix to modify the mechanical and thermal properties of PHBV [25]. With the continuous development of new PHBV-based blends and composites and new processing technologies, an even broader range of applications are anticipated for biobased and biodegradable PHBV.

bioplastics MAGAZINE [01/12] Vol. 7

Materials

TT Technical Research Centre, Espoo, Finland and Aalto University, Espoo/Helsinki, Finlandm have developed a method which for the first time enables manufacturing of a wood-based and plastic-like material in large scale. The method enables industrial scale roll-to-roll production of nanofibrillated cellulose film, which is suitable for e.g. food packaging to protect products from spoilage. Nanofibrillated cellulose typically binds high amounts of water and forms gels with only a few per cent dry matter content. This characteristic has been a bottleneck for industrial-scale manufacture. In most cases, fibril cellulose films are manufactured through pressurised filtering but the gel-like nature of the material makes this route difficult. In addition, the wires and membranes used for filtering may leave a so-called ‘mark’ on the film which has a negative impact on the evenness of the surface.

www.vtt.fi

Transparent plastic-like packing material from birch fibril pulp magnetic_148,5x105.ai 175.00 lpi 45.00° 15.00° 14.03.2009 75.00° 0.00° 14.03.2009 10:13:31 10:13:31 Prozess CyanProzess MagentaProzess GelbProzess Schwarz

c i t e n tics g s a a l P M for

According to the method developed by VTT and Aalto University nanofibrillated cellulose films are manufactured by evenly coating fibril cellulose on plastic films so that the spreading and adhesion on the surface of the plastic can be controlled. The films are dried in a controlled manner by using a range of existing techniques. Thanks to the management of spreading, adhesion and drying, the films do not shrink and are completely even. The more fibrillated cellulose material is used, the more transparent films can be manufactured. Several metres of fibril cellulose film have been manufactured with VTT’s pilot-scale device in Espoo. All the phases in the method can be transferred to industrial production processes. The films can be manufactured using devices that already exist in the industry, without the need for any major additional investment. VTT and Aalto University are applying for a patent for the production technology of NFC film. Trial runs and the related development work are performed at VTT.

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The invention was implemented in the Naseva – Tailoring of Nanocellulose Structures for Industrial Applications project by the Finnish Funding Agency for Technology and Innovation (Tekes) that is included in the Finnish Centre for Nanocellulosic Technologies project entity formed by UPM, VTT and Aalto University. Nanofibrillated cellulose grade used was UPM Fibrilcellulose supplied by UPM.

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bioplastics MAGAZINE [01/12] Vol. 7

Show Preview

PE’2012 will take place April 1-5, 2012 at the Orange County Convention Center in Orlando, USA, after 40 years in Chicago. The improved economies and logistics of this new venue have encouraged many NPE’2012 exhibitors to bring more machinery to the show, much of it to be operated on-site, according to John Effmann of ENTEK Manufacturing Inc, who is chairman of NPE’2012. But not only machinery will be presented in Orlando. Besides conventional plastics NPE will again be a showcase and technology exchange for polymers derived from corn, castor beans, soybeans, potatoes, tapioca, and other natural resources. Again bioplastics will be one of the most interesting topics in this year‘s NPE‘2012, The International Plastics Showcase organized by SPI (The Society of the Plastics Industry).

bioplastics MAGAZINE will not only be an exhibitor (please come and see us at booth 58047, South & North Halls) but will also offer a comprehensive show preview below (including a floor plan as a centerfold in this issue) and a show review in issue 03/2012. On our website you will find more bioplastics related info about NPE as we approach the show …

Teknor Apex The Bioplastics Division of Teknor Apex will be highlighting the following new products:

Resirene The BIORENE® family of Resirene are hybrid resins of PS or PP and thermoplastic starch, and they represent a biobased alternative to traditional plastics. The PS-Starch blend, Biorene HA-40 is ‘OK Biobased’ certified and be used to produce a wide range of everyday products, such as disposables, pen barrels, cutlery and the like. BIORENE resins deliver a competitive performance versus traditional plastics and can be processed in the same machinery as ordinary plastics. Another benefit is that Biorene uses lower processing temperatures, up to 50°F, thus enhancing productivity and saving energy costs. The benefits using Biorene: Easy to process Competitive performance OK-Biobased certified (editor’s note:) However, Biorene products should not be marketed as biodegradable, as they content non biodegradable PS or PP

www.resirene.com 63027 South & North Halls

High-impact, high-heat PLA: Enhanced PLA compounds overcome the inverse relationship between heat distortion temperature (HDT) and Izod impact strength that is typical in standard PLA. Injection molding grades provide up to two times the HDT and up to six times the Izod impact strength of standard PLA resins. Extrusion/thermoforming grades exhibit up to two times the HDT and more than four times the Izod impact strength. Compostable compound for blown film: A blend of thermoplastic starch (TPS) and biodegradable copolyester (PBAT) degrades more rapidly than the copolyester alone, broadening application possibilities for film products intended for composting. Additives for PLA: A series of pellet masterbatches with PLA carrier resins enhance the processing and enduse performance of PLA. The additives include products for increasing impact strength, enhancing melt strength, and serving as a release agent in molding and extrusion.

bioplastics MAGAZINE [01/12] Vol. 7

www.teknorapex.com 58038 South & North Halls

Show Preview IDES

RTP Company

The IDES Prospector Plastics Search Engine includes 84463 plastic material datasheets from 864 global resin manufacturers. At NPE 2012 IDES will be highlighting the bioplastics search functionality in their Prospector Plastics Database. The number of bioplastics listed in the system has grown tremendously and there are now nearly 2500 grades that are biodegradable, include recycled content or are derived from renewable resources. Additionally, several bioplastics within the database are available for medical and healthcare applications.

Global custom engineered thermoplastics compounder RTP Company has received ‘USDA Certified Biobased Product’ labels for two of its PLA-based bioplastic specialty compounds through the USDA‘s BioPreferred™ Voluntary Labeling Initiative. Following the program‘s requirements, RTP Company‘s compounds were thirdparty tested in accordance with ASTM D6866 procedures and renewable biobased carbon content is reported as a percent of total carbon content.

www.ides.com 34020 South & North Halls

RTP 2099 X 121249 C Natural, is a 30% glass fiber reinforced PLA grade. Because the glass fiber component of this compound does not contain any carbon, this product has been certified to have a biobased carbon content of 99%. With tensile strength and flexural modulus properties exceeding those of 30% glass fiber reinforced polypropylene (PP) and comparable to 30% glass fiber reinforced polybutylene terephthalate (PBT). RTP 2099 X 126213 Natural, is a polylactic acid/ polycarbonate (PLA/PC) alloy with a biobased carbon content of 26%. With shrinkage, impact, and heat distortion temperature similar to many PC/ABS alloys www.rtpcompany.com 39027 South & North Halls

Photo courtesy of Brooks Sports Inc.

Merquinsa Merquinsa presents several commercial applications from large global brands applying Bio TPU from renewable sources (bio content from 20% up to 90% according to ASTM D6866). One example is Ford Motor Company’s use of renewable-sourced materials which prompted the selection of Pearlthane® ECO for the Lincoln MKZ tambour console door. Other sports, footwear, automotive & industrial companies have adopted and turned to Bio TPU since then: Bio TPU is now a commercial reality globally. Merquinsa’s Bio TPU is used for example by Brooks Sports in running goods. The Bio TPU product portfolio includes UV-stabilized grades in a wide range of hardnesses for molding and extrusion applications: In addition, Bio TPU allows part weight reduction up to 7%. From 80 Shore A up to 95 Shore A hardness, Bio TPU offers lower density, and thus, is a lower cost solution. See data below on standard petroleum-based Pearlthane vs. Renewable-sourced Pearlthane ECO TPU grades: Merquinsa was recently acquired by The Lubrizol Corporation. The Merquinsa products will be integrated into Lubrizol’s Engineered Polymers business.

Leistritz Wide ranging twin screw extrusion technologies will be displayed at the Leistritz NPE 2012 exhibit. A partial list of what will be exhibited includes: A ZSE-50 MAXX twin screw extruder configured for both reactive and direct extrusion. The model as exhibited is particularly suited for the processing of biopolymers The ZSE-40 MAXX on display will be equipped with a new swing-gate strand die assembly. The co-rotating twin screw extruder is ideal for masterbatch and custom compounding production. The swing gate frontend assembly is ideal for processing shear sensitive bioplastics. In a special Lab-scale twin screw extruder display area Leistritz will display a nano-16 twin screw extruder system (particularly beneficial for processing biopolymer compounds in the early stages of development when material availability is limited to 100 grams or less), a ZSE-18 twin screw extruder: and a Micro-27 modular, multi-mode twin screw extruder. The co-/counterrotating feature of the Micro 27 facilitates wide ranging development efforts for biopolymer compounds.

www.leistritz –extrusion.com 5975 West Hall

www.merquinsa.com 35004 South & North Halls

bioplastics MAGAZINE [01/12] Vol. 7

Show Guide North & Shouth Halls

Austin Novel Materials, North America

52059 27

Entrance

24000

bioplastics MAGAZINE

58047 33

Biopolymers & Biocomposites Research Team

62044 42

Braskem

59042 38

Braskem

22006 44

Chase Plastic Services, Inc.

37027 19

Chemtrusion, Inc.

30015 11

DuPont

35013 16

DuPont

57046 33

Eastman Chemical Co.

39013 23

Ecospan, LLC

58044 36

EMS

35021 17

Evonik Degussa Corporation

34023 15

Evonik Degussa Corporation

55020 29

Ex-Tech Plastics

33027 13

Extrusa

59048 37

FKuR Kunststoff GmbH

57042 32

FKuR Plastics Corporation

57042 32

Hallink RSB Inc.

19013

Heritage Plastics Inc.

19004

IDES

34020 14

Jamplast, Inc.

26033

Jarden Plastic Solutions

57009 31

Kal-Trading

36009 18

Kingfa Sci. & Tech. Co., Ltd

19008

Kureha America Inc.

21013

LTL Color Compounders, Inc.

50020 25

Mathelin Bay Associates LLC

61000 40

Merquinsa North America, Inc.

29022 10

Minima Technology Co., Ltd.

53048 28

Nanobiomatters Industries, S.L.

50046 26

NatureWorks LLC

57048 33

Nexeo Solutions

61002 41

Phoenix Plastics L.P.

38008 20

PolyOne Corporation

15030

PolyOne Corporation

39006 22

Polyvel, Inc.

31022 12

Purac

54048 28

Resirene, S.A. de. C.V.

63027 43

Rhe Tech Inc

60044 39

RTP Company

39027 24

SPI Bioplastics Council

60047 37

Teinnovations Inc. (PSM Bioplastic)

19027

Teknor Apex Company

58038 35

West Hall

TP Composites, Inc.

38023 21

Gneuss, Inc.

6685

Tradepro, Inc.

13013

IndiaMART.com

1386

Leistritz

5975

Recycling Solutions

3687

South Hall

55039 30

Zhejiang Hangzhou Xinfu Pharmaceutical Co., Ltd 60042 38

bioplastics

North Hall

United Soybean Board

South Hall

BASF

MAGAZINE

NPE /SPI

Food Court Recycling Center

Not in the North & South Halls, but still active in bioplastics:

Shaping the future of biobased plastics

On this floor plan you find the majority of companies offering bioplastics related products or services, such as resins, compounds, additives, semi-finished products and much more. For your convenience, you can take the centerfold out of the magazine and use it as your personal â&#x20AC;&#x2DC;Show-Guideâ&#x20AC;&#x2122; .

www.purac.com/bioplastics

North Hall

South Hall

Entrance

(Source: www.npr.org)

2nd PLA World

C o n g r e s s

15 + 16 MAY 2012 * Munich * Germany

Show Preview

Purac New applications, new markets and improved product performance have always been the focus of Purac’s continuous innovation efforts and partnerships. At the NPE 2012 Purac will present solutions for the heat-resistant PLA. High purity PLLA and PDLA are now commercially available. The technology offers the unique possibility to increase the heat-stability of PLA to reach 80 - 150 °C. D-Lactide can be used to develop a range of heat-resistant PLA products for plastics, films, fibers and foam applications. To learn more about this technology meet Purac team at the booth in the “What’s hot in the Plastics Technology” zone.

PSM Bioplastic (Teinnovations)

www.purac.com 54048 South & North Halls

PSM Bioplastic, gives manufactures the flexibility to achieve a wide variety of environmental goals. PSM biodegradable resins (HL-300 series) are specially designed to be run as a standalone material where endof-life disposal is the primary consideration. These resins can be used to produce parts that are 100% compostable by ASTM standards (e.g. D6400, D5338). PSM bio-based resins (HL-100 series) increase the bio content of products traditionally made entirely of petroleum based plastic, while still remaining extremely cost competitive. Blending a high percentage of PSM with a small amount of conventional plastic, yields excellent results. But using even just a small amount of PSM Biobased material will add an ecologically friendly aspect to just about any product, and has very little impact on part cost, performance, and production. (editor’s note:) However, the material will not be biodegradable. All PSM materials have a very high temperature tolerance for demanding injection molding, thermoforming, and flexible film applications.

www.psmna.com 19027 South & North Halls

bioplastics MAGAZINE [01/12] Vol. 7

SPI Bioplastics Council The SPI Bioplastics Council is the leading North American bioplastics group focused on the development of bioplastics as an integral part of the plastics industry. At NPE’2012 the SPI Bioplastics Council will be hosting the ‘Business of Bioplastics’ educational program on Tuesday, April 3 as part of SPI’s Business of Plastics Conference. The session, focused on the state of the industry, will include leaders from the bioplastics industry and U.S. government as well as a highly interactive panel discussion. In addition, representatives from the SPI Bioplastics Council will be in the booth to talk about the Council’s activities and its 2012 focus on education, awareness, communication and policy/government issues that are impacting the industry.

www.bioplasticscouncil.org. 60047 South & North Halls

Show Preview LTL Color Compounders

Biopolymers and Biocomposites Research Team The Biopolymers and Biocomposites Research Team (BBRT) at Iowa State University will introduce new biorenewable plant containers developed for the specialty crop industry. The containers are a sustainable replacement for petroleum-based containers and degrade harmlessly when planted in a garden. This research was recently awarded a $1.9 million grant from USDA’s National Institute of Food and Agriculture. BBRT will also display other biobased materials including carbon fibers, self-healing biorenewable polymers, biobased coatings and plastics; and composites made from natural oils, fibers, and agricultural coproducts. BBRT promotes research and development of new formulations and processes for biorenewable polymers and composites. BBRT focuses on renewable oils polymerization, protein-based plastics processing, protein-based adhesives, and cellulosic-based composites. The team has a broad range of knowledge including polymer chemistry, characterization, and processing.

www.biocom.iastate.edu 62044 South & North Halls

Gneuss Gneuss is a specialist for filtration, processing and measurement technology. The patented Gneuss Rotary Filtration Systems enable fully automatic, process and pressure constant filtration. Gneuss Melt Pressure and Temperature Sensors are characterized by their extremely high precision, combined with a high degree of robustness. Both, Gneuss filtration and measurement technology have been applied for bioplastics such as PLA since several years. The patented MRS Multi Rotation System offers completely new possibilities with regard to the efficient degassing and extrusion of polymer melts and has been tested with PLA as well.

LTL Color Compounders is a custom color compounder of engineered thermoplastic resins including biopolymers. Standard product lines include ColorFast®, ColorRx® medical and non-biocompatible grade resins, Surlyn Reflection Series® thermoplastic alloy, and EcoFast recycled compounds. Some markets served are electronics, lawn & garden, medical, personal recreational vehicles, automotive, optical, sports, and agricultural. LTL offers live customer service, no minimum orders, short lead times, and toll compounding. Labs are staffed with experienced color matchers and lab technicians, and lab extrusion equipment is available for customer trials. The company is ISO9001:2008 and ISO13485:2003 certified. Dongguan LTL Color Compounders in China is ISO9001:2008 certified and their operation mirrors LTL’s US operation. In 2010 LTL celebrated its 20th anniversary, and they have many years of experience manufacturing a multitude of resins and color matching to their customers’ requirements. LTL‘s R&D department is continually developing new products, many of which are UL listed.

www.ltlcolor-com 50020 South & North Halls

NatureWorks NatureWorks, the world’s leading supplier and innovator of biopolymers, plastics made from plants, not oil, is displaying a host of extruded, thermoformed, injection molded, and spun bond and melt blow films, fibers, durable, and semi-durable products. Finished goods include everything from baby wipes to iPhone covers and food-service cutlery to deli containers. Since 2003, NatureWorks has been producing world scale commercial quantities of Ingeo™ biopolymer and working with the supply chain to develop best practices for conversion of these new grades of resin into the broadest possible range of products. The NatureWorks technical sales team will be on hand to answer questions from engineers, designers, product managers, and plant personnel about the latest in resin grades and developments in converting. There will also be information about the second Ingeo production facility scheduled to come online in 2015, feedstock diversity, and production volume increases. Visitors can compare the price stability aspects of Ingeo with petroleum-based polymers.

www.natureworksllc.com 57048 South & North Halls

www.gneuss.com 6685, West Hall

bioplastics MAGAZINE [01/12] Vol. 7

Show Preview FKuR Bioplastics specialist FKuR Plastics Corp. will be presenting a broad variety of biodegradable, biobased and natural fiber reinforced compounds. “During the last few months we have concentrated our development work on new formulations for injection molding and film applications“, says Patrick Zimmermann, Director Marketing & Sales at FKuR. ”These intelligent and tailor made compounds made from renewable resources enable our customers to capture new applications and markets“, explains Mr. Zimmermann. Besides the already well-established product lines Bio-Flex® and Biograde® FKuR will present new tailor-made green polyethylene compounds under the brand name Terralene™, based on Braskems’ Green PE.

www.fkur.com 57042 South & North Halls

United Soybean Board Minima Technology Minima Technology has expertise in biodegradable and 100% compostable polymer applications with innovative compounding techniques and International certifications. Minima Technology has built its research and development center to include a broad range of mechanical options which give prospective clients flexibility when discussing environmental options. A family of likeminded companies in different fields of processing expertise assist Minima Technology with manufacture is required. The options available include: Extrusion, Printing, Resin Compounding, Conversion, Physical/Chemical foaming, Thermoforming, Blow Molding, Injection Molding. The core philosophy of the company is to find a relatively simple way of ‘Love Earth Directly’ as ‘along nature by nature’ is the best way, by means of biodegradable plastic to replace and minimize conventional Petrol-plastic to be continually impacting onto earth environment. The registered readers of bioplastics MAGAZINE get this issue in an envelope sponsored by Minima Technology and made from one of their film blowing grades.

www.minima-tech.com 53048 South & North Halls

bioplastics MAGAZINE [01/12] Vol. 7

Kansas State University Installs Soy-Based Turf on Athletic Facilities. The University installed about five acres of AstroTurf® GameDay Grass™, which features BioCel® technology, a soy-based polyurethane backing. From professional-level to high-school sports, hundreds of teams in 42 states across America compete on more than 365 hectares (900 acres) of soy-backed AstroTurf. Soy-Based Composites Used in Waterless Urinals. Soy represents a versatile feedstock for any company looking to replace petrochemicals with environmentally friendly alternatives. Waterless Company represents an example, using soy-based products in their urinal products. Waterless offers urinals with up to 35% Envirez®, a soybased resin from Ashland Chemical. Soy-Based Polyols Offer Green Gasket Options to Auto Industry. Soy continues to grow in its role in the automotive industry, with soy-based gaskets, in addition to soy foam in seats, soy plastics in body parts and other uses. The auto industry continues to look to soy-based products to provide sustainable products that meet or exceed the requirements and performance of petrochemical products.

www.soynewuses.org 55039 South & North Halls

NPE2012, the worldâ&#x20AC;&#x2122;s largest plastics conference, exposition and technology exchange, blasts into Orlando, Florida USA this April to reshape the future of our industry! Showcasing more than 2,000 exhibitors, NPE is the only global event that allows you to: See large-scale, running machines in action Explore more than 2 million square feet of solutions for every segment of the plastics industry supply chain Discover new and emerging technologies among hundreds of on-site demos every day Meet 75,000 plastics professionals from more than 120 countries Access hundreds of timely programs, from business development to the latest technical advances Connect with the entire lifecycle of the plastics industry And much, much more!

Co-located at NPE2012:

Application News

Biocomposite canoe An all natural composite canoe designed and manufactured in the UK using flax fibre and a linseed oil based resin was be showcased at the recent Composites Europe trade show. The canoe has been built by Flaxland and is made from a flax fabric (Biotex Flax 4x4 Hopsack) supplied by Composites Evolution, Bridge Way, UK, and a UV cured bioresin (EcoComp UV-L) supplied by Sustainable Composites, Redruth, UK. It is constructed using a marine plywood and European pine frame that is covered using the Biotex flax material and then impregnated with the linseed based resin. Simon Cooper, owner of Flaxland, is a traditional boat builder with a strong interest in using all natural materials. “I became interested in the use of Flax as a sustainable crop for the production of oil and fibre to make a boat. I wanted to find new, novel, but natural materials, and in my search found the Biotex website” he explained. Flaxland trialled many flax fabrics and found that Biotex suited the needs of the project best. Owner, Simon Cooper felt that Biotex had good impregnation, wet out and very good tear strength which was equal to the synthetic materials allowing for a flexible yet strong canoe which could be been made without the use of a mould tool. Flaxland have made a total of seven prototypes so far, using both the Biotex Flax 4x4 Hopsack and Biotex 3H Satin weaves. The Hopsack version offers a resilient and durable canoe which has a net weight of just less than 12 kg and the Satin version gives a lighter weight option, at just 8 kg, for racing. The canoe is currently undergoing long term durability and water resistance tests and, according to Simon, has shown good results for over one year already. He is now looking to roll out the design to larger rowing boats. www.compositesevolution.com www.flaxland.co.uk www.suscomp.com

bioplastics MAGAZINE [01/12] Vol. 7

Designer headphones with PLA Advertised as the World’s first recyclable designer over-ear headphones the Noisezero 0+ Eco edition headphones were recently introduced. The headphones were developed by British-born and Hong Kong based Designer Michael Young, in collaboration with music technology brand EOps (New York and Hong Kong) and marketed through the Paris/France based online store Colette. The Noisezero 0+ Eco edition are made from stainless steel, aluminium and PLA, all of which are recyclable. The headphones feature 50mm titaniumcoated HD drivers with a neodymium iron-boron magnet for a great sound without unwanted vibration. The PLA ear chambers and sheep leather ear pads improve the sound quality and give a unique feeling of comfort. The headphones are compatible with iPhone, iPad and iPod and come with a microphone and a three-button remote module to control playback and volume. “The majority of all hard plastic parts including the earcup chamber, the mic housing, the cable plug are made of PLA,” as Michael Young told bioplastics MAGAZINE. And asked for his motivation to use this material he added that PLA is “eco friendly as it‘s made from renewable resources, it’s recyclable and its biodegradeable compared to traditional plastics like ABS that is not eco friendly.” Concerning his future plans, Michael Young said that he would like to try to use bio plastics as much as he can, but it is a little limited. Michael: “If we accept changes it is fine, for example, colors are harder to control, but that is ok — it‘s just a change. Production access can also be limited but more manufacturers are prepared to spend time with the process to make it work.” So Michael Young is absolutely willing to proceed onwards. MT www.michael-young.com www.eopstech.com www.colette.fr

Application News

New Cellulose Acetate for frames Mazzucchelli 1849, Castiglione Olona, Italy is a worldwide leader in the production and distribution of the plastic material traditionally used for the production of optical frames: Cellulose Acetate (CA). Mazzucchelli is the most important consumer of this polymer derived from Cellulose, derived from renewable sources widely present in nature. The process covers the treatment of two types of fibres: fibres from seeds (cotton) and fibres from wood (conifers and broadleaves). The company today is the most important manufacturer of Cellulose Acetate granules used in optical market and other industrial areas. Now Mazzucchelli introduced a new eco-friendly product: M49®, a new CA-material, for which an application of an International Patent has been filed. The new material is especially suited for the production of spectacle frames

M49 is phthalate-free and is therefore compatible with other polymers, such as the polycarbonate or polymethylmetacrylate. Such plasticizers tend to migrate from CA into PC or PMMA resin of the glasses, making them hazy over time.

Standard Acetate frame with Polycarbonate lenses, after the accelerated aging process

M49 Acetate frame with Polycsrbonate lenses, after the accelerated aging process

Biobiojoux Designer Lili Giacobino has launched her own business making jewellery out of kitchen cupboard staples such as flour, tapioca and chocolate. The 31year old entrepreneur turns the everyday items in our homes into individual, biodegradable and eco-friendly beauty accessories. From her tiny kitchen in Surbiton, UK, the Kingston University graduate creates eye catching earrings, bracelets and necklaces using food ingredients that are completely natural and skin friendly. Lili said: “I spent hours slaving over a hot stove – not to make tasty food but to create fantastic jewellery. People don’t believe me when I say I make earrings from potato flour – but I do. “I’m using ingredients that our mothers and grandmothers were familiar with. The jewellery is made from such simple ingredients that the end products are harmless to eat, good for your skin and look great when you wear them.” Lili’s creations are already proving popular among fashion conscious south Londoners thanks to her stall at the Greenwich Market on Fridays. One of Lili’s favourite ingredients is bio-glycerine which has been used for centuries in thousands of common items such as soap, desserts and cough mixture. Lili’s bio formula creates a bendy raw material which is also known under the expression ‘bioplastic’ which takes a week to set before it can be crafted into a piece of jewellery. Exsocial worker Lili is originally from Switzerland and moved to the UK in 2008 to study product and furniture design at Kingston University – MT www.lili-design.com

The new material M49 has undergone exhaustive tests at specialized laboratories (OWS) and has been declared 100% biodegradable according to EN/ISO 14855. But M49 is also recyclable and can be re-worked with different technologies giving life to many other products. The natural derivation of M49 can also be ‘touched’ with a pleasant effect of ‘warm and silky’, which allows the user with a sense of luxury which can only come out from natural substances. The material can be manufactured with all Mazzucchelli technologies, and the working processes are the same as the traditional acetate sheet. It can be used in all the markets of fashion accessories, from frames to costume jewellery and design items. As far as the spectacle frames are concerned, M49 is compatible with all types of lenses. – MT www.m49.it

bioplastics MAGAZINE [01/12] Vol. 7

Report

biocore – a biorefinery

The FP7 European project BIOCORE (BIOCOmmodity REfinery), managed by INRA (French National Institute for Agricultural Research), has been built to conceive and analyze the industrial feasibility of a biorefinery concept that will allow the conversion of cereal by-products (straws etc), forestry products and short rotation woody crops into 2nd generation energy, chemical intermediates, polymers and materials. The first challenge for Biocore is to demonstrate the feasibility of an advanced biorefinery operation that uses diverse biomass feedstocks. To achieve this, activities in Biocore are focusing on important areas, such as feedstock supply, using a case study approach, which accounts for variations in biomass type and annual availability, and transport logistics. Case studies are currently underway in several European regions and in India. From a technical point of view, Biocore is developing and optimizing a series of technologies to perform the different stages of lignocellulosic biomass refining and to extract maximum value and products from available resource.

By Michael O’Donohue, Coordinator of Biocore

Regarding the initial extraction of the biomass components: cellulose hemicellulose and lignin, Biocore is using patented technology developed by CIMV S.A., Levallois Perret, France, a specialist in lignocellulosic biomass fractionation, which supplies the three components as separate, refined platform intermediates. To further transform these into useful products Biocore partners are focusing on a variety of chemical, thermochemical and biotechnological processes that will lead to the production of a wide range of products including 2nd generation fuels and other chemicals that can be used to make polymers (bio-PVC, bio-polyolefins, polyurethane, polyesters etc), detergents, food ingredients and wood panels. Beyond the development of individual processes and technologies, Biocore is also in the business of demonstrating the feasibility of value chains. Focusing on a certain number of mature technology that form part of the Biocore portfolio, pilot scale testing is being used to further establish industrial feasibility in conditions that are close to the market. Additionally, process engineering is being used to model the whole Biocore biorefinery process and to scope for process optimization, notably through unit operation integration, the reduction of energy consumption and the reduction and/or recycling of waste streams. Finally, beyond the performance of unit operations and manufacturing efficiency, tomorrow’s biorefineries will have to conform to all of the criteria of sustainability, which take into account environmental, economic and sociopolitical impacts.

Final products 2nd generation fuels

and

Ethanol

Aurelie Faure, European Project Manager, INRA Transfert, Paris, France

Resins/Adhesives Cereal byproducts

Forestry waste

SRC wood

bioplastics MAGAZINE [01/12] Vol. 7

Hemicellulose

Food additives

Cellulose

Detergents

Lignin

Wood panels Ethanol

Packaging

Chemistry Biotechnology

Building

Intermediates

Adhesives and paints

Fractionation

Materials

Thermoplastics PVC, polyolefins, polyurethanes, polyesters

Varied biomass

Application sectors

Energy

oday, concerns linked to climate change and modern society’s excessive dependency on fossil resources are providing the necessary impetus for the transition towards a new economy that will use biomass as its primary source of carbon and energy. In this respect, biomass (plant and animal-derived resources alike) is completely unique, because it is the only naturally renewable energy source that can also supply carbon for the production of the chemicals and products that are vital for our daily life.

Report

concept

Residues of rice straw in the Punjab region (photo: courtesy Michael Carus)

Therefore, Biocore researchers are analyzing the whole of the biorefinery process, from the production of the feedstock through to the ultimate use of the biorefinery products, using a variety of assessment methods in order to ensure that a comprehensive appraisal of the benefits of the Biocore concept will be available at the end of the project.

Bioproducts and bioplastics In Biocore, white biotechnology and chemical technologies are major workhorses that form the basis of sophisticated integrated processes that will manufacture products for various market sectors. In particular, Biocore focuses on the production of key chemicals such as organic acids, aromatics and olefins. Those compounds are major building blocks for many commonly used thermoplastics (e.g. polyolefins, polyurethanes, PVC, etc.) which together represent 70% of the global plastic market. Additionally, Biocore will provide pipelines for 2nd generation biofuels, adhesives, resins and feed ingredients.

PU PVC

Other PS

PET

70%

PE (HD and LD)

PE: polyethylene (high and low density) PP: polypropylene PU: polyurethane

PVC: polyvinylchloride PET: poly(ethylene terephthalate) PS: polystyrene

The EU plastics resin market: Biocore activities focus on four of the â&#x20AC;&#x2DC;big fiveâ&#x20AC;&#x2122; polymers (PVC, PET, PE and PP) that make up the EU plastics resins market. Together with polyurethane (PU) these represent 70% of this market.

EREMA will present more details on their PLA activities at the

2nd PLA World Congress 15 + 16 MAY 2012 * Munich * Germany

Contact marketing@erema.at, to get a 15% discount on the conference fee. organized by bM

Bio meets plastics. The specialists in plastic recycling systems. An outstanding technology for recycling both bioplastics and conventional polymers

bioplastics MAGAZINE [01/12] Vol. 7

Report N° Organisation name

Short name Country

Organisation type

Institut National de la Recherche Agronomique

INRA

France

Res

Valtion teknillinen tutkimuskeskus

VTT

Finland

Res

Energy research Centre of the Netherlands

ECN

The Netherlands Res

Compagnie Industrielle de la Matière Végétale

CIMV

France

SME

Chimar Hellas AE

Chimar

Greece

SME/end-user

Arkema SA

Arkema

France

MNI/end-user

National Technical University of Athens

NTUA

Greece

Institute for Energy and Environmental Research Heidelberg

IFEU

Germany

Res

Katholieke Universiteit Leuven

KULeuven

Belgium

10 Syral SAS

Syral

France

MNI/end-user

11 SYNPO, akciová společnost

Synpo

Czech Republic

Res

12 Stichting Dienst Landbouwkundig Onderzoek

DLO

The Netherlands Res

13 Chalmers Tekniska Hoegskola AB

Chalmers

Sweden

14 Latvian State Institute of Wood Chemistry

IWC

Latvia

Res

15 INRA Transfert

France

Other

16 The Energy and Resources Institute

TERI

India

Res

17 CAPAX environmental services

CAPAX

Belgium

SME

18 nova-Institut GmbH

NOVA

Germany

SME

19 Institut für Umweltstudien - Weibel & Ness GmbH

IUS

Germany

SME

20 Imperial College London

Imperial

United Kingdom

21 Solagro Association

SOLAGRO

France

NGO

22 Szent Istvan University

SZIE

Hungary

23 Tarkett SA

Tarkett

Luxemburg

MNI/end-user

24 DSM Bio-based Products & Services B.V.

DBPS

The Netherlands MNI/end-user

Regarding olefins, Biocore develops a portfolio of original processes and engineered microor-ganisms that produce ethylene, a polyethylene precursor and isopropanol, a precursor of propylene, which is the building block of polypropylene. Moreover, using pilot scale equipment and smart integration pathways for both biotechnological and chemical pro¬cesses, Biocore will demonstrate a cellulose to bio-PVC value chain.

Development of Lignin-based Polymers When applied to wheat straw, the CIMV organosolv process provides a lignin fraction that is composed of linear polymers. Coherent with Biocore’s ambition to develop new ligninbased polymers, researchers from Synpo, Czech Republic, have developed a solvent-free method for the preparation of a polyurethane formulation. The integration of CIMV biolignin into a conventional PU formulation has provided elastomers with enhanced mechanical product properties, in particular increased tensile strength and toughness, with surface hardness being significantly increased. Synpo’s novel formulation, particularly appropriate for the manufacture of flooring materials and electrical appliances, constitutes one of Biocore’s first commercially-promising inventions.

New bio-based PVC PVC is manufactured using ethylene, thus logically this well-known polymer can be produced partly from biomass. In Biocore, a combined research effort involving several partners is focused on the development of PVC from 2nd generation ethanol. In this process, ethanol is first dehydrated to afford ethylene, then the ethylene is converted into vinyl chloride monomers, which are finally polymerized to obtain PVC. The aim of work in Biocore is to first determine how the use of 2nd

bioplastics MAGAZINE [01/12] Vol. 7

The Team 15 Research organizations, 8 companies, 1 NGO

generation ethanol can influence the quality of the ethylene obtained, and also to establish the economic sustainability of the whole process, within the framework of a multiproduct refining scheme. In a further effort to make ‘greener’ PVC, Biocore researchers are also working on bio-based alternatives to DEHP, which is a widely-used additive that plasticizes PVC. Using biomass as raw material, chemists from DLO (Wageningen, The Netherlands) have synthesized a biobased phthalate, which is actually more efficient in making PVC flexible than DEHP. In tests, PVC containing 30% of the new plasticizer is about twice as flexible as PVC containing a similar amount of DEHP, without compromising the strength of the product.

Biocore: Indian case studies Biocore aims to reveal how biorefineries can be implemented within defined local contexts. To achieve this, critical factors such as feedstock availability and logistics, but also social impacts and policy, will be examined and accounted for during the course of the Biocore project. Specific actions aim to critically analyze regional availability of lignocellulosic biomass feedstocks (straws, hardwood and SRC (short rotation coppice) wood) in different parts of Europe and India and optimize their supply for Biocore biorefineries in an economically-, socially- and environmentally-sustainable way. Bioenergy is an excellent opportunity for India and so the Biocore project aims to play a part in its development, by providing an analysis of how a biorefinery could work, and thus provide benefits, in India. To achieve this, the Indian case study will focus on rice straw, which is a major resource in India, and more widely in Asia. Currently rice straw is

not exploited by Indian farmers, being burnt in the field, thus provoking significant environmental pollution and wasting precious biomass resources. The Energy and Resources Institute (TERI), the Indian partner of Biocore, will investigate feedstock provision potential at regional level and availability requirements, providing cost-supply curves for different scenarios in Punjab and Haryana. Evaluation of agronomical and environmental impacts and benefits related to the use of rice straw will be studied. As well as contributing to benchmarking studies and supply chain modeling, TERI will be active in the definition of the settings for a comprehensive sustainability assessment that will take into account social, legal and political factors, key points that will ultimately determine public acceptability and market diffusion of new technologies. To probe some of these aspects, a meeting was held in India in November 2011, at which Indian stakeholders (including policymakers, farmers and NGOs) and Biocore partners discussed biorefinery and exchanged views on the opportunities and hurdles that would characterize the implementation of a next generation biorefinery plan in India. bioplastics MAGAZINE will watch the development and keep the readers updated. www.biocore-europe.org/ www.international.inra.fr/

Michael Carus of nova-Institute during the meeting in India, Nov. 2011 (photo: courtesy Michael Carus)

O O O

Di-2-ethylhexyl phthalate (DEHP)

bioplastics MAGAZINE [01/12] Vol. 7

From Science & Research Figure 1: Principal steps in realization of PLA-gypsum AII-clay (nano)composites via melt-compounding technology in a co-rotating twin-screw extruder

(1) Gypsum AII + clays (dry-mixing) Drying all components

(2) Gravimetric dosing PLA and AII - clay

(3) Melt compounding in twin-screw extruder Leistritz type ZSE 18 HP-40D (ø=18 mm, L/D=40)

(4) Granulating (granules for injection molding)

PLA nanocomposites Tailored with specific end-use properties by Philippe Dubois, Marius Murariu Laboratory of Polymeric and Composite Materials Center of Innovation and Research in Materials and Polymers (CIRMAP) University of Mons (UMONS) & Materia Nova Research Center Mons, Belgium

The ‘green’ challenge: polylactide (PLA)-based (nano)composites Polylactide or polylactic acid (PLA) is currently receiving considerable attention for rather conventional utilizations such as packaging materials as well as production of textile fibers, and more recently PLA has attracted increased interest for technical applications as well. [1-3] Actually, novel grades of PLA and related high performance PLA-based materials with higher added value are continuously searched for engineering applications such as electronic devices, electrical accessories, automotive parts, household appliances, etc. Consequently, the profile of PLA properties need to be tuned up for specifically reaching the end-user demands, and the combination of PLA with micro- and/or nano-fillers together with either flame retardants, impact modifiers, plasticizers or even other (bio)polymers represents a straightforward and readily scalable technical approach [2-8]. It is worth noting that the University of Mons (UMONS), through both the Center of Innovation and Research in Materials and Polymers (CIRMAP) and Materia Nova center, has significantly contributed to the field of bio(nano) composites. This involvement is exemplified by the large panel of R&D activities and projects ranging from the fundamental/laboratory level to industrial scale production mostly performed by reactive processing (particularly reactive extrusion, so-called REx). Additionally, to allow the rapid implementation of novel products, UMONS and Materia Nova have recently created NANO4 S.A., a spinoff company specialized in production, functionalization, characterization and processing of nanofillers, incl. renewable biosourced nanoparticles, and their related masterbatches. Accordingly, NANO4 S.A. allows for the up-scaling of new bio(nano)composites characterized by specific end-use properties such as gas barrier, flame retardancy (FR), UV absorption, antibacterial action, tailored electrical behavior, etc.

bioplastics MAGAZINE [01/12] Vol. 7

From Science & Research

Case study 1: PLA-gypsum-clay (nano)composites with specific flame retardant properties The traditional technology for the production of lactic acid (LA) leads in the formation of large amounts of hydrated calcium sulphate, i.e., for each kilogram of LA, about one kilogram of gypsum is formed as a by-product [4, 5]. In response to the demand for extending the range of PLA applications, while reducing production cost, it has been demonstrated that commercially available PLA can be effectively melt-blended with previously dehydrated gypsum (so-called CaSO4 β-anhydrite II (hereafter noted AII), thus the by-product directly issued from LA fabrication process [4]. For achieving high performance PLA composites and for preventing polyester chain degradation by hydrolysis, it is important to specifically use AII microparticles, which is actually formed by dehydration of gypsum hemihydrate at 500 °C. These two products (PLA and AII) from the same source as origin can lead by melt-mixing to polymer composites characterized by remarkable thermal stability, high rigidity, good tensile strength and barrier properties even at high AII content (up to 40 wt%). Such performances could be ascribed to the fine microfiller dispersion and good interfacial characteristics. Moreover, like for other mineral-filled polymers, addition of a third component into PLA–AII compositions, e.g., plasticizers, flame retardants, nanofillers, has been considered in order to generate new PLA grades with specific end-use performances. It was discovered (WO 2008/095874 A1 and US 2010/0184894 A1 patents: ‘Polylactide-based compositions’) that co-addition of dehydrated CaSO4 (AII form) and adequately selected organo-modified layered silicates (OMLS) triggers synergistic effects on PLA fire-resistant properties. [5, 6] Interestingly enough, the production of these ternary PLA-AII-OMLS bio(nano)composites, has been successfully conducted by melt-compounding in a co-rotating twin-screw extruder as illustrated in Figure 1. The different starting materials that were investigated are: PLA, was supplied by NatureWorks LLC as PLA 3051D (Mn(PS) = 112 000; Mw/Mn = 1.95; D-isomer = 4.3 %). Calcium sulphate hemihydrate, the by-product obtained from lactic acid production process (d50 of 9 μm) was provided by Galactic S.A. Starting from this filler, β-anhydrite II (AII) was obtained by drying at 500 °C for 1 h. A natural calcium sulphate anhydrite (USG CAS-20-4, d50 of 4 μm) kindly supplied by USG Company was also studied. This product was used only as alternative for gypsum from

350 RHR (kW/m2)

Two selected key-results, relying upon the original production of innovative bio(nano)composite materials using PLA as polyester matrix, with targeted applications in packaging, in textile fibers and in the field of engineering sector, are summarized hereinafter.

300 250

PLA

PLA- AII - clay (nano(composites: Decrease of pRHR, higher ignition time ...

200 150

PLAAII - clay

100 50 0

Time (s) 0

100

200

— PLA — PLA- 40% AII (9) - 3% B104 — PLA- 40% AII (4) - 3% C10A

300

400

500

600

700

(a)

Figure 2: RHR plotted against time: neat PLA compared to PLA- gypsum AII- clay (nano)composites (by courtesy, tests performed by Dr. Antoine Gallos –ENSC Lille)

lactic acid production process and as microfiller of lower dimensions. Bentone 104 (Elementis Specialties) and Cloisite 10A (Southern Clay Products, Inc.), two montmorillonite-type clays organo-modified with benzyl dimethyl hydrogenated tallowalkyl ammonium, respectively coined as B104 and C10A, were investigated as OMLS. Highly filled (nano)composites, i.e., PLA with 40 wt% in AII and 3 wt% in clay, were thus produced at semi-pilot scale in a twin-screw extruder (Leistritz type ZSE 18 HP-40D, Ø = 18mm, L/D = 40) and the so-produced granules were characterized using various techniques. Firstly, it is worth mentioning that the good thermo-mechanical performances, comparable to those of conventional filled engineering polymers, are ascribed to the excellent filler (AII and OMLS) dispersion throughout the polyester matrix as evidenced by electronic microscopy [4, 5]. By considering the high content in inorganics (e.g., 40% and 3% in micro- and nanofillers, respectively), these materials are characterized by good tensile strength (≈ 37 MPa), whereas the rigidity, i.e., Young’s modulus, is above 6300 MPa, that means an increase of 125% with respect to neat PLA (2800 MPa). Besides, as evidenced by thermogravimetry analysis (TGA) these (nano)composites are characterized by improved thermal stability (e.g., following as criterion the temperature for 5% weight loss- T5%), whereas DSC analyses attest for the preservation of principal thermal parameters with even some increase of the PLA crystallization rate, property that can be considered as very promising in the perspective of further applications. Remarkably, the co-addition of gypsum AII and OMLS largely improves the fire-resistance of PLA as evidenced by cone calorimetry testing (Figure 2). The time to ignition (tig) is increased and the peak of maximum rate of heat release (pRHR) is reduced by almost 50% with respect to neat PLA. In addition, the horizontal fire test UL94 HB reveals a low speed of burning (29-31 mm/min) - corresponding to

bioplastics MAGAZINE [01/12] Vol. 7

From Science & Research PLA 3051D

PLA - 40% AII- 3% B104

Residual specimens

Figure 3 (A-C): UL94 HB fire testing: specimens (~3.1 mm thickness) of (a) neat PLA burning with dripping and without char formation; (B) PLA- 40% CaSO4 AII (9 μm) - 3% B104 (nano)composites burning without any dripping and with intensive charring (as shown on the residue remaining at the end of the test (C))

HB classification (max. admissible value of 40 mm/min), together with the total absence of dripping and the formation of an intensive char (Figure 3). On one hand, the specimen samples based on either unfilled PLA or PLA filled only with AII (even at content as high as 40-50 wt%) burned with intensive dripping (continuous formation of burning droplets) and without charring. On the other hand, even if no flamed droplet was generated upon burning the binary PLA-OMLS nanocomposites, their burning rate increased preventing HB classification [5, 6]. Therefore, only the ternary PLA-AII-OMLS (nano)composites reached HB classification and displayed intensive charring attesting for the unique synergistic effect between the CaSO4 microfiller and organo-modified nanoclay. In relation to other key-properties, it is firmly believed that these novel PLA-based (nano)composites are perfectly suited for technical applications (e.g., electronic devices, electrical accessories, automotive parts, household appliances, etc.) due to their thermal stability and excellent processing ability evidenced using traditional techniques such as extrusion, injection and compression molding.

bioplastics MAGAZINE [01/12] Vol. 7

Case study 2: PLA-ZnO nanocomposite films and fibers: anti-UV and antibacterial properties ZnO nanoparticles are well-known environmentally friendly and multifunctional inorganic additives that could be considered as nanofillers for PLA providing properties like antibacterial action or intensive ultraviolet absorption. However, ZnO as well as other Zn derivatives are known as very efficient catalysts in ring-opening polymerization of lactide but also in ‘unzipping’ depolymerization of PLA. Indeed, preliminary studies revealed that addition of untreated ZnO nanoparticles into PLA at melt-processing temperature led to severe degradation of the polyester matrix, i.e., drastic reduction of PLA molecular weight, resulting in a sharp reduction of their thermo-mechanical characteristics [7]. Noteworthy, to make PLA matrix less susceptible to the catalytic action of ZnO during the melt blending process and any subsequent film/fiber processing, various filler surface treatments with selected additives (stearic acid, stearates, (fatty) amides, etc.) were tested with relatively low effectiveness. Remarkably, ZnO surface-treated by triethoxy caprylylsilane (i.e., commercial grade Zano 20 Plus supplied by Umicore Zinc Chemicals) leads to PLA-based nanocomposites characterized by very good preservation of the intrinsic molecular parameters of PLA and related physicochemical characteristic features. Furthermore, the surface-coated ZnO nanoparticles proved to finely and regularly disperse within the polyester matrix as highlighted by TEM (Figure 4). Additionally, whatever the nature of the PLA matrix, i.e., spinning or extrusion grade, the nanocomposites filled from 1 to 3 % surface-treated ZnO show mechanical properties, e.g., a tensile strength in the range 55 - 65 MPa, at least comparable and even somewhat higher than those obtained for the neat polyester matrix [7]. Noticeable, these nanocomposites show the onset of thermal degradation (T5%) at significantly higher temperature (from 20 to 40 °C) with respect to the samples containing untreated ZnO. Such improvements represent a real interest in the perspective of their utilization in production of films or fibers, and are mainly attributed to the effect of the –Si-O-Si-O- layers that cover the nanofiller surface and behave as a protecting barrier limiting the catalytic effect of ZnO able to promote unzipping of the nearby PLA chains. Interestingly, the related PLA-ZnO nanocomposite films as produced by compression molding or extrusion, proved to be characterized by very effective anti-UV action (Figure 5), in fact a total anti-UV protection is obtained for an amount of nanofiller as low as 1%. On another hand, PLA-ZnO nanocomposites have been also melt-spun and a highly efficient antibacterial protection on knitted fabrics was evidenced to both gram positive and gram negative bacteria [7].

From Science & Research Further prospects: PLA-based hybrid nanocomposites Other nano-reinforcements for PLA are under development, but the most extensively studied so far, remain natural clays (like montmorillonite, sepiolite and halloysite) or carbon-based nanoparticles, mostly carbon nanotubes (CNT) and expanded/ exfoliated graphite. As illustration, exfoliated graphite as nanofillers combine the lower price and the layered structure of clay nanoplatelets with the superior thermal and electrical performances of CNT, whereas other specific end-use properties, e.g., mechanical rigidity, lower coefficient of friction, better abrasion resistance, have been highlighted. Also, PLA-expanded graphite (EG) nanocomposites proved to be characterized by increased kinetics of crystallization as well as thermo-mechanical properties allowing the application of these materials at higher temperature [8]. Furthermore, co-addition of EG and CNT into PLA paves the way to hybrid nanocomposites characterized by an interesting set of properties: higher tensile strength and rigidity, improved FR, conductive electrical characteristics even in presence of tiny amount of CNT. Again, the extent of the nanoparticle dispersion throughout the matrix remains a challenge where adequate surface treatment and/or addition of interfacial compatibilizers represent the best tools to get rid of filler aggregation.

Conclusion Following the recent expansion of bioplastics and in response to the demand for enlarging PLA applications, it has been emphasized that PLA can be effectively melt-blended with selected micro- and nano-fillers to produce novel bio(nano) composites. Successful up-scaling of laboratory results via continuous twin-screw extrusion technology has been achieved paving the way to industrial applications. In this contribution, two case studies are discussed: i) PLA filled with CaSO4 (AII) and selected organo-modified clays yielding high performance (nano) composites, and ii) PLA-(surface-treated) ZnO nanocomposites leading to nanocomposite films and fibers with specific end-use properties : anti-UV protection and antibacterial action. Based on these illustrations, very promising developments in the synergy aspects are clearly expected from the combination of nanofillers and more efforts are to be consented in this direction.

80 70 60 50

Transmittance (%)

90 neat PLA

0% Zn0 1% Zn0 3% Zn0

40 on PLA films (0.2 - 0.3 mm thickness)

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500

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Figure 5: UV-vis spectra of selected samples of PLA-ZnO (silane treated) films compared to neat PLA evidencing total anti-UV protection

800

Figure 4: TEM picture of PLA (spinning grade) -1% ZnO (silane treated) attesting for good nanofiller dispersion into PLA matrix

http://morris.umons.ac.be/CIRMAP www.materianova.be Authors thank the Wallonia Region, Nord-Pas de Calais Region and European Community for the financial support in the frame of the INTERREG – MABIOLAC and NANOLAC projects. They thank all partners, especially to ENSC Lille and ENSAIT- Roubaix (France), for technical/ scientific support and helpful discussions, and all mentioned companies for supplying raw materials. CIRMAP acknowledges supports by the Région Wallonne in the frame of OPTI²MAT program of excellence, by the Interuniversity Attraction Pole program of the Belgian Federal Science Policy Office (PAI 6/27) and by FNRSFRFC. References 1. Platt D. Biodegradable Polymers - Market report. Smithers Rapra Limited UK, Shawbury, Shrewsbury, Shropshire, 2006. 2. Madhavan Nampoothiri K, Nair NR, John RP. Biores. Tech. 2010;101:8493–501. 3. Dubois Ph, Murariu M. JEC Composites Magazine 2008;45:66-9. 4. Murariu M, Da Silva Ferreira A, Degée Ph, Alexandre M, Dubois Ph. Polymer 2007;48(9):2613-8. 5. Murariu M, Bonnaud L, Yoann P, Fontaine G, Bourbigot S, Dubois Ph. Polym. Degra.d Stabil. 2010;95:374-81. 6. Dubois Ph, Murariu M, Alexandre M, Degée Ph, Bourbigot S, Delobel R, Fontaine G, Devaux E. Polylactide-based compositions. WO Patent 095874 Al, 2008. 7. Murariu M, Doumbia A, Bonnaud L, Dechief AL, Paint Y, Ferreira M, Campagne C, Devaux E, Dubois Ph. Biomacromolecules 2011;12:1762-71. 8. Murariu M, Dechief AL, Bonnaud L, Paint Y, Gallos A, Fontaine G, Bourbigot S, Dubois Ph. Polym. Degrad. Stabil. 2010;95:889-900.

bioplastics MAGAZINE [01/12] Vol. 7

Materials M Electrodialysis Feed Solution H2O Anode -

E. Coli

C C

Dilute

+ + + + + + + +

+ H2O + OH + + + + Cathode + +

O O

Concentrate

Biomass

Fermentation A

Separation / Purification B

Conversion C

Resin Manufacturing D

Schematic diagram of (A) fermentation, (B) Separation and Purification, (C) Lactide Conversion and (D) PLA polymerisation.

Four-unit process technology for PLA manufacturing www.hyundai.com

olylactide (PLA) is one of the most important biodegradable and biocompatible polyesters derived from annually renewable resources. The most efficient method for preparation of PLA is ring-opening polymerisation of the dimeric cyclic ester of lactic acid, i.e. lactide. Fermentative production of the PLA precursor, lactic acid, offers the great advantage of producing optically pure L-or D-lactic acid depending upon the strains selected for fermentation. The optical purity of lactic acid is crucial for the physical properties of PLA. Though L-lactic acid can be polymerised to give a crystalline product (PLLA) suited to commercial uses, its application is limited by its low melting point. Complexing PLLA with poly-D-lactic acid (PDLA), however, raises the melting point thus presenting an attractive solution to the heat sensitivity of PLA. However, fermentation of sugars to D-lactic acid has been studied very little and its microbial productivity is not well known. Therefore, Hyundai路Kia Motors investigated D-lactic acid fermentation with a view to obtaining improved strains capable of producing D-lactic acid with enhanced productivity, and finally a maximum lactic acid production of 60 g/l was achieved.

By Hong, Chae Hwan Kim, Si Hwan Soe, Ji Yeon Han, Do Suck CAE & Materials Research Team Hyundai路Kia Motors Gyeonggi-do Uiwang Samdong, South Korea

bioplastics MAGAZINE [01/12] Vol. 7

A fermentation-based process requires maintenance of a near neutral pH for high productivity and this necessitates the addition of alkali in most of the cases. Alkali addition produces a salt of lactic acid instead of lactic acid itself. To overcome this salt problem, the processes based on electrodialysis that do not require then addition of acid or alkali to convert lactate salts into lactic acid was tested. Electrodialysis technology (see picture) is based on electromigration of ions through a stack of cation and anion exchange membranes. Basically, it involves two steps. The first step called conventional electrodialysis (CED) separates and concentrates lactate salts. The second step called bipolar electrodialysis (BED) converts lactate salts into lactic acid. These two processes were adopted and D-lactic acid was produced. Lactide is prepared in a two-stage process: first, the lactic acid is converted into oligo(lactic acid) by a polycondensation reaction; second, the oligo(lactic acid) is thermally depolymerised to form the cyclic lactide via an unzipping mechanism. Through catalyst screening test for polycondensation and unzipping depolymerisation reaction a new method was developed to shorten the whole reaction time to 50% of the conventional method. Poly(L-)lactide was obtained from the ring-opening polymerisation of L-lactide. Various catalysts and polymerisation conditions were investigated resulting in the best catalyst system and the scale-up technology.

Report 75,000 tonnes/a Lactide plant (plant overview)

Successful start New 75,000 tonnes lactic acid plant started operation

By Lex Borghans Manager Corporate Marketing Purac, Gorinchem, the Netherlands

Shirts with tie – supporting high heat fibers

bioplastics MAGAZINE [01/12] Vol. 7

urac, Gorinchem, the Netherlands, has successfully completed the construction of its new 75,000 tonnes/ year Lactide plant in Thailand. The construction of this EUR 45 million state-of-the-art plant started in March 2010 and has recently been finalized. At the moment the plant is being commissioned and the first test runs have already been finalized. Several batches of high quality PURALACT® Lactides have been produced and actual deliveries of Puralact to customers are scheduled to start early 2012. This investment is driven by the commitment of Purac and its parent company CSM to play a leading role in the development of the market for lactic acid based bioplastics (Poly Lactic Acid or PLA). PLA contributes, with commercially viable and readily available products, to a significantly lower carbon footprint compared to traditional fossil-based plastics. The PLA market is highly attractive as many Brand Owners are increasingly developing and launching sustainable products. The new plant will produce Lactide monomers for biobased resins and plastics, which will be supplied to Purac business partners in the polymer and chemical industry. The PLA polymers made from the Puralact L and Puralact D monomers aim at gaining a significant share of today’s plastics market and enables Purac’s partners to produce PLA with application temperatures up to 180 °C (266 °F). François de Bie, Marketing Director Bioplastics comments: “This new Lactide plant will take us to the next step in developing the PLA market, together with our partners. In addition, we have made good progress in our application development program for bioplastics. Based on our proprietary technology we have demonstrated the benefits of Purac’s PLA building blocks in demanding applications in the packaging, foam, fiber and consumer products industries.”

Report Food containers – supporting high heat food tray

in Thailand PLA homopolymer resin produced from Purac’s stereo chemically pure L-Lactide has recently been tested and validated in a range of high end applications. In the segment of fiber spinning, a technical performance comparison was made between a regular, commercial PLA fiber grade and a comparable Puralact L based PLLA homo-polymer. With the PLLA homo-polymer, fully-drawn yarn with excellent mechanical and thermal properties was successfully made, due to the significantly higher melting point of PLLA homo-polymer. The fast crystallization and high levels of crystallinity of the PLLA provide important benefits to physical properties of fibers and fabrics.

75,000 tonnes/a Lactide plant (detailed visual)

In close co-operation with partners in the packaging arena, a product formulation was developed based on blends of PLA homo-polymer resins i.e. Puralact based PLLA and PDLA. This blend was extruded into a sheet material and subsequently thermoformed on an industrial production line for applications such as hot food trays. This demonstrates that when using Puralact based PLA resin, it is possible to meet the high heat requirements typical for these type of applications. “The successful start up of our 75,000 ton Lactide plant marks another milestone in Purac’s commitment to the development of the PLA market” says Jeroen Jonker, Vice President Bioplastics at Purac, “We are now able to supply monomers that can be transformed into high performance PLA, whilst providing the scale and security of supply as required by the end use markets. I am particularly excited that we are increasingly able to attract customers in the high end markets, a clear confirmation of our high performance PLA strategy” www.purac.com

Purac will present more details on their PLA activities at the

2nd PLA World

C o n g r e s s

15 + 16 MAY 2012 * Munich * Germany

Contact f.de.bie@purac.com at Purac, to get a 15% discount on the conference fee. organized by bM

bioplastics MAGAZINE [01/12] Vol. 7

Basics

LA (polylactide or polylactic acid) belongs to the group of biopolymers chemically prepared from biobased, renewable raw materials. In this class of materials PLA is today’s most important thermoplastic biopolymer on the market. PLA is an aliphatic polyester based on lactic acid, a natural acid, that is mainly produced by fermentation of sugar or starch with the help of micro-organisms. Lactic acid exists in two optically active enantiomeric forms, i.e., as L-(+)- or (S) lactic acid and as D-(―)- or (R)-lactic acid.

STARCH, SUGAR, BIOGENIC WASTE MATERIALS

CONDITIONING OF SUBSTRATES Fermentation

MiCroorganismS

IsolATION

InoCulATION

PLA MATERIAL

ProduCt

PROCESSING

Basics of PLA By Michael Thielen This article is based on a chapter in the new book “Engineering Biopolymers” [1] as well as personal information of Sicco de Vos (Purac) and Andreas Grundmann (Uhde-Inventa-Fischer)

O (R,R)- lactide or D-lactide

O (S,S)- lactide or L-lactide

(Source: Purac)

bioplastics MAGAZINE [01/12] Vol. 7

O O (R,S)- lactide or meso-lactide

PLA

Blending/ AdditivES

SynthesIS

PolymeriZation

LactidE

Polymerisation Most of the lactic acid today is being produced by fermentation. Here biological material is being converted with the aid of bacteria, fungal or cell structures, or by adding enzymes. However, to manufacture lactic acid and — in the next step — polylactide a certain amount of process engineering is necessary (see graph). The biological feedstock, this engineering as well as the purity of the lactic acid play an important role on the quality, the properties and not least the cost of the final PLA. In the last 10-15 years, mainly by optimising the process technology and the ‘economy of scale’ with larger manufacturing capacities, the price of PLA could be reduced significantly. Further significant reductions in the manufacturing cost seem possible in the future, especially when raw material costs are reduced, i. e., by the use of biogenic residues or wastes, such as whey, molasses, or wastes containing lignocellulose. In order to convert lactic acid into PLA, the lactic acid is in a first step prepolymerised to form small prepolymers by socalled oligopolycondensation and then depolymerised into cyclic lactides. This means two lactic acid molecules form a cyclic dimer, lactide, which, depending on the constituting isomers, can be a D-D-lactide, an L-L-lactide or a mesolactide (having one D and one L isomer). These lactides are then connected in a ringopening polymerization process, producing long, linear macromolecules: the PLA resin. This process can be performed using stirred tank cascades or horizontal reactors as they are known from polyester chemistry. The majority of the industrially relevant production processes for PLA have

(Source: [1])

LACTIC ACID

Basics

in common that they are continuous melt processes, operated at high temperatures without the use of solvents. The capacity of such plants varies from 5,000 to 140,000 tonnes per annum. Apart from some exceptions, like clear film and fiber, virgin PLA resin as it exits the polymerization reactor, cannot be directly processed into final plastic products. Hence, as is usual with most plastics, virgin PLA resin is modified for specific applications by compounding with functional additives and/or by blending with other polymers (bioplastics or traditional, oil-based polymers). Such modifications have already resulted in PLA compounds with sufficient performance to replace PET, HIPS, PP and even ABS. In order to prevent the PLA pellets from sticking together during storage and transportation, virgin resin pellets are commonly crystallized. The resulting semi-crystalline, heat resistant granulate can be shipped around the globe without problems. In its crystalline state the chemical stability of PLA – and PLLA homopolymer in particular - is higher and its water absorption, swelling behavior, and rate of biological degradation are lower than those of amorphous PLA.

PLA production For the production of PLA approximately 0.1 to 0.25 ha (in Europe rather 0.2 to 0.5 ha) of agricultural area is needed for 1 tonne. For comparison, cotton requires almost 3x more land for the production of the same quantity. Hence, PLA exhibits very high land use efficiency and other comparisons can be found in [1, 2]. The world’s first large PLA production unit with a capacity of 140,000 tonnes per annum began production in the USA in 2002. Industrial PLA production facilities can now also be found in the Netherlands, Japan and China. For example one Dutch company is going to expand their 5,000 t/a capacity to 35 – 70,000 t/a. A recent announcement from China was about an expansion of their PLA capacity to 50,000t/a in 2013 from 5,000 t/a currently. In Germany a 500 t/a industrial pilot plant started operation in 2011 and in Switzerland a 1000 t/a industrial pilot plant will become operational in the first quarter of 2012.

Gattinoni Obama Dress 100% NatureWorks Ingeo PLA (Picture: Gattinoni)

Properties Advantages of PLA are its high level of rigidity, transparency of the film, cups and pots, as well as its thermoplasticity and good processing performance on existing equipment in the plastics converting industry. Nevertheless PLA has some disadvantages at the moment: as its softening point is around 60°C, the unmodified material is not suitable for the manufacture of cups for hot drinks. Modified PLA types can be produced by the use of additives like nucleating agents or impact modifiers, or by a blending PLLA and PDLA, the homopolymers of of L- and D- lactides (stereocomplexing), which then have the required morphology for use at higher temperatures (see bM 02/2008). A second characteristic of PLA together with other bioplastics is its low water vapour barrier. Whilst this characteristic would make it unsuitable, for example, for the production of bottles, its ability to “breathe” is an advantage in the packaging of bread or vegetables.

Applications Transparent PLA is very similar to conventional mass produced plastics, like PS, PP, PET and PMMA, not only in its properties but it can also be

bioplastics MAGAZINE [01/12] Vol. 7

Basics processed on existing machinery without modification. PLA and PLAblends are available in granulate form, and in various grades, for use by plastics converters in the manufacture of film, moulded parts, drinks containers, cups, bottles and other everyday items. In addition to short life packaging film or deep drawn products (e.g. beverage or yoghurt pots, fruit, vegetable and meat trays) the material also has great potential for use in the manufacture of durable items. Examples here are casings for mobile phones, possibly reinforced with natural fibres, desktop accessories, lipstick tubes, and lots more. Even in the automotive industry we are seeing the first series application of plastics based on PLA. Some Japanese car manufacturers have developed their own blends which they use to produce dashboards, door tread plates, etc. (see bM 02/2008). Fibres spun from PLA are even used for textile applications, because PLA offers several interesting benefits over the traditional polyester fiber material, PET, and cotton. On the market we can already find all kinds of textiles from articles of clothing through childrenâ&#x20AC;&#x2122;s shoes to car seat covers. Furthermore there are lucrative special markets, for example in medical and pharmaceutical applications where PLA has been successfully used for decades. From screws etc. that are slowly resorbed into the body, to nails, implants and plates made from PLA or PLA copolymers, the parts are used to hold broken bones in place as they heal. The PLA is broken down within the body and assimilated by the human metabolism, so saving the patient the problem of a second surgery to remove the previously implanted parts.

End of life [1] Endres, H.-J., Siebert-Raths, A.: Engineering Biopolymers, Hanser Publsihers, 2011 [2] Patel, M.: Ă&#x2013;kobilanzierung von Biopolymeren und biogenen Rohstoffen; 4. BioKunststoffe (conference), Hannover/ Germany, 12-13 April 2011

Uhde Inventa-Fischer will present more details on their PLA activities at the

2nd PLA World

C o n g r e s s

Basically PLA is recyclable, biodegradable and compostable, and can be incinerated for energy recovery and accelerated carbon recycling. However, copolymers or blends of polylactides are rapidly, slowly, or not at all biodegradable, depending on their composition, morphology, geometry, and not in the least the environmental conditions. Whilst PLA is actually quite stable under typical, dry, indoor conditions for years, it can be degraded under industrial composting conditions in a few weeks. Blends of PLA with non-biodegradable plastics, such as PLA/PC, are commonly not biodegradable let alone compostable, but that is also not the purpose of such a durable compound. This underlines the special diversity of this bio-based bioplastic that can be used in a form that rapidly degrades in industrial composting, or, if required, in a more durable composition that can be used for years and will most likely be recycled or incinerated in the end. As soon as significant amounts of PLA can be collected, recycling becomes feasible and worthwile. That is why for instance brand owners like Danone encourage their competitors to use PLA, in order to achieve a critical mass for recycling as soon as possible. Besides material recycling, where PLA is ground up and reprocessed into new products, also chemical (or feedstock) recycling is possible. Here the PLA is converted back into lactide monomers and lactic acid, and can be used for PLA again or for completely different purposes.

15 + 16 MAY 2012 * Munich * Germany

Contact andreas.grundmann@thyssenkrupp.com at Uhde Inventa-Fischer to get a 15% discount on the conference fee. organized by bM

bioplastics MAGAZINE [01/12] Vol. 7

www.ifbb-hannover.de www.purac.com www.uhde-inventa-fischer.com

Did you know ?

From the field to the wheel: Photovoltaic is 40 times more efficient than the best biofuel (source: shutterstock/alphaspirit)

By Michael Carus Managing Director nova-Institute Hürth, Germany

Solar radiation in Germany in gigajoules per hectare per year 36,000 (+/- 10 to 12 % depending on region)

Photosynthesis About 2% of 20,000 GJ per hectare and cultivation period: 400 GJ per hectare per year

Photovoltaic cell > national grid Total degree of efficiency about 10%: 3,600 GJ per, hectare per year

Mechanical and chemical processes > Biofuels 50 to 135 GJ per hectare per year (bioethanol, biodiesel, BTL)

Inverter (DC > AC) Efficiency 90% Network losses: 6% Remainder for the car battery: 3,050 GJ per hectare per year

hat will be the future of mobility? Which solution is both land-efficient and sustainable? On the one hand we have all different kinds of biofuels, like biodiesel, bioethanol and BTL (biomass to liquid), and on the other hand there is e-mobility sourced by renewable energy sources. Today we would like to compare the land efficiency, or the average energy yield per hectare for different biofuels, with that of a solar driven electric car - from the agricultural field to the car wheel. As a region we have chosen Germany just as an example. For most other regions the relationship of the results will not be so different - if there is more sun, the yield of the crops (as long they have enough water) and of the solar panels will increase almost in the same order. In regions with very long growing periods, or even two growing seasons per year, and sufficient water supply, the yield will be relative higher. In Germany the average solar radiation per hectare per year is about 10,000,000 kWh or 36,000 Gigajoules (GJ). This energy is used by the leaves of the crops as well as by the photovoltaic cell to transform and store energy.

1) Biofuels Degree of efficiency of distribution and combustion engine (fuel > wheel) About 35%

18 – 47 GJ per hectare per year (bioethanol, biodiesel, BTL)

From battery to vehicle wheel Total efficiency about 60%

1,800 GJ per hectare per year (solar electric car)

The yield per hectare per year varies between a factor of 40 (BTL) and 100 (biodiesel)

bioplastics MAGAZINE [01/12] Vol. 7

The leaves of crops use the solar radiation by photosynthesis. The theoretical maximum conversion efficiency of solar energy to biomass is 4.6% for C3 crops and 6% for C4 crops (maize, sugar cane, miscanthus), the best yearround efficiencies realized are no more than 3% (Langeveld 2010). So a realistic value of the photosynthesis in plant cells is about 2%, this is not very efficient. Because crops normally are only 100 – 150 days in the fields (spring and summer) the full yearly solar radiation cannot be taken into

Did you know ?

account – we have to reduce the 36,000 GJ to around 20,000 GJ per hectare and growing period. That means that 400 GJ per hectare per year (2% of 20,000 GJ) are transferred to bioenergy in biomolecules. Further mechanical and chemical processing to biofuels will reduce the efficiencies and the yields significantly. In the range covering biodiesel from rapeseed/canola, bioethanol from wheat, and sugar beet to BTL (biomass to liquid) the energy yields are between 50 and 135 GJ per hectare per year. That means that between 0.3 and 0.7% of the solar energy is converted to biofuel. Finally the internal combustion engine has an efficiency of about 35% (biofuel to wheel). 65% of the energy is lost as heat. This brings us a final yield of between 18 and 47 GJ per hectare per year or a total efficiency of between 0.1% and 0.2% related to the solar radiation of 20,000 GJ per hectare over the growing period. This does not look like the solution for the future!

(biodiesel) more efficient compared to the system of energy crops plus a biofuel driven car! That is one reason why the nova-Institute thinks that biofuels are an intermediate technology that should be substituted by solar (and wind) energy in the next 20 – 30 years. To switch from biomass to solar will set free huge amounts of land for other applications, such as bioplastics: we should rather use biomass for bio-based chemistry and materials which cannot be produced by sun and wind. Sources: Langeveld, J.W.A. 2010: Biomass availability. In: Langeveld et al. (editors): The Biobased Economy. Earthscan, London 2010.

Remark: Where is the energy lost in the crop? Light-use efficiency of the average leaf of a crop is similar to that of the best photovoltaic (PV) solar cells transducing solar energy to charge separation (approx. 37%). In photosynthesis most of the energy is lost, being dissipated as heat during synthesis of biomass. (Langeveld 2010)

2) Solar electricity Photovoltaic panels have a realistic efficiency of 10% as a yearly average today, and they work during the full year. The latest commercial systems have already efficiencies up to 15% and it is expected this will increase to 20 – 40% in the future. Today from the 36,000 GJ average solar radiation solar panels can earn 3,600 GJ of electricity (DC) and an inverter transforms this to AC electricity, suitable to feed into the national grid. Modern electrical inverters have efficiencies of ca. 90%. There are also losses in the grid, typically in Germany about 6%. Thus, of the original solar radiation about 3,050 GJ reached the battery of the car. The system battery (ca. 65%) and electric motor (ca. 95%) have a total efficiency of ca. 60%. That means that finally 1,800 GJ are transmitted to the car wheel – or as a percentage of the solar radiation: 5%. This is much better than with biofuels. Conclusion: Crops and solar panels are using the same source of energy to transform, via biofuels or electricity, into mobility, i.e. solar radiation. The photovoltaic panel and electric car system is 40 times (BTL) to 100 times

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bioplastics MAGAZINE [01/12] Vol. 7

Interview

Pilar Echezarreta What makes Biolice unique for you?

ilar Echezarreta is a recognized Spanish architect. Recently she made some ‘inflatable architecture’ from film material made of Biolice, a bioplastic manufactured by Limagrain Céréales Ingrédients from maize flour using a unique process in the bioplastics sector. Pilar was born in Barcelona and lived in Mexico City for around 20 years. After graduating in Architecture, she studied, worked and lived between Paris, New York and Shanghai. Parallel to these activities she’s been working during the last 12 years in an on-going research project on inflatable structures with materials that are not usually considered for Architecture: air, paper, and plastics. Every unit is 100% handmade. How did you discover Biolice? What triggered the idea of using Biolice in your art ? During the month of December, you can buy in Paris decorative plastic bags that are used as decoration at the bottom of the Christmas tree. Once holidays are over, you can place the tree inside and throw the whole to the waste, all being biodegradable. During January you’ll find these trees dressed in gold [golden pearls] under the rain. When I had the opportunity to build an inflatable in Mexico, I decided to contact Biolice. To my surprise, Biolice was very supportive to my initiative and sent me the necessary amount of material. The use of biodegradable film gave a new scope to the design and construction: inflatable architecture can also be biodegradable!

I guess it is very simple. Biolice is a noble material. If I can compare it to textiles, Biolice will be the silk of films. Biolice’s films have a great balance between weight, resistance, performance at warehouse, and color, and most important, it is biodegradable. Where did you show this kind of art? In Mexico City in 2009 the solo exhibition Golden Pearl and other prototypes proposed a colony of inflatable architectures built with polymer, one of them built real size with capacity for 8 people. The installation remained one month installed at the gallery. Later in 2010 I was invited by the Istituto Europeo di Design [Madrid] to teach the Air Workshop. The constraint I gave to the students was to build an inflatable structure out of 32 golden bags. The final presentation was a performance in the Plaza de El Callao — one of the most crowded squares in Madrid The most recent construction was last November at the IV Festival Architecture and Performance, at Madrid. The project presented is a site specific unit called Assemblage with Air, an inflatable concert hall. The unit measures around 20m long, by 5m high and 5m wide. If not confidential, can you tell us what is the next step with using bioplastics: working with ‘biosac by calcia’ bag, the innovative compostable cement bag, in order to find a link between architecture and raw materials for construction ? Being a rigid material, biosac makes me think in the use of paper in Architecture. Traditional Japanese architecture has impressive examples on this. We’re still on a study phase, and promise to keep you posted on the next biosac construction.

PDF

This is an abridged version of a longer interview with Pilar Echezarret. The complete interview as well as more pictures can befound at www.bioplasticsmagazine.com/201201.pdf www.biolice.com

bioplastics MAGAZINE [01/12] Vol. 7

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Suppliers Guide Simply contact:

1.4 starch-based bioplastics

1. Raw Materials

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For Example:

Showa Denko Europe GmbH Konrad-Zuse-Platz 4 81829 Munich, Germany Tel.: +49 89 93996226 www.showa-denko.com support@sde.de

FKuR Kunststoff GmbH Siemensring 79 D - 47 877 Willich Tel. +49 2154 9251-0 Tel.: +49 2154 9251-51 sales@fkur.com www.fkur.com

Limagrain Céréales Ingrédients ZAC „Les Portes de Riom“ - BP 173 63204 Riom Cedex - France Tel. +33 (0)4 73 67 17 00 Fax +33 (0)4 73 67 17 10 www.biolice.com

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110

DuPont de Nemours International S.A. 2 chemin du Pavillon 1218 - Le Grand Saconnex Switzerland Tel.: +41 22 171 51 11 Fax: +41 22 580 22 45 plastics@dupont.com www.renewable.dupont.com www.plastics.dupont.com

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Zhejiang Hangzhou Xinfu Pharmaceutical Co., Ltd No. 50 Qinshan Road, Jincheng The entry in our Suppliers Guide is Town, Lin‘an, 311300, China bookable for one year (6 issues) and extends automatically if it’s not canceled Tel.: +86 571 6106 2167 three month before expiry. Fax.: +86 571 6106 7360 grace@xinfupharm.com www.xinfupharm.com 6 issues x 234,00 EUR = 1,404.00 €

120

130

140

Kingfa Sci. & Tech. Co., Ltd. Gaotang Industrial Zone, Tianhe, Guangzhou, P.R.China. Tel: +86 (0)20 87215915 Fax: +86 (0)20 87037111 info@ecopond.com.cn www.ecopond.com.cn FLEX-262/162 Biodegradable Blown Film Resin!

Jean-Pierre Le Flanchec 3 rue Scheffer 75116 Paris cedex, France Tel: +33 (0)1 53 65 23 00 Fax: +33 (0)1 53 65 81 99 Natur-Tec® - Northern Technologies biosphere@biosphere.eu www.biosphere.eu 4201 Woodland Road Circle Pines, MN 55014 USA Tel. +1 763.225.6600 Fax +1 763.225.6645 info@natur-tec.com www.natur-tec.com

1.1 bio based monomers 150

160

PURAC division Arkelsedijk 46, P.O. Box 21 4200 AA Gorinchem The Netherlands Tel.: +31 (0)183 695 695 Fax: +31 (0)183 695 604 www.purac.com PLA@purac.com

170

180

Transmare Compounding B.V. Ringweg 7, 6045 JL Roermond, The Netherlands Tel. +31 475 345 900 Fax +31 475 345 910 info@transmare.nl www.compounding.nl

190

1.2 compounds 200

210

API S.p.A. Via Dante Alighieri, 27 36065 Mussolente (VI), Italy Telephone +39 0424 579711 www.apiplastic.com www.apinatbio.com

220

230

PolyOne Avenue Melville Wilson, 2 Zoning de la Fagne 5330 Assesse Belgium Tel.: + 32 83 660 211 www.polyone.com 1.3 PLA

240

250

www.facebook.com www.issuu.com

260

www.twitter.com 270

www.youtube.com

bioplastics MAGAZINE [01/12] Vol. 7

www.cereplast.com US: Tel: +1 310.615.1900 Fax +1 310.615.9800 Sales@cereplast.com Europe: Tel: +49 1763 2131899 weckey@cereplast.com

PSM Bioplastic NA Chicago, USA www.psmna.com +1-630-393-0012

Shenzhen Brightchina Ind. Co;Ltd www.brightcn.net www.esun.en.alibaba.com bright@brightcn.net Tel: +86-755-2603 1978

Grace Biotech Corporation Tel: +886-3-598-6496 No. 91, Guangfu N. Rd., Hsinchu Industrial Park,Hukou Township, Hsinchu County 30351, Taiwan sales@grace-bio.com.tw www.grace-bio.com.tw 1.5 PHA

Division of A&O FilmPAC Ltd 7 Osier Way, Warrington Road GB-Olney/Bucks. MK46 5FP Tel.: +44 1234 714 477 Fax: +44 1234 713 221 sales@aandofilmpac.com www.bioresins.eu

Telles, Metabolix – ADM joint venture 650 Suffolk Street, Suite 100 Lowell, MA 01854 USA Tel. +1-97 85 13 18 00 Fax +1-97 85 13 18 86 www.mirelplastics.com

Suppliers Guide 3. Semi finished products

6. Equipment

3.1 films

6.1 Machinery & Molds Tianan Biologic No. 68 Dagang 6th Rd, Beilun, Ningbo, China, 315800 Tel. +86-57 48 68 62 50 2 Fax +86-57 48 68 77 98 0 enquiry@tianan-enmat.com www.tianan-enmat.com 1.6 masterbatches

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

Huhtamaki Forchheim Sonja Haug Zweibrückenstraße 15-25 91301 Forchheim Tel. +49-9191 81203 Fax +49-9191 811203 www.huhtamaki-films.com

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

Cortec® Corporation 4119 White Bear Parkway St. Paul, MN 55110 Tel. +1 800.426.7832 Fax 651-429-1122 info@cortecvci.com www.cortecvci.com

Eco Cortec® 31 300 Beli Manastir Bele Bartoka 29 Croatia, MB: 1891782 Tel. +385 31 705 011 Fax +385 31 705 012 info@ecocortec.hr www.ecocortec.hr

2. Additives/Secondary raw materials

Arkema Inc. Functional Additives-Biostrength 900 First Avenue King of Prussia, PA/USA 19406 Contact: Connie Lo, Commercial Development Mgr. Tel: 610.878.6931 connie.lo@arkema.com www.impactmodifiers.com

Taghleef Industries SpA, Italy Via E. Fermi, 46 33058 San Giorgio di Nogaro (UD) Contact Frank Ernst Tel. +49 2402 7096989 Mobile +49 160 4756573 frank.ernst@ti-films.com www.ti-films.com 3.1.1 cellulose based films

The HallStar Company 120 S. Riverside Plaza, Ste. 1620 Chicago, IL 60606, USA +1 312 385 4494 dmarshall@hallstar.com www.hallstar.com/hallgreen

Rhein Chemie Rheinau GmbH Duesseldorfer Strasse 23-27 68219 Mannheim, Germany Phone: +49 (0)621-8907-233 Fax: +49 (0)621-8907-8233 bioadimide.eu@rheinchemie.com www.bioadimide.com

Sukano AG Chaltenbodenstrasse 23 CH-8834 Schindellegi Tel. +41 44 787 57 77 Fax +41 44 787 57 78 www.sukano.com

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

alesco GmbH & Co. KG Schönthaler Str. 55-59 D-52379 Langerwehe Sales Germany: +49 2423 402 110 Sales Belgium: +32 9 2260 165 Sales Netherlands: +31 20 5037 710 info@alesco.net | www.alesco.net

Minima Technology Co., Ltd. Esmy Huang, Marketing Manager No.33. Yichang E. Rd., Taipin City, Taichung County 411, Taiwan (R.O.C.) Tel. +886(4)2277 6888 Fax +883(4)2277 6989 Mobil +886(0)982-829988 esmy@minima-tech.com Skype esmy325 www.minima-tech.com

NOVAMONT S.p.A. Via Fauser , 8 28100 Novara - ITALIA Fax +39.0321.699.601 Tel. +39.0321.699.611 www.novamont.com

WEI MON INDUSTRY CO., LTD. 2F, No.57, Singjhong Rd., Neihu District, Taipei City 114, Taiwan, R.O.C. Tel. + 886 - 2 - 27953131 Fax + 886 - 2 - 27919966 sales@weimon.com.tw www.plandpaper.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

Roll-o-Matic A/S Petersmindevej 23 5000 Odense C, Denmark Tel. + 45 66 11 16 18 Fax + 45 66 14 32 78 rom@roll-o-matic.com www.roll-o-matic.com

MANN+HUMMEL ProTec GmbH Stubenwald-Allee 9 64625 Bensheim, Deutschland Tel. +49 6251 77061 0 Fax +49 6251 77061 510 info@mh-protec.com www.mh-protec.com 6.2 Laboratory Equipment

MODA : Biodegradability Analyzer Saida FDS Incorporated 3-6-6 Sakae-cho, Yaizu, Shizuoka, Japan Tel : +81-90-6803-4041 info@saidagroup.jp www.saidagroup.jp 7. Plant engineering

President Packaging Ind., Corp. PLA Paper Hot Cup manufacture In Taiwan, www.ppi.com.tw Tel.: +886-6-570-4066 ext.5531 Fax: +886-6-570-4077 sales@ppi.com.tw

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

bioplastics MAGAZINE [01/12] Vol. 7

Suppliers Guide 8. Ancillary equipment

10. Institutions

9. Services

Osterfelder Str. 3 46047 Oberhausen Tel.: +49 (0)208 8598 1227 Fax: +49 (0)208 8598 1424 thomas.wodke@umsicht.fhg.de www.umsicht.fraunhofer.de

Institut für Kunststofftechnik Universität Stuttgart Böblinger Straße 70 70199 Stuttgart Tel +49 711/685-62814 Linda.Goebel@ikt.uni-stuttgart.de www.ikt.uni-stuttgart.de

10.2 Universities

10.1 Associations

narocon Dr. Harald Kaeb Tel.: +49 30-28096930 kaeb@narocon.de www.narocon.de

BPI - The Biodegradable Products Institute 331 West 57th Street, Suite 415 New York, NY 10019, USA Tel. +1-888-274-5646 info@bpiworld.org

nova-Institut GmbH Chemiepark Knapsack Industriestrasse 300 50354 Huerth, Germany Tel.: +49(0)2233-48-14 40 Fax: +49(0)2233-48-14 5

European Bioplastics e.V. Marienstr. 19/20 10117 Berlin, Germany Tel. +49 30 284 82 350 Fax +49 30 284 84 359 info@european-bioplastics.org www.european-bioplastics.org

Bioplastics Consulting Tel. +49 2161 664864 info@polymediaconsult.com

Michigan State University Department of Chemical Engineering & Materials Science Professor Ramani Narayan East Lansing MI 48824, USA Tel. +1 517 719 7163 narayan@msu.edu

University of Applied Sciences Faculty II, Department of Bioprocess Engineering Heisterbergallee 12 30453 Hannover, Germany Tel. +49 (0)511-9296-2212 Fax +49 (0)511-9296-2210 hans-josef.endres@fh-hannover.de www.fakultaet2.fh-hannover.de

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Feb. 20-22, 2012

April 23-24, 2012

Innovation Takes Root 2012

Biopolymer World Congress

Omni ChampionsGate Resort in Orlando, Florida, USA.

NH Laguna Palace Hotel, Mestre-Venice (Italy)

www.innovationtakesroot.com

www.biopolymerworld.com

Feb. 28-29, 2012

April 25-26, 2012

Solpack 1.0

Durable Bioplastics

Munich, Germany

Minneapolis, MN, USA

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March 7-8, 2012

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Bioplastics Compounding & Processing

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May 9-10, 2012

5. BioKunststoffe Hannover, Germany

www.hanser-tagungen.de/

March 13-14, 2012

World Biofuels Markets

May 10-11, 2012

www.worldbiofuelsmarkets.com

2nd Congress on Biodegradable Poplymers Packaging

March 14-15, 2012

www.biopolpack.unipr.it/preregistration.htm

Rotterdam, The Netherlands

5th International Congress on Bio-based Plastics and Composites Cologne, Germany

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Centro Congressi Fiera di Milano – Rho, Milano, Italy May 14-18, 2012

SPE Bioplastic Materials Conference

Renaissance Seattle Hotel - Seattle, Washington USA www.4spe.org

March 20-22, 2012

Green Polymer Chemistry

May 15-16, 2012

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2nd PLA World Congress presented by bioplastics MAGAZINE

March 21-22, 2012

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Maritim Hotel, Cologne, Germany

Holiday Inn City Center, Munich Germany

Plastics in Automotive Engineering Mannheim, Germany

May 16-18, 2012

www.kunststoffe-im-auto.de

SPE Bioplastic Materials Conference

March 27-30, 2012

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BioPlastek 2012

Renaissance Seattle Hotel, Seattle, Washington USA

An Interactive Forum on Bioplastics Today & Tomorrow Westin Arlington Gateway, Arlington, VA, USA

June 13-15, 2012

http://bioplastek.com

Hilton - Downtown, San Francisco, USA www.BioPlastix.com

March 29-30, 2012

Sus Pack 2012 Conference on Sustainable Packaging Cologne, Germany www.suspack.eu

Orlando, USA

June 19-20, 2012

Biobased materials WPC, Natural Fibre and other innovative Composites Congress Fellbach, near Stuttgart, Germany

April 1-5, 2012

NPE 2012

BioPlastics: The Re-Invention of Plastics

visit bioplastics MAGAZINE at booth 58047

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naro.tech 9th International Symposium

April 18-21, 2012

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Erfurt, Germany Oct. 2-4, 2012

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April 19-20, 2012

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2nd Congress on biodegradable polymer packaging

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bioplastics MAGAZINE [01/12] Vol. 7

Companies in this issue Company

Editorial Advert

A&O FilmPAC Ltd

Company Gneuss, Inc.

34,37

Company

Editorial Advert

plasticker

Aalto University

Grace Biotech Corporation

Polyone

6, 34

ADM

3, 5

Hallink

Polyvel, Inc.

Aeskulap

alesco GmbH & Co. KG API S.p.A.

Hallink RSB Inc.

President Packaging Ind., Corp.

Heritage Plastics

PTT MCC Biochem

Hochschule Bremen

PTT Public Company

45, 63

Huhtamaki Forchheim

Purac

6, 34, 36, 52, 54

Recycling Solutions

Reifenhäuser

Renault

Resirene, S.A. de. C.V.

32, 34

Rhe Tech Inc

Arkema

15, 43

Ashland Chemical

Hutchinson

AstroTurf

Hyundai-Kia Motors

6, 50

Austin Novel Materials, North America

IAC (International Automotive Components)

Automanager.tv

IDES

33, 34

Avantium

igus

BASF

Imperial College London

BASF Color Solutions

IndiaMART.com

BioAmber

Innovia Films

BIOCORE

INRA Transfert

Biomer

Institut for bioplastics & biocomposites

10, 21, 54

Institut für Umweltstudien Weibel & Ness GmbH

Biopolymers & Biocomposites Research Team 34,37 Biosphere

BMBF

BMELV

10, 21, 22

BPI - The Biodegradable Products Institute

Braskem

16, 34, 38

Brooks Sports

CAPAX environmental services

Cereplast

Chalmers Tekniska Hoegskola AB

Chase Plastic Services, Inc.

Chemtrusion, Inc.

Chimar Hellas AE

Chinaplas

CIMV

CIRMAP

Coca-Cola

Colette

Composites Evolution

Continental Tyres Germany

Cortec® Corporation

CTAG

Denso

Deutsches Kunststoff Institut

DSM Bio-based Products & Services B.V.

DuPont

13, 15, 34 62

Eastman Chemical Co.

Ecole des Mines de Douai

Ecomann 34

EMS

Energy research Centre of the Netherlands

Eops

Erema

43 64

Evonik

8, 34

ExTech

Extrusa

FAS Converting Machinery AB

Iowa State University

34,37

Jamplast, Inc.

Jarden Plastic Solutions

Julius Kühn Institut

Kal

Katholieke Universiteit Leuven

Kingfa Sci. & Tech. Co., Ltd

Kunststoffwerk Voerde Hueck & Schade

Kureha America Inc.

Latvian State Institute of Wood Chemistry

Leistritz

33, 34

Lili Giacobino

Limagrain Céréales Ingrédient

LipoFIT Analytic

LTL Color Compounders, Inc.

34,37 33

LyondellBasell

M-Base Engineering + Software

Materia Nova Research Center

Mathelin Bay Associates LLC

Max-Plack-Institute for Plant Breeding

Mazzucchelli

Mercedes-Benz

Merquinsa North America, Inc.

33, 34

Metabolix

5, 28

Michael Young

Michigan State University

Minima Technology Co., Ltd.

4, 34, 38

Mitsubishi Chemical

Mitsui & Co.

7 8

Nano4

Nanobiomatters Industries, S.L.

narocon

National Technical University of Athens

FkUR

6, 9, 34, 38 2, 62

Flaxland

FNR

10, 21, 22

Ford

10, 20, 33

Nexeo Solutions

Four Motors

nova-Institut

Fraunhofer ICB

8, 16, 43, 58

16, 59, 64

Fraunhofer IME

Novamont

63, 68

Novozymes

16 5

NatureWorks

6, 34, 37, 47, 55

Fuji Xerox

Galactic

6, 47

OWS

Gattinoni

Phoenix Plastics L.P.

Plastic Suppliers

Gevo

Plastic Technologies, Inc.

bioplastics MAGAZINE [04/11] Vol. 6

64 62

Optimum

Southern Clay Products

SPI (NPE)

SPI Bioplastics Council

34, 36

Stichting Dienst Landbouwkundig Onderzoek

Südzucker

Sukano AG 40

SYNPO, akciová společnost

Synthomer

Syral

Szent Istvan University

Taghleef Industries SpA, Italy

Tarkett SA

Technical University Clausthal

Teinnovations Inc. (PSM Bioplastic)

34, 36

Tekes

Teknor Apex Company

32, 34

Telles

3, 5

The Energy and Resources Institute

62 63 63

15, 23

TP Composites, Inc.

Tradepro, Inc.

Transmare Compounding B.V.

62 6,54

Uhde Inventa-Fischer GmbH

63 34, 38

Universität Stuttgart

University of Mons

University of Wisconsin-Madison

21, 28

University Stuttgart

UPM

Valtion teknillinen tutkimuskeskus

Virent

Volkswagen

VTT

Wacker Chemie

Waterless Company

Wei Mon

WEI MON INDUSTRY CO., LTD.

Werzalit

Wisconsin Institute for Discovery

Zhejiang Hangzhou Xinfu Pharmaceutical Co., Ltd

Toyota

Uhde Inventa-Fischer

Sustainable Composites

Wuhan Huali 63

Solagro Association

United Soybean Board

10, 54

Natur-Tec® - Northern Technologies

Tianan Biologic

Möller

Simcon Kunststofftechnische Software

Tianan Biologic

62 62

The HallStar Company

Fiat

Sidaplax

FH Hannover

Fraunhofer UMSICHT

Shenzhen Brightchina

MODA

33, 34

Institute for Energy and Environmental Research Heidelberg

RTP Company Showa Denko Europe GmbH

Lubrizol

17 5

Roll-o-Matic A/S

Institut National de la Recherche Agronomique 43

Rheinchemie Rodenburg

62,63 63

Rhein Chemie Rheinau GmbH 63

MANN+HUMMEL ProTec GmbH

Ecospan, LLC

European Bioplastics e.V.

Editorial Advert

26 34

2nd PLA World

C o n g r e s s

15 + 16 MAY 2012 * Munich * Germany

PLA

is one of the bioplastics with the largtest market significance. The versatile bioplastics raw material is made almost completely from renewable resources. It is being used for packaging applications, for fibres in woven and non-woven applications. Even the automotive industry and consumer electronics are already applying PLA. Blending PLA with other bioplastics or other blendpartners as well as mixing it with natural fibres such as flax, hemp or kenaf broadens the range of applications even more.

Experts from all involved fields will share their knowledge and contribute to a comprehensive overview of today‘s opportunities and challenges and discuss the possibilities, limitations and future prospects of PLA for all kind of applications.

Latest developments Market overview High temperature behaviour Barrier issues Additives / Colorants Applications Reinforcements End of life options

The 2 full-day-conference will be held on the 15th and 16th of May 2012 in the Holiday Inn Munich City Centre Munich, Germany.

Online registration is open at www.pla-world-congress.com

That‘s why bioplastics MAGAZINE is now organising the 2nd PLA World Congress.

The 2nd PLA World Congress is the must-attend conference for everyone interested in PLA, its benefits, and challenges. The conference offers high class presentations from top individuals in the industry and also offers excellent networkung opportunities.

www.pla-world-congress.com

Tel.: +49 (2161) 6884469