bioplastics MAGAZINE 03-2014 by bioplastics MAGAZINE

03 | 2014

ISSN 1862-5258

May/June

Highlights Injection Moulding | 10

bioplastics

MAGAZINE

Vol. 9

Thermoset | 34

1 countries

... is read in 9

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Editorial

dear readers Busy days – these days! … After Chinaplas, interpack and quite a number of conferences even our 3rd PLA World Congress will be over when you read this. For this issue we promised a comprehensive review for both Chinaplas and interpack. However, as Chinaplas did not show very much breaking news apart from what we covered in the show preview, we just have a small review for this event. All in all it could be noticed that an increasing number of Chinese companies (suppliers as well as visitors/buyers) are more and more interested in the biobased origin of raw materials and are not so much focused only on the biodegradability any more. Suppliers of PBAT for example are looking for biobased 1,4-BDO … May/June

ISSN 1862-5258

For interpack there is no review at all. It turned out that the preview already covered most news. The few items that are related to interpack in this issue are marked with a small interpack icon. The other editorial focus topics in this issue are thermoset and injection moulding.

03 | 2014

Highlights Injection Moulding | 10 Thermoset | 34

bioplastics

We hope you enjoy reading bioplastics MAGAZINE

MAGAZINE

As usual this issue is once again rounded off by a number of industry and applications news…

Vol. 9

Some recent news and reports raise new questions and will certainly be discussed in our upcoming issues. These are the news about “renewable polyoleﬁns” and other conventional thermoplastics by applying a mass balance e approach. Please read my comment on page 6 and stay tuned…

Sincerely yours

... is read in 91 countries

Michael Thielen

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bioplastics MAGAZINE [03/14] Vol.9

Content

03|2014

May/June

Injection Moulding Injection moulding of PTT . . . . . . . . . . . . . . . . . . . . . . . . . . . .10 The blend makes the difference . . . . . . . . . . . . . . . . . . . . . . .14

From Science & Research New biocomposites for car interior . . . . . . . . . . . . . . . . . . . .18 PHA from sunlight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .20 Talc ﬁlled PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .24 Editorial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

Supercritical Fluid assisted injection moulding . . . . . . . . . . .38

News . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 - 7 Application News . . . . . . . . . . . . . . . . . . . . . 22

Applications

Event Calendar . . . . . . . . . . . . . . . . . . . . . . . 53

White teeth – Naturally! . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .23

Suppliers Guide . . . . . . . . . . . . . . . . . . . . . . 50

Materials

Companies in this issue . . . . . . . . . . . . . . . 54

New high heat resistance grade . . . . . . . . . . . . . . . . . . . . . . .27 Green biocomposites for architects. . . . . . . . . . . . . . . . . . . . .28

Events

PHA Modiﬁers for PLA Fiber . . . . . . . . . . . . . . . . . . . . . . . . . .21

Biobased packaging 2015 . . . . . . . . . . . . . . . 8

Renewable 5-HMF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .41

Biobased materials for automotive . . . . . . . 8 applications 2015

Thermoset

Chinaplas 2014 - Review . . . . . . . . . . . . . . . 17

Co-creation makes bio-resins work . . . . . . . . . . . . . . . . . . . .34 Biobased Epoxy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .37

Market European and Global Markets 2012 and Future Trends. . . . .42

Microplastic Microplastics in the Environment . . . . . . . . . . . . . . . . . . . . . .46

Basics

bioplastics MAGAZINE [02/14] Vol. 9

Cover: Monika Gniot (Shutterstock)

Cover

A part of this print run is mailed to the readers wrapped in BoPLA envelopes sponsored by Taghleef Industries, S.p.A. Maropack GmbH & Co. KG, and SFV Verpackungen

Envelopes

Editorial contributions are always welcome. Please contact the editorial ofﬁce via mt@bioplasticsmagazine.com.

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

The fact that product names may not be identiﬁed in our editorial as trade marks is not an indication that such names are not registered trade marks.

bioplastics MAGAZINE is read in 91 countries.

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Injection Moulding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .49

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News

Biofore Concept Car uses biomaterials The Biofore Concept Car, presented at the Geneva International Motor Show 2014, showcases the use of UPM’s (Helsinki, Finland) innovative biomaterials in the automotive industry. The majority of parts traditionally made from plastics are replaced with high quality, safe and durable biomaterials, UPM Formi and UPM Grada, which can signiﬁcantly improve the overall environmental performance of car manufacturing. The Biofore Concept Car is designed and manufactured by students from the Helsinki Metropolia University of Applied Sciences.

the past four years of building the Biofore Concept Car, our students have come to see that these biomaterials are of high quality, durable and also offer new design opportunities,” says Pekka Hautala, Project Director from Metropolia.

Parts made of UPM Grada thermoformable wood material are the passenger compartment ﬂoor, centre console, display panel cover and door panels. Grada technology revitalises the forming of wood with heat and pressure, and opens up new opportunities for designs not achievable with traditional methods. UPM Grada’s unique forming properties enable high quality ecological designs which are also visually appealing.

“According to our Biofore strategy, we create value from renewable raw material - wood from responsibly managed forests - and strive for a more resource efﬁcient future. The Biofore Concept Car is a ﬁne manifestation of this. We are proud of the cooperation with Metropolia’s automotive engineering and industrial design students, and what we have achieved together,” Nilsson concludes.

Parts made of UPM Formi biocomposite include front mask, side skirts, dashboard, door panels and interior panels. UPM Formi is a durable, high quality biocomposite for injection moulding, extrusion and thermoforming production. Consisting of renewable ﬁbres and plastic, the material is non-toxic, odourless and uniform in quality. UPM Formi is ideal both for industrial and consumer applications. UPM‘s responsible supply chain combined with use of renewable raw materials ensure a small carbon footprint.

“The Biofore Concept Car showcases the potential of UPM’s biomaterials. Not only for the automotive industry, but also for various other end-uses including design, acoustics - a wide range of industrial and consumer applications. The possibilities are endless,” says Elisa Nilsson, Vice President of Brand and Communications at UPM.

bioplastics MAGAZINE will report in more detail about the biomaterials in upcoming issues. www.bioforeconceptcar.upm.com

“Sustainability is a major subject globally. We were excited to be able to design and build a vehicle that would demonstrate that already today we have biomaterials that are a real alternative to traditional oil-based materials. During

Bio-succinic acid market volume is expected to reach 710,000 tonnes Allied Market Research recently published a new market research report titled “Bio-succinic Acid Market - Size, Share, Trends, Opportunities, Global Demand, Insights, Analysis, Research, Report, Company Proﬁles, Segmentation and Forecast, 2013 - 2020.” As per the study, the global bio-succinic acid market volume is expected to grow at a CAGR of 45.6% between 2013 and 2020. The market revenue was estimated to be $115.2 million in 2013 and is expected to grow to $1.1 billion by 2020. Increase in demand of bio-based chemicals is the major driver for this market. In addition, rising crude oil prices, adoption in newer industrial applications namely, 1,4-Butanediol (BDO), PBS, polyester polyols (polyurethane), and plasticizers will enable faster growth of the market

“The potential for bio-succinic acid market is in the replacement of existing succinic acid and adoption in newer industrial application areas, namely, 1,4-butanediol (BDO), PBS, polyesterpolyols (polyurethane), alkyd resins and plasticizers. These factors together will provide faster growth thrust to the market” states Allied Market Research analyst Sarah Clark. “Presently, price of bio-succinic acid may hinder market growth as it costs higher than petroleum based succinic acid. However, mass production and improvement in production techniques will quickly address the cost viability issue of the bio-succinic acid market” adds Ms. Clark. Moreover, lower volatility of feedstock prices will add to its stable adoption in various application segments. www.alliedmarketresearch.com/bio-succinic-acid-market

bioplastics MAGAZINE [03/14] Vol. 9

News

SABIC launches renewable polyoleﬁns

BASF presents biobased Ultramid

SABIC (headquartered in Saudi Arabia) recently announced that it will launch its first portfolio of certified renewable polyolefins, certified under the ISCC Plus certification scheme, which involves strict traceability and requires a chain of custody based on a mass balance system. The portfolio, which includes renewable polyethylenes (PE) and polypropylenes (PP), responds to the increasing demand for sustainable materials from SABIC’s customers, most notably in the packaging industry, and is applicable for all its polyolefins grades, potentially for all market applications.

BASF now offers high performance Ultramid® (polyamide), which is derived from renewable raw materials. BASF uses an innovative approach that replaces up to 100% of the fossil resources used at the beginning of the integrated production process with certified biomass. The share of renewable raw materials in the sales product is then indicated in the respective quantity. A third-party certification confirms to customers that BASF has used the required quantities of renewable raw materials which the customer has ordered in the value chain.

SABIC is the ﬁrst petrochemicals company to be able to produce renewable second generation PP & PE. SABIC has a unique position in Europe to be able to crack heavy renewable feedstocks made from waste fats and oils in its assets.

The resulting Ultramid, which is produced according to the so called mass balance approach, is identical in terms of formulation and quality but associated with lower green house gas emissions and saving of fossil resources. Also, existing plants and technologies along the value chain can continue to be used without changes.

SABIC worked closely with the International Sustainability and Carbon Certification (ISCC) organization to prove the sustainability of the new feedstock. Independent third party auditors checked and ensured the reliable use of the mass balance system within SABIC. In addition, SABIC worked closely with the Dutch Ministry of Economic Affairs under a Green Deal, on the concept of ‘sustainability certificates’, with the ultimate objective to encourage the production and use of bio-based polyolefins within the industry.

“Consumer demand for products made of renewable raw materials continues to rise,” says Joachim Queisser, Senior Vice President of the Polyamides and Precursors Europe regional business unit. “This offering opens excellent possibilities for packaging ﬁlm manufacturers to market their products accordingly.” MT www.basf.com

The ISCC Plus certiﬁed polypropylene (PP) and polyethylene (PE) materials will be produced initially at SABIC’s production facilities at Geleen in the Netherlands. MT interpack - review

www.sabic.com

Editor‘s note on these two news What new kind of (tricky ?) new approach is this? Or is it not at all tricky but quite reasonable at the end of the day? The idea is to throw a biobased carbon source (from oil crops or even from used oils and fats) into a cracker, which typically stands at the beginning of a complex chemical site with many outlets and inter-connections. Whilst usually running on fossil oil or gas, now a speciﬁc amount of a biomass derived input is fed into it for a while. This biobased content is then allocated to and assigned to a respective output, here an amount of produced renewable plastic. This is completely independent from whether a scientist would detect or not any biobased carbon in the respective product when applying the radio carbon method. At least no one can tell how much biobased content is actually in the end product. The claims however inform about “renewable polyoleﬁn” or a product “Derived from up to 100% renewable feedstock”. It’s all done by calculation. Think about the competitive product, which might be a biobased carbon containing product. Is it OK to call a Mass Balance e calculated product renewable polymer? What do you think needs to be the legitimation for such claims? You may be aware about the CEN TC 411 standardisation which is ongoing and which tries to answer such questions through science and broad stakeholder and expert agreements. The whole approach seems like a huge black box: there is (biobased) input on one end and there is assigned d biobased plastics as output on the other end. It is comparable to 100% renewable electricity. I do buy 100% renewable electricity, knowing well that the power coming from my outlet is being produced by a nearby coal power station... is this OK? This new approach poses a lot of questions. Let this editor’s note be food for thought and let’s discuss these questions in detail in the upcoming issues of bioplastics MAGAZINE. Michael Thielen

bioplastics MAGAZINE [03/14] Vol. 9

News

New online platform at bioplasticsmagazine.com Tap into the online resources of the new bioplastics MAGAZINE news platform! On our website bioplasticsmagazine.com we used to have a News-section, that was, however, not well maintained. This is has changed now. A new platform at news.bioplasticsmagazine.com now offers a new online resource targeted at readers seeking a medium that answers the need for reliable news and informative content with immediate appeal. Visitors will ﬁnd new news-items every day now. Together with the printed bioplastics MAGAZINE, and the new, biweekly bioplastics MAGAZINE newsletter, it offers a platform for professionals in the industry to reach out to prospective partners, suppliers and customers across the globe. The bioplastics MAGAZINE newsletter reaches a targeted audience of some 7000 international bioplastics professionals across all continents. The platform offers readers up-to-date news and advertisers the power to create integrated campaigns, built on interaction between the different media channels and taking advantage of the different strengths of each. For advertisers, a perfect means to add value to opportunity. Visit news.bioplasticsmagazine.com (without www) every day to stay up-to-date.

Newlight Technologies sprints ahead US telecom giant Sprint takes pride in its reputation for bringing sustainable options to market. The company, just recently announced that it is becoming one of the first to use AirCarbon, a new carbon-negative PHA made from greenhouse gas to create plastic products. The material will be used to produce cell phone cases for the iPhone 5 and iPhone 5s. Sprint is the first telecommunications company in the world to launch a carbon-negative product using AirCarbon. AirCarbon is manufactured by California-based sustainable materials producer NewlightTechnologies, using a proprietary carbon capture process to convert air and greenhouse gases (GHGs) into a plastic that has similar durability and performance characteristics to petroleumbased plastics. The conversion technology can synthesize high-performance thermoplastics from a wide range of sources, including methane and/or carbon dioxide from agricultural operations, water treatment plants, landfills, anaerobic digesters, or energy facilities. The PHA material has wide applications, as it can then be formed and moulded into almost any given design. Newlight announced on January 1st of this year that it had achieved successful commercial scale-up of its technology. Today, its commercial site is a four-story operation with a

multi-million pound per year nameplate production capacity, using air and captured methane-based carbon emissions from a farm to produce AirCarbon. “AirCarbon offers a new paradigm in which products we use every day, like cellphone cases, become part of the environmental solution,” said Mark Herrema, Newlight Technologies co-founder and CEO. “Newlight’s mission is to replace petroleum-based plastics with greenhouse gasbased plastics on a commodity scale by out-competing on price and performance – harnessing the power of our choices as consumers to make change. We’re thankful for companies like Sprint, which are helping us realize our founding vision of taking greenhouse gases and turning them into commercially useful products that generate both an environmental and economic beneﬁt.” As Herrema pointed out: “We have spent over a decade optimizing our technology. Today, we have a four-story plant capturing carbon that would otherwise go into the air, using that carbon to make products that would otherwise be made from oil. As a result, our efforts have shifted from technology development to commercial expansion.” KL www.newlight.com

bioplastics MAGAZINE [03/14] Vol. 9

bio PAC bio CAR Biobased packaging

Biobased materials for automotive applications

conference may 2015 amsterdam

conference

» Packaging is necessary.

» The amount of plastics in modern cars is constantly increasing.

» Packaging protects the precious goods during transport and storage. » Packaging conveys important messages to the consumer.

fall 2015

» Plastics and composites help achieving light-weighting targets. » Plastics offer enormous design opportunities.

» Good packaging helps to increase the shelf life.

» Plastics are important for the touch-and-feel and the safety of cars.

BUT:

Packaging does not necessarily need to be made from petroleum based plastics.

consumers, suppliers in the automotive industry and OEMs are more and more looking for biobased alternatives to petroleum based materials.

biobased packaging » is packaging made from mother nature‘s gifts. » is packaging made from renewable resources.

That‘s why bioplastics MAGAZINE is organizing this new conference on biobased materials for the automotive industry.

» is packaging made from biobased plastics, from plant residues such as palm leaves or bagasse. » offers incredible opportunities.

www.bio-pac.info

www.bio-car.info

2014

P R E S E N T S

THE NINTH ANNUAL GLOBAL AWARD FOR DEVELOPERS, MANUFACTURERS AND USERS OF BIO-BASED PLASTICS.

Call for proposals

til Please let us know un

August 31st:

and does rvice or development is se t, uc od pr e th at Wh 1. n an award development should wi or ce rvi se t, uc od pr is 2. Why you think th ganisation does oposed) company or or pr e th (or ur yo at Wh 3. ay also (approx 1 page) and m s rd wo 0 50 ed ce ex t d/or Your entry should no marketing brochures an t be s, ple m sa , hs ap gr oto The 5 nominees mus be supported with ph (cannot be sent back). ion tat en m cu do l ica techn 30 second videoclip prepared to provide a ded from try form can be downloa More details and an en ine.de/award www.bioplasticsmagaz

The Bioplastics Award will be presented during the 9th European Bioplastics Conference December 2013, Brussels, Belgium

Sponsors welcome, please contact mt@bioplasticsmagazine.com

Enter your own product, service or development, or nominate your favourite example from another organisation

supported by

bioplastics MAGAZINE [04/13] Vol. 8

Injection Moulding

Injection moulding of PTT Combining the beneﬁts of renewability with processing and performance advantages

The DuPont PTT contains 20% to 37% renewable content made from starch, using proprietary fermentation and chemical processes, resulting in high-performance resins sui-

Sorona EP is currently available in a selection of grades including unreinforced, medium toughened, and15%, 30% and 45% glass-ﬁber reinforced grades. Table 1. shows grade properties, and comparison with equivalent glass-reinforced PBT and PET polymers.

Diagram 1:

Drying curve of 15% glassreinforced Sorona EP at 120°C

0.05

Moisture e Conten Content (%)

Toyota chose DuPont™ Sorona EP for instrument panel vent louvre vanes on the Prius hybrid electric car to ensure scratch resistance and excellent surface appearance

Grades and properties

0.20

With Sorona EP, DuPont achieved a new combination of advantages in one product – a renewably sourced engineering plastic that can be processed in the same way as PBT and PET, and also offers very low shrinkage and warpage, plus enhanced surface ﬁnish, gloss, and scratch resistance in ﬁnished parts.

Renewably sourced Sorona was one of the bio-based polymers independently certiﬁed to meet the United States Department of Agriculture (USDA) BioPreferred program standards for biobased content. In addition to replacing petrochemical based ingredients with those made with renewable resources, the DuPont PTT also provides a 30% reduction in energy use and a 63% reduction in carbon dioxide emissions compared to incumbent materials such as nylon 6.

0.15

DuPont took up the challenge in developing a new biobased engineering thermoplastic —Sorona® EP PTT (poly trimethylene terephthalate) — working closely with plastics processors and parts manufacturers to prove several key processing and ﬁnished part beneﬁts versus PBT (polybutylene terephthalate), PET (polyethylene terephthalate) and PC/ ABS (polycarbonate/acrylonitrile butadiene styrene) in developmental and commercial programs.

table for engineering applications. A DuPont cradle-to-gate study indicates that the bio-based Sorona EP has a smaller carbon footprint than the traditional fossil route used to make the same polymer. Using bio-feedstock makes Sorona EP less dependent on fossil fuels, yet the performance of these products more than competes with conventional PBT, PET and PC/ABS.

0.10

s the demand for bio-based polymers with renewable materials content, smaller carbon footprint and reduced dependence on fossil fuels continues to grow, the challenge for advanced polymer producers is to offer these environmentally friendly attributes without compromising processing and end-use performance.

During at 120 °C, -40 °C Dew Point DuPont Sorona 3015G NC010 [Melt Temperature / Residence Time]

bioplastics MAGAZINE [03/14] Vol. 9

ISO

Sorona 3301 Unreinforces

Sorona 3015G

PBT-GF15

Sorona 3030G

PBT-GF30

PET-GF30

Sorona 2045G

Stress at Break, MPa

60*

125

109

165

140

158

180

Strain at Break, %

3.5

2.5

2.7

2.5

1.6

2,400

6,500

5,800

11,000

10,000

11,000

16,000

Tensile Modulus, MPa Notched Charpy, kJ/m2 Melting Temperature, °C Density, g/cm3 Mold Shrinkage, 2 mm, %

5.5

228

227

225

227

225

252

227

1.3

1.4

1.56

1.53

1.56

1.7

Parallel

1.3

0.2

0.4

0.2

0.3

0.2

Normal

1.4

0.7

1.1

0.7

1.1

0.8

0.5

Commercial successes “The end-use advantages of Sorona EP — higher strength and stiffness at elevated temperatures, lower warpage and shrinkage, and improved scratch resistance and surface appearance — are already being seen in successful commercial programs,” said Thomas Werner, Business Development Manager, DuPont Performance Polymers. “These attributes make Sorona EP an excellent choice for many precision molded industrial and consumer products, including automotive parts such as instrument panel air conditioning vent louvers — chosen by Toyota for the Prius — electrical/electronic components like connectors, switches, plugs, mobile phone housings, and for furniture.” In its renewably sourced ﬁber form, Sorona is already widely used in residential and commercial carpets, apparel and automotive mats and carpets. Mohawk Group, the worlds largest ﬂooring manufacturer, HBC Bulckaert and Godfrey Hirst Carpets, specify the DuPont biopolymer for durability and stain resistance. In automotive, the Toyota SAI® has ceiling surface skin, sun visor and pillar garnish of Sorona, complementing the car’s eco-friendly design.

Table 1: Properties of currently available Sorona EP grades, and comparison with equivalent glass-reinforced PBT and PET polymers

* Stress at Yield

Processing characteristics and recommendations Material preparation Like PET polyester, pellets of Sorona EP must be dried to a moisture content below 0.02%, using a dehumidiﬁer drier with direct material transfer in a closed hopper, to ensure that optimum mechanical properties are achieved. The dew point of the drier must remain below -20°C. A drying temperature of 120°C is recommended, allowing 4 hours drying for a newly opened bag, and 6-8 hours for a bag that has been opened for more than 1 week.

Flow length Sorona EP exhibits good flow properties, allowing parts with long flow paths and narrow wall thicknesses to be molded easily. Good flow also contributes to generating a high surface finish and glossy appearance, even with glass-fiber reinforced grades. Using a standard 1mm thickness spiral flow test, Sorona EP exhibited 20% greater flow than standard PBT, allowing:

Diagram 3:

Strain at break of Sorona EP as a function of melt temperature and residence time

Recommended cylinder temperature setting as a function of residence time 280 270 260 250 240

Molding Settings

90 °C 270 °C

<2 min

250 °C

2-5 min

235 °C

> 5 min

230

275 °C / 10 min

270 °C / 6 min

250 °C / 15 min

250 °C / 10 min

250 °C / 6 min

ain at Bre

15 0

T Temperat ture

Diagram 2:

Residence Time

Front

Center

Rear

[Melt Temperature / Residence Time] bioplastics MAGAZINE [03/14] Vol. 9

improved ﬁlling of longer cavities

This has been demonstrated in Erichsen scratch hardness testing showing that increasing the mold temperature from 70°C to 90°C increases the scratching force by up to 8N.

reduced part thickness reduced melt temperatures to ﬁll the same cavity, enabling shorter molding cycle time

Effect of mold temperature on shrinkage and warpage

gating simpliﬁcation.

Melt stability - mechanical properties

Shrinkage is caused by thermal contraction and crystallisation of the polymer during the hold pressure and cool down phase. Uneven wall thickness and anisotropic ﬁllers will reinforce a tendency to deform.

Sorona EP exhibits good melt stability without signiﬁcant change in mechanical properties up to a residence time of 10 minutes, when dried to below 0.02% moisture content and molded at a recommended melt temperature of 250°C. The melting point of Sorona EP is 227°C, close to PBT at 225°C.

Non-reinforced Sorona EP exhibits approximately 0.4 to 0.5% lower shrinkage than standard PBT, while parts molded in glass-reinforced Sorona EP have shown less warpage versus standard glass-reinforced PBT. To produce molded parts of Sorona EP with optimum characteristics and low postshrinkage requires a sufﬁcient degree of crystallization. This is inﬂuenced to a large extent by mold temperature.

Melt stability - cylinder proﬁle When molding semi-crystalline polymers such as PBT and Sorona EP PTT, the cylinder temperature proﬁle should be adjusted as a function of residence time to minimize degradation, maintain stability, and achieve an optimum balance of homogeneity while maintaining the high molecular weight of the molten material.

A mold temperature of 80°C is sufﬁcient to produce parts with low postshrinkage. Higher mold temperatures (>85°C) contribute to reduced dimensional changes caused by post-crystallization (post-shrinkage).

Effect of mold temperature on aesthetics Superior surface quality and a high gloss effect require a minimum temperature of 80°C in a polished mold. Increasing the mold temperature to 90°C will further improve the excellent scratch resistant properties of the DuPont PTT.

Meeting growing demand for bio-based polymers With Sorona EP, DuPont has developed a PTT polymer that meets the growing demand for a sustainable bio-based

Photo 1: excellent high gloss ﬁnish of unreinforced Sorona EP pigmented using a masterbatch

engineering plastic with in-use performance equivalent to, or better than, PBT, PET or PC/ABS polymers. It also exhibits a molding behavior similar to high-performance PBT in conventional injection molding equipment. Processing conditions are essentially the same with some minor adjustments, following DuPont processing recommendations. Compared to PBT, glass-ﬁber reinforced Sorona EP exhibits better mechanical properties at elevated temperatures including enhanced strength and dimensional stability, stiffness, lower warpage and shrinkage, and improved surface appearance. The new backbone chemistry of PTT provides new functionality to a PBT-like polymer. A skilled molder with PBT expertise should have no concerns about testing Sorona EP. The reward will be in the added value of higher quality ﬁnished components. www.dupont.com

Backbone chemistry of Sorona EP PTT

Shrinkage and post-shrinkage of Sorona EP PTT polymers Annealing conditions: 1 hour in an oven at 120°C

Standard PBT after annealing Standard PBT

C OH

1,3 Propanediol

Terephthalic Acid

(PDO)

O O

DuPont Sorona 3301 NC010 after annealing DuPont Sorona 3301 NC010

1.20

O O

1.60

Polytrimenthylene terephtalate

1.00

0.80

1.40

HO HO

1.80

Diagram 4:

Shrinkage e (%)

Diagram 5:

110

Melt elt Temperature (°C)

bioplastics MAGAZINE [03/14] Vol. 9

9th & 10th September 2014 Thon EU Hotel, Brussels

Bioeconomy in Action – from Rhetoric to Reality e Bio-based Global Summit will inform decision akers from the Bio Chemical, Plastic, Polymer d Packaging markets of the real potential d viability of the Bio economy – in terms of emicals, plastics and fuels. Speaking at the Bio-based Global Summit will be: O Maira Magnani, Ford Research & Advanced Engineering Europe O esse Putzel, Senior Sustainability Manager, BAM (Packaging Design Agency) O Dr John Williams, Group Technical Director, Sinvestec O Rulande Henderson, PhD, Commercial Director, Econic Technologies and many more Book your place now delegates rates are: ore 23rd June 2014 – Early bird delegate rate of €895 elgian VAT or after 23rd June 2014 – Normal delegate rate of €1,000 elgian VAT can book online at:

www.biobased-global-summit.com Organised by

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Media partners

Injection Moulding

ith the exception of niche applications, bioplastics have so far failed to make a breakthrough on mass markets – often due to their unsatisfactory material properties or the lack of cost-effective production processes. Using sophisticated chemical techniques, the Munich (Germany) based chemical company WACKER has developed a solution for eliminating the inherent weaknesses of bioplastics. The improved physical properties of these materials mean they can now be processed like standard thermoplastics, using methods such as injection molding, extrusion or thermoforming.

The blend W makes the difference Selectively optimizing the material properties of bioplastics

In order to expand their potential, bioplastics must possess properties that justify their use over traditional plastics. In addition to that requirement, however, bioplastics also have to be compatible with processes commonly used in the polymer industry, such as injection molding. A material that meets some of these requirements is polylactic acid (PLA), which is similar to traditional thermoplastics, and can easily be processed in existing plants. An inherent disadvantage of pure PLA, however, is that it is very rigid and its impact strength is low. Attempts have already been made to compensate this drawback through the use of suitable blends. One US patent, for instance, identiﬁes a variety of aliphatic polyesters that can be blended with PLA to increase the impact strength of the material or make it more ﬂexible [1].

Thermostability of PBS/PLA/Vinnex blends compared to PLA and PBS

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PLA used: Ingeo 4043 D by Nature Works LLC; PBS used: GS Pla FZ 91 PD by Mitsubishi Chemical; binder used: Vinnex 2504 and Vinnex 2510 by Wacker Chemie AG

New Polymers Must Be Compatible with Polymer Industry Processes

4 weeks

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Injection Moulding

Another disadvantage of PLA is its poor resistance to heat, as amorphous PLA begins to soften at temperatures of approximately +60°C, making the material unsuitable for wide range of applications Crystallization generally improves PLA‘s thermostability. However, crystallization results in long processing times, which reduce the cost-effectiveness of the process. Therefore, the goal of development was to avoid costly thermal posttreatment.

Eliminating Poor Heat Resistance and the Miscibility Gap Wacker developers discovered that the heat resistance of PLA increases from +58°C to +65°C when blended with polybutylene succinate (PBS). Further research at Mitsubishi Chemicals (an important PBS manufacturer) demonstrated that this effect can be magniﬁed – increasing heat resistance to +100°C – through the use of a different grade of PBS (see Fig. 1). Making use of this effect, however, meant overcoming yet another hurdle. One study showed that PLA/PBS miscibility is limited and that a miscibility gap arises when PBS is blended with PLA at a concentration of 20% [2]. Researchers also found that the amount of PBS required to produce the desired properties falls within that miscibility gap.

Also, a partially crystalline PBS grade was used with a largely amorphous grade of PLA, which meant that another issue had to be resolved: long-term stability. Studies showed that the properties of PLA/PBS blends containing Vinnex had not changed within eight weeks, and that Vinnex apparently suppresses effectively post-crystallization of the PBS portion of the blend (see Fig. 2). Unlike PLA, PBS is not yet available on the market in large quantities, consequently making it expensive. That situation is set to change in the near future, however. The PTT Public Company Limited of Thailand and Mitsubishi Chemicals are already planning a joint venture (PTT MCC) involving the construction of a production facility in southeast Asia for manufacturing PBS from renewable raw materials.

Improving Cost-Effectiveness with the Right Fillers In order to optimize the cost-effectiveness of the process, studies were performed with the aim of maximizing the PLA content of blends without affecting the thermostability g costs achieved with PBS. One other project involved diluting by adding ﬁllers such as calcium carbonate (chalk) or talc

4000

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A solution to this problem is provided by VINNEX®, a Wacker binder system based on polyvinyl acetate. Studies have demonstrated that Vinnex is compatible with both PLA

and PBS, and that the addition of 15 to 20% Vinnex eliminates the miscibility gap. This results in visibly homogeneous polymer blends in which both polymers can be combined in any mixing ratio and essentially adjusted to the application at hand. The resulting blend combines the advantages of both components.

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Charpy impact strength bioplastics MAGAZINE [04/14] Vol. 9

Injection Moulding

in concentrations of up to 30%. Talc was found to be a particularly good fit, as it significantly increases both the elastic modulus (a measure of rigidity) and impact strength at concentrations of up to 20% (see Fig. 3a/b). Thanks to this effect, manufacturers can now achieve property profiles comparable to those of a number of standard plastics [3].

Fig. 4: Thermoformed parts made of PBS/PLA blends with Vinnex (right) and without Vinnex (left)

The effect on processing was found to be similar: thanks to Vinnex, PLA/PBS polymer blends can easily be processed using traditional injection molding, thermoforming or extrusion equipment. And because Vinnex effectively suppresses recrystallization while improving melt strength, the polymer blend can be thermoformed to yield stable, three-dimensional structures.

Thermoforming Opens the Door to Mass Markets With the aid of a series of prototypes, Wacker developers have now been able to demonstrate that blends of PLA and PBS can be thermoformed to create containers suitable for hot ﬁlling applications (see Fig. 4), opening up mass markets for products such as coffee cups and soup containers. Future consumer behavior may provide an additional tailwind as well: a recent study conducted by consulting ﬁrm Frost & Sullivan showed that food products represent the primary area where consumers demand biodegradable packaging. This requires food-contact approval for use in foods from the EU and the US Food and Drug Administration (FDA), which have already approved selected Vinnex grades. For PBS, food-grade approval in the US is still pending from the FDA, but this is expected in 2015 at the latest.

Conclusion: Modular System for a Broad Range of Applications Polymers based on renewable resources may represent a sustainable alternative to petrochemicals. Until now, however, the properties and processing characteristics of pure biopolymers have often failed to match those of standard thermoplastics. Thanks to the Vinnex binder system, polymers based on renewable raw materials can now be processed just like conventional thermoplastics. The system improves the physical properties of the bioplastics and also makes the materials compatible with each other – the use of Vinnex for optimizing polymer blends is not limited to just the PLA/PBS system, after all. Quite the contrary: a variety of Vinnex grades can be combined with one or more biopolyesters and fillers. This modular concept makes it possible to combine polyhydroxyalkanoates (PHAs) with cellulose acetate (CA) or starch to create polymer blends that, depending on their composition and Vinnex content, exhibit better impact strength, melt strength and flexibility than conventional biopolymers. Vinnex thus opens up an expanding range of applications for bioplastics. For example, the new blends can be processed into food packaging materials, brochures, office supplies and promotional items, parts for electronic appliances or self-degradable gardening and agricultural containers.

bioplastics MAGAZINE [02/14] Vol. 9

Karl Weber Wacker Chemie AG References: [1] Li Shen, Juliane Haufe, Martin K. Patel: Product overview and market projection of emerging biobased plastics. PRO-BIP 2009, Final Report, June 2009. [2] McCarthy et. al, United States Patent 5,883,199 (Mar. 16, 1999). [3] Bhatia, A, Gupta, R, Bhattacharya, S, and Choi, H 2007, “Compatibilty of biodegradable poly(lactic acid) (PLA) and poly(butylene succinate) (PBS) blends for packaging applications,” Korea-Australia Rheology Journal, vol. 19, no. 3, pp. 125-131. [4] Pfaadt, Marcus, Tangelder, Robert, European Patent EP 2 334 734 B1 of October 14, 2009.

Show Review The booth of NatureWorks (Photo: Adsale)

Chinaplas 2014 Review

HINAPLAS 2014, Asia’s largest plastics and rubber fair was running its 28th edition in Shanghai on 23-26 April, setting a number of new records. The exhibition attracted 130,370 visitors during the 4-day show, up 14.26% as compared with last year in Guangzhou. It also sets a new record since its debut in 1983. With the exhibition becoming increasingly international, the number of overseas visitors soars by 19.73% to 36,841 which accounts for 28.26% of total visitors. They are coming from 143 countries and regions mainly from Hong Kong, India, Indonesia, Iran, Japan, Korea, Malaysia, Taiwan, Thailand, Russia, etc. The number of domestic visitors maintains a strong figure of 93,529 with an increment of 12.24%. Besides, CHINAPLAS also marks the new records in terms of exhibition scale and number of exhibitors participated. This year, over 3,000 exhibitors from 39 countries and regions participated in the show, of which over 400 are new to the show. In addition to occupying all 17 exhibition halls in Shanghai New International Expo Center (SNIEC), 13 additional outdoor halls and 6 exhibition suites were also set up at the Central Square of SNIEC to cope with the ever increasing number of exhibitors, resulting in a total exhibition area over 220,000 sqm for this year. In a special Bioplastics Zone in hall N3 again more than 30 companies were listed in the show catalogue to present their products and services in terms of biobased and/or biodegradable plastics. In contrast to previous years the number of companies offering traditional PE or PP filled with starch, straw or bamboo, as well as oxo-degradable additives and compounds was significantly smaller. On the contrary, it could be noticed, that the Chinese companies (suppliers as well as visitors/buyers) do no longer focus just on the biodegradability, but consider the biobased origin of raw materials as increasingly important. Suppliers of PBAT for example are looking for biobased 1,4-BDO …

In addition to the Chinaplas Preview published in the last issue, you can find a few more highlights here. As a first time exhibitor at Chinaplas 2014, Reverdia (a JV between DSM and Roquette) demonstrated the benefits of Biosuccinium™ sustainable succinic acid with 100% bio-based content and lower environmental footprint. The company highlighted the value of partnership with the Chinese plastics industry. Biosuccinium™ enables the production of a biobased PBS (polybutylene succinate), a biodegradable polymer that can be used as a single polymer or in compounds for both durable and biodegradable applications. Other applications include polyols for polyurethanes, coating and composite resins and phthalate-free plasticizers. End products include footwear, packaging, paints and many more. Hydal Biotech is the first and only industrial technology for production of biopolymers in the world which uses waste, used cooking oil, as a source and doesn’t exhaust raw materials from the food chain. It also exhibits highest productivity and yield of the polymer thanks to patented know-how and used resources. Hydal Biotech is a Czech-Chinese Joint Venture founded by two partners that reached significant synergic effects. Its founders are Nafigate Corporation and Jiangsu Clean Environmental Technology Co., Ltd. Czech Company Nafigate Corporation, specialized in the transfer of high-tech technologies, has introduced its unique Hydal biotechnology to the Chinese market. Nafigate has partnered on this project with China-based Suzhou Cleanet, a company that collects and processes waste cooking oil at an increasing number of locations in China. Shanghai Disoxidation Enterprise Development Co., Ltd., introduced a UV-stabilized grade of their PBAT based BSR 09 material. Thus it is now perfectly suited for mulch film applications. Tests run in northern part of China showed very positive results. BSR 09 has been successfully produced since 2010, and acquired certificates of EN13432, ASTM D6400 and AS4736.MT

www.chinaplasonline.com

bioplastics MAGAZINE [06/13] Vol. 8

From Science & Research

New biocomposites for car interior

he development of novel biocomposites based on new biopolymers, reinforced with natural fibers, nanofillers and additives, for applications in automotive interior parts was the goal of the European Research Project ECOplast, which is now successfully nearly completed. The project consortium incorporates 13 partners coming from 5 European countries and is led by the Spanish Galician Automotive Technological Centre (CTAG, (Porriño Pontevedra, Spain) Requirements for interior parts in automotive are manifold: mechanical stability, odor, fogging and temperature resistance are only a small sample of what the producers have to take care for. Bioplastics which are available nowadays do not meet the requirements of the automotive industry. Pablo Soto from Grupo Antolin, a Spanish automotive supplier who was a partner in the Ecoplast consortium, states: “We recognize that the automotive industry wants to use bio-based plastics and natural fibers on the condition that they pass the requirements for materials in interior parts that are really challenging, at a level of price similar to current materials“. Before Ecoplast started, the insufficient temperature resistance of PLA, for example, and the fogging behavior and volatile emissions of PHB prevented their use in car interiors.

Improvements of PHB and PLA In the past, the odor and fogging of PHB limited its use in cars. Within the scope of the Ecoplast project, AIMPLAS (Paterna, València, Spain) studied the efficiency of supercritical CO2 (sc-CO2) in the reduction of the volatiles. A significant reduction of the organic volatile substances by up to 80 % was achieved. However, the process was too expensive and instead of it a new formulation of PHB which reduces volatiles was developed. The components that lead to fogging or volatiles emissions were successfully identified and replaced by others. As a result BIOMER (Krailling, Germany) now offers a new formulation of PHB for car interior parts. Corbion (Gorinchem, The Netherlands) improved the temperature resistance of PLA by using PDLA nucleated PLLA materials, so-called nPLA. A separately developed high impact blend (n-PLAi) was used to overcome the low impact strength of PLA.

material showed increased impact and tensile strength values. With rising amount of fibers the heat resistance, heat deflection temperature, HDT (A), of the composite material increases (see fig. 1).

Fig. 1: Heat deﬂection temperature in dependence of ﬁber amount

All in all, great improvements in the proprieties of the PLAcellulose ﬁbre composites were achieved, just a few of the requirements for car interiors, as fogging or resistance to humidity, need further developments.

PHB long natural fiber composites Compression molding appeared as the best option to reinforce PHB with fiber mats. The best results were achieved by Aimplas with impregnated flax mats. Using this process the PHB penetrates completely through the mats. The obtained samples show good mechanical properties and a nice appearance (see fig. 2). Values for unnotched Charpy impact reached more than 40 kJ/m2 and the flexural modulus over 3 GPa.

Compatibilty of wood fibers The incompatibility of hydrophilic wood fibers and hydrophobic thermoplastic matrices causes weakness to composite material strength properties, especially impact strength. VTT (Espoo, Finland) modified the cellulose fiber surface to be more compatible with polymer matrix utilizing a new dry compacting method and reactive plasticizers or additives capable of forming bridges between fiber and polymer matrix. The resulted PLA-cellulose fiber composite

bioplastics MAGAZINE [03/14] Vol. 9

Fig. 2: PHB with ﬂax mats

From Science & Research Improvements using nanocellulose and nanoclays First trials with compounds of n-PLAi with nanocellulose indicated favourable results but the compound has to be optimized, which needs more research work. Preliminary tests of using nanocellulose as an additive in silk-elastin-like polymer matrices were promising, too. NBM has developed the first organomodified clays for the use in PLA compounds (see fig. 3). The preparation included the formulation, optimization and fabrication of the nanofillers according to proprietary purification and surface modification technology. A compound based on n-PLAi with 5 wt % of this new nanoadditive based on natural clays complies with all requirements defined in the project.

Fig. 3: TEM image of nanoclay in PLA matrix

New protein-based copolymer Basic research for the development of a new protein-based copolymer using silk-like crystalline and elastin-like ﬂexible blocks (silk-elastin-like polymers, SELP), performed by the University of Minho, and for the scale-up of SELP production revealed good results. More details of this can be found in Casal et al. (2014). Additionally, the methodology and knowhow to produce biocomposites based on these novel polymers was developed within the Ecoplast project in collaboration with PIEP.

New approaches to the biocomposites processing technologies PIEP addressed the possibility of processing the target biocomposites using a more energy efficient technology – iCIM: integrated twin screw extruder and in-line injection molding (see fig. 4) - and hence profit from the inherent advantages for this type of materials provided by iCIM: shorter residence times, lower shear stresses and superior maintenance of fiber morphology. For the studied n-PLA biocomposite it was possible to obtain, at least, the same level of mechanical performance, when compared to the results achieved with conventional technologies, sustaining the potential of this technology.

Fig. 4: iCIM: integrated twin screw extruder and in-line injection molding Literature: M. Casal, A. Cunha, R. Machado: „Future Trends for Recombinant Protein-Based Polymers: The Case Study of Development and Application of Silk-Elastin-Like Polymers“ in: Kabasci, S. (Ed.): Biobased Plastics: Materials and applications. (Wiley series in renewable resources, 11) Chichester: Wiley, 2014, S. 311; ISBN 978-1-119-99400-8.

Conclusion Ecoplast project results are very promising and may lead to the production of innovative completely bio-based composites which are validated for the automotive industry: Organomodified clays for PLA were developed. A compound based on n-PLAi with 5 wt % of this new nanoadditive complies with all requirements defined in the project. A great improvement of PHB properties was achieved, especially for PHB reinforced with short fibers which yielded results far better than expected. Additionally, of special importance is the development of a new PHB formulation that meets the automotive fogging requirements. PHB reinforced with mats shows interesting results. The materials can be used in different applications. For both materials under investigation in the Ecoplast project, n-PLA and PHB, the cycle times have been remarkably reduced during the project. Material prices are still high but are expected to be drastically reduced upon large-scale industrial commercialization of polymer production. Additionally, the reduction of processing costs has to be one of the principal lines of investigation in the near future.

The partners involved in the project are: Centro Centro Tecnológico Teccnoló ógico o de Automoción Automocción d de e Ga Galicia alicia a (CTAG), (CT TAG),, Spain Spa ain (coordinator) (ccoord dinato or) Asociación de Investigación Investig gació ón de e Materiales Materia ales P Plásticos lástticos y Con Conexas nexass – A AIMPLAS, IMPLAS, Spain PIEP Associação Assocciaçã ão – Polo de Inovação em E Engenharía ngenharría de Polím Polímeros, mero os, Po Portugal ortug gal Biom Biomer, mer, G Germany erm many FKuR Kuns Kunststoff tsto off GmbH, German Germany ny Fra raunhofer-Institut aunhofer-Institut ffür ür U Umwelt-, mwelt-, SicherheitsSicherhe eits- und Energietechnik Energietechn nik UMSICHT, Ger Germany rman ny G Grupo rupo o Antolín Antolín – Ingeniería Ing genie ería S.A., Spain Megat Me egatech ech Indus Industries striess Am Amurrio murrio S.L S.L. L. (MEGATECH), (MEGAT TECH H), Spain NanoBioMatt NanoBioM Matters ers R R&D &D (NMB), S Spain pain Pallmann Maschinenfabrik Mascchine enfab brik GmbH Gmb bH & Co, Germany Germ manyy Cor Corbion rbion (Purac), (Purac), Netherla Netherlands ands Univ University ersitty of Minh Minho ho (U (UMINHO), UMINHO),, Por Portugal rtugal VTT – T Technical ech hnica al Research Centre of Finla Finland, and, Finla Finland and

www.ecoplastproject.com

bioplastics MAGAZINE [03/14] Vol. 9

From Science & Research

I PHA from sunlight New route for bioplastics production in cyanobacteria via photosynthesis By: Minami Matsui RIKEN Center for Sustainable Resource Science Yokohama, Japan

Cyano bacteria

Heterotrophic bacteria

Carbon source

Photosynthesis

(sugars)

Acetyl-CoA

Malonyl-CoA

PhaA Cupriavidus necator

Acetoacetyl-CoA

PhaB

NphT7 Streptomyces sp.

Cupriavidus necator

(R)-3-Hydroxybutyryl-CoA

PhaC Chromobacterium sp.

Polyhydroxyalkanoate (PHA)

Figure 1:

n the past few decades, among all of the bio-based polymers, polyhydroxyalkanoates (PHA) have gained significantly in interest since they were shown to be completely biodegradable in appropriate environments. Another attractive feature of PHAs, apart from their biodegradability, is that they can be synthesized from renewable resources, allowing a sustainable production on a large scale. PHA is a type of storage inclusion that is naturally synthesized by numerous micro-organisms under unfavorable growth conditions. However, the commercialization of PHA has been ongoing, but with limited success due to its high production cost. The use of heterotrophic bacteria for PHA production calls for culture requirements and the supply of carbon sources that contribute significantly to the cost of production. Cyanobacteria, endowed with a photosynthetic system to fix carbon dioxide in a reduced form, are an ideal biosynthetic machine for sustainable production of various industrially important products, such as PHA. The conversion of atmospheric carbon dioxide into a biopolymer by cyanobacteria eliminates the use of costly external carbon sources and helps to achieve a carbon neutral bioplastic production process. The current bottleneck for photosynthetic PHA production using plant and other photosynthetic micro-organisms is to achieve production at an economically viable level. Minami Matsui, Nyok Sean Lau and colleagues from the RIKEN Synthetic Genomics Research Team in collaboration with Sudesh Kumar at Universiti Sains Malaysia have genetically engineered a cyanobacterium to address the challenges in terms of cost and productivity. The genetically modified variant of the cyanobacterium, Synechocystis sp. strain 6803, synthesized an encouraging level of PHA as high as 14% of the dried cellular biomass. So far, this is the highest level achieved in completely photoautotrophic PHA production without the provision of any carbon source. The addition of a carbon source in a small amount (0.4% acetate) had improved PHA production to 41% of the dry weight. Although cyanobacteria have relatively simple nutrient requirements, the provision of exogenous carbon source was found to boost PHA production approximately three-fold. Nonetheless, the amount of carbon source provided was very much lower compared to that required by heterotrophic bacteria to achieve the same PHA production level. In this modified strain, the carbon flux to PHA biosynthetic pathway was enhanced by the introduction of acetoacetyl-CoA synthase from Streptomyces sp. CL190, an enzyme that catalyzes the irreversible condensation of acetyl-CoA and malonyl-CoA to give acetoacetyl-CoA. In addition, a highly active PHA polymerizing enzyme, PHA synthase from Chromobacterium sp., was also introduced to improve the strain’s production efficiency.

Metabolic pathways for PHA production. For the production of PHA in cyanobacteria, the genes, phaA, phaB and phaC were introduced. The condensation reaction of two acetyl-CoA compounds to form acetoacetyl-CoA by PhaA was hypothesized to be thermodynamically unfavorable in cyanobacteria under photosynthetic conditions. Therefore, PhaA was replaced by NphT7 that catalyzes the irreversible condensation of acetyl-CoA and malonyl-CoA to give acetoacetyl-CoA.

bioplastics MAGAZINE [03/14] Vol. 9

To better understand the mechanism that leads to the enhanced photoautotrophic PHA production, gene expression in the PHA overproducer was compared with its unmodiﬁed counterpart. It is surprising to ﬁnd that the activities of enzymes directly involved in PHA synthesis are not the critical factors responsible for the overproduction of PHA in

From Science & Research

Figure 2:

Microscope image shows the likely accumulation of PHA in genetically modiﬁed cyanobacteria. Upper left: Image of cells after staining with nile-red pigment that shows lipid and polymer inclusions. Upper right: Image of cyanobacterial cells. Bottom: Merged image of upper two images. It shows that PHA is accumulating in cyanobacterias cells.

the modified strain. On the other hand, genes encoding proteins involved in several aspects of photosynthetic activities were significantly upregulated in the PHA overproducer compared to the control strain. Results from this study suggest that cyanobacterial cells may utilize enhanced photosynthesis capability to drive the product formation. During PHA formation, the pool of carbon in cyanobacterial cells was constantly being used for the synthesis. In order to cope with the higher production demand, the cyanobacterial cells may increase the carbon fixing capacity to replenish the pool of carbon that was lost to PHA synthesis. At the same time, the flow of newly fixed carbon into cellular processes other than PHA (e.g. amino acids biosynthesis) was limited. Based on the findings of this study, future work can be done to engineer cyanobacteria for the production of various chemicals or biofuels and a similar approach can likely be extended to higher plants. It is hope that the development of a new route for the production of biopolymer only by solar energy will provide a platform for the shift of production process from petroleum-based to bio-based.

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Reference Lau, N.S., Foong, C.P., Kurihara, Y., Sudesh, K. & Matsui, M. RNA-Seq analysis provides insights for understanding photoautotrophic polyhydroxyalkanoate production in recombinant Synechocystis sp. PLoS One. 2014 Jan 22; 9(1): e86368. doi: 10.1371/journal.pone.0086368 (2014).

bioplastics MAGAZINE [03/14] Vol. 9

Application News

Biobased cork – but not from bark Most bottles of wine savored by consumers today reach them in a standard format that was first adopted in the 17th century: glass bottles and cork closures. However, in recent years debate has intensified on the ideal method for sealing bottles and the problems involving this type of cork. Cork is made from oak bark. The tree takes 25 years to give up its first harvest and then every nine years its cork bark can be harvested once again. The long production process and the presence of trichloroanisole (TCA), a fault of cork closures that imparts the aroma of mold (wine taint), has intensified the search for alternatives to ensure the longevity of the beverage, which has given rise to the use of engineered alternatives for bottle stoppers. Now wine lovers have a more sustainable option for their beverage. Nomacorc, the world’s leading producer of synthetic corks, has found an entirely new way to use Braskem’s sugarcane based polyethylene (Green PE) in its products. Called Select Bio, the closures are recyclable and feature the same oxygen-management performance as the conventional line, while also preventing deterioration and waste caused by processes such as oxidation and reduction. “The use of Braskem’s green polyethylene made from sugarcane gave us the materials we needed to offer our customers carbon-neutral corks, which not only helps guarantee the consistency and quality of the wines, but also supports the development of a more sustainable packaging solution,” explained dr. Olav Aagaard, Principal Scientist at Nomacorc. To Braskem, using Green Plastic helps strengthen environmental awareness around the world. “Choices such as Nomacorc’s attest to the high viability and excellent growth potential of this technology, which can be fully employed as a sustainable alternative to the use of fossil fuels,” said Marco Jansen, Renewable Chemicals interpack - review Commercial Director at Braskem. www.braskem.com

www.nomacorc.com

bioplastics MAGAZINE [02/14] Vol. 9

New toys for babies Bioserie (Hong Kong) is first to market with a line of toys that will provide health-conscious parents the safety they demand for their babies by using only plant based, renewable resources in their production. Toys and nursing aids is a significant milestone in Bioserie’s diversification into new consumer product markets and it marks a significant step in the availability of fully biobased toys and nursing aids for babies. For these products Bioserie is using Ingeo™ PLA by NatureWorks and a proprietary blend of biobased components. Even the coloring materials used are specially developed for biopolymers; they are based on sustainable raw materials and meet several global industry and composting standards, including EN 13432 (European Union), ASTM D6400 (USA), BPS GREENPLA (Japan). Stephanie Triau Samman, co-founder of Bioserie says “Most available toys are made of oil based plastics. As a parent, it’s very hard to know for sure that a product won’t have any negative health effects on your baby now or later. The information on toy packages are either inadequate, too technical for a normal person to understand or at times misleading. Bioserie puts an end to this with products derived from plants that are naturally free of any harmful substances associated with oil based plastic toys.” “We believe it is possible to enjoy technology without harming our children’s health and fragile ecosystems of our Earth,” says Kaya Kaplancali, Bioserie CEO. “We are exploring the cutting edge of bioplastics technology to develop products that allow consumers to enjoy life in a healthier, environmentally-responsible way.” Bioserie’s launch product line consists of a Rattle toy, a Stacker toy, a Teether and a Cutlery set. Since the launch of its first accessories for smartphones, starting with iPhone covers in 2010, Bioserie has won international recognition for its technological achievements in the field of bioplastics. It’s one of the first brands in the world to achieve 100% biobased certification by USDA’s BioPreferred program. Bioserie was also nominated for bioplastics innovation awards in 2013 in Germany by Nova Institut and in USA by SPI Bioplastics Council, for developing injection moulded bioplastic products with high durability and heat resistance. MT www.bioserie.com

Applications

White teeth – Naturally! Bio-polymers for high precision injection moulding

Interbros toothbrush are made primarily from renewable plastics. Furthermore, the packaging consists of a 100 % biobased plastic blister combined with a FSC certified carton board. This high value integrated product is the result of expert knowledge in a broad range of bioplastic materials and their processing on existing production equipment. As a result of its recently extended portfolio, FKuR Kunststoff GmbH, Germany, can now provide integrated material solutions fulfilling the requirements of even the most complex products. For many years Interbros GmbH from Schönau/Germany has been pursuing the strategy of developing an integrated toothbrush system made completely from bioplastics. The most important requirements were the use of the existing high end injection moulding and assembling lines while maintaining the quality of the toothbrushes. However, the fitting of the bristle filaments into the injection moulded handle would be a tough challenge for any new material as it has to be within a 10 µm tolerance.

existing high performance lines with the bio based PA ﬁlaments produced by Hahl-Pedex, Germany, and packed into the transparent PLA blister and carton board. If customers require a more heat stable blister pack then a bio-based PET could be used for as a technically proven alternative. This toothbrush impressively demonstrates the success of a combination of several industrial scale plastics manufacturing processes to create an integrated solution from bioplastics. It is another success which proves that the tolerance and stability of FKuR’s materials’ is good enough for industrial scale processing and the injection moulding of very high precision ﬁttings, even with state- of-theart hot-runner moulds. Furthermore, this added value toothbrush has been created without the need for any further investments in moulds or other expensive processing equipment.

By:

After successfully proving the processability of several biomaterials from FKuR’s portfolio for the injection moulding of the handles, Interbros decided on one of the transparent BIOGRADE® materials as it is the best solution to demonstrate the performance of bioplastics for a toothbrush. This material offers a very good

Christoph Lohr FKuR, Willich,Germany Hannes Hauser Sunstar-Interbros, Schönau, Germany

www.sunstarinterbros.com www.hahl-pedex.com www.fkur.com

bioplastics MAGAZINE [03/14] Vol. 9

From Science & Research

Talc T ﬁlled PLA

he limited service temperature of standard PLA is narrowing the application opportunities in many disposable items (i.e. hot beverages cups) as well as in durable applications where service temperature is a relevant property. In general, for semi-crystalline polymers, by increasing the degree of crystallinity it is possible to improve the service temperature. Because of the limited crystallization kinetic of PLA, such polymer is not able to crystallise during standard shaping processes (such as in injection moulding). The usage of nucleating agent improves the crystallization speed, allowing PLA to enhance its properties. Highly micronized talc is a common nucleator for many semi-crystalline polymers (the most common one is polypropylene) and some properties of micronized talc as nucleator for PLA were investigated.

Micronized talc: a functional ﬁller for PLA nucleation

Talc is a natural mineral and it can be identified as an hydrated magnesium sheet silicate. Talc is ranked as the softest mineral (Mohs scale) and it is hydrophobic and chemically inert. Thanks to its platy structure, talc is able to improve mechanical performances of polymers, offering quite high specific surface to better interact with the polymer. Because of its affinity with polymers, talc surface is a perfect substrate for crystal growth.

Experimental Concerning PLA, the ability of different talc grades to enhance crystallization in such polymer was measured. The basic evaluation performed on PLA was related to differential scanning calorimeter (DSC) experiments. DSC is an easy method to evaluate crystallization, recording the exothermic peak, typically observed periment for most of semi-crystalline polymers. But when the cess is very slow, polymer chain structure re-organization can urther melting experiment. to neat PLA, once the polymer is in molten state and the history completely erased, if cooled under controlled conditions rystallization doesn’t take place. By melting the sample still olled conditions, it is possible to record an exothermic peak at °C, showing the PLA crystallization (Fig. 1). ntal evaluation, three different talc grades were considered: talc icronized talc), talc HTPultra5c (ultrafine talc) and talc NTT05 nce talc). By modifying PLA with minor amounts of micronized sible to improve the crystallization behaviour, allowing modified hieve crystallization under cooling conditions. Two different talc rates were evaluated: 1% and 5%, by weight. Modification was rmed by dispersing talc in PLA via a 25mm twin screw extruder, ding talc upstream together with resin; also neat PLA was xtruded, as a reference for the process conditions.

Table 1: half crystallization time for PLA modiﬁed with talc at different isothermal holding temperatures

bioplastics MAGAZINE [03/14] Vol. 9

t1/2 @ 90°C [s]

t1/2 @ 100°C [s]

t1/2 @ 110°C [s]

Neat PLA

596

222

268

PLA + 1% HTP1c

107

PLA + 5% HTP1c

<20

From Science & Research Fig. 1:

DSC curves of neat PLA 50 — Heat FlowEndo Up (mW) 45 — 40 —

In Fig. 2 it is possible to see the different DSC patterns for talc modified PLA at 1% talc HTP1c loading. In general all the three samples of talc gave same results in terms of crystallization temperature. By increasing the talc loading (5%), a higher crystallization temperature is recorded with no specific distinctions between the three talc samples. Talc loading plays a major role in PLA nucleation rather than the talc fineness.

Crystallization

35 — 30 — 25 — 20 — 15 — 10 —

Melting 5— 0—

A relevant experiment, in order to better understand the crystallization conditions of talc modified PLA, is related to isothermal crystallization. Only talc HTP1c was considered as PLA modifier in this experiment. In DSC, the samples were heated up to 200°C at 10°C/min, held 5 min at 200°C and cooled rapidly (at 100°C/min) down to the testing temperature, holding the specimen at testing temperature for a certain time, until crystallization takes place. Time was recorded and it quantifies the crystallization kinetic. Crystallization occurs at a temperature higher than glass transition temperature (Tg) because below Tg, molecular mobility is virtually zero, with no possibility of chain folding. PLA Tg is in the range of 6070°C and experiments were performed from 90 to 110°C as testing (hold) temperature for the isothermal crystallization on PLA modified with talc HTP1c at both 1% and 5% loading. In this experiment, the presence of talc significantly reduces the time to crystallization (generally expressed as time to achieve 50% of crystallization, t1/2) allowing nucleated PLA to achieve crystallinity in a more reasonable time for practical process purposes. In Fig. 3, the behaviour of PLA modification with talc HTP1c at both 1% and 5% loading is shown. For each type of modification, three different temperatures were investigated. In table 1, the t1/2 values are summarized. The behaviour of the other two talc grades is basically similar to HTP1c. Talc loading plays a relevant role in shortening t1/2. Based on such experiments, it appears that moulded PLA items must be kept at relatively high temperature for a certain time to develop the expected degree of crystallinity. Such process can be performed either from the melt of from quenched state, with a visible impact on production costs. The presence of a talc (as nucleator) in the resin helps to shorten such time improving the productivity. The reduction of crystallization time is also driven by the talc concentration. The minimum crystallization time is recorded at 100°C.

-50

-20

100

120

140

160

180 °C

Fig. 2:

DSC crystallization curves of talc modiﬁed PLA 60 — Heat FlowEndo Up (mW) 55 — 50 —

neat PLA

45 — 40 —

PLA + 1% HTP1c

35 — 30 — 25 — 20 —

PLA + 5% HTP1c

15 — 10 — 5— 0— 40

100

120

140

160

180

°C

Fig. 3:

Isothermal crystallyzation curves of talc modiﬁed PLA at different crystallization temperatures

100°C 110°C

140 — Heat FlowEndo Up (mW)

120 —

neat PLA

100 —

80 —

PLA + 1% HTP1c 60 —

40 —

PLA + 5% HTP1c

20 —

0— 0.2

min

bioplastics MAGAZINE [03/14] Vol. 9

Market For nucleation process the type of talc plays a minor role, while for both mechanical and thermal performances the situation is different and the three considered talc grades gave peculiar set of properties.

Impact notched 1 % 5 % Charpy notched @ 23 °C [kj/m2] 8—

In order to have comparable data, all specimens were injected by holding the mould at 30°C, to quench the molten polymer. In such condition, the crystallization didn’t take place in the mould. Specimens were annealed in oven at 110°C per 3 hours to post crystallize PLA.

7—

6—

5—

4—

3—

Neat PLA

HTP1c

HTPultra5c

NTT05

Fig. 5: Charpy noched (according to ISO 179/1eA) of PLA modiﬁed with different loadings of micronized talc. Specimens were annealed 3h@110°C before testing

HDT A (@ 1.82 MPa)

1% 5%

HDT B [°C] 72 — 71 —

In terms of stiffness, the flexural modulus behaviour is shown in Fig. 4. The modification with 1% of talc didn’t affect PLA rigidity, while 5% talc loading recorded a visible improvement, up to 15% for talc NTT05 modification. Thanks to its platy structure, talc is able to improve PLA rigidity. Stiffness enhancement is generally linear with talc loading, but higher loading rates than 5% have not been investigated in this experimental work. The presence of a nucleator let the impact resistance improve versus the neat resin, because of better organized polymer structure. All the samples containing talc gave higher impact resistance than reference (Fig. 5). 1% talc loading is enough to record a significant improving in impact resistance. Ultrafine talc sample (HTPultra5c) shows better results thanks to its very tight particle size distribution. Concerning the evaluation of the service temperature, Heat Distortion Temperature (HDT) has been considered. HDT is the temperature at which a specimen, under a three point bending experiment at a specific load conditions, records a deflection of 0.25mm; it gives an easy indication about the service temperature.

70 — 69 — 68 — 67 — 66 — Neat PLA

HTP1c

HTPultra5c

NTT05

Fig. 6: Heat Distortion Temperature (HDT A 1.82 MPa (according to ISO 75) of PLA modiﬁed with different loadings of micronized talc. Specimens were annealed 3h@110°C before testing

In Figure 6, HDT A (@ 1.82 MPa) data are listed. 1% talc modification doesn’t improve HDT of PLA, while the 5% talc modification offers a visible variation in service temperature. The modification with a high performing talc such as NTT05 allows to record a significant variation in HDT temperature versus the same loading of a highly micronized talc as HTP1c.

Conclusions To allow PLA utilization in applications where service temperature plays the major role, the addition of highly micronized talc represents a good methodology for improving its thermal and mechanical properties, making such composites more interesting for technical applications. The incorporation of talc signiﬁcantly accelerates the crystallization of PLA.

Stiffness 1 % 5 % Flexural Modulus [Mpa] 4900 — 4700 —

From the experimental evidences, it appears that a small amount of talc (1%) is enough to achieve crystallization during molten PLA cooling process. In order to record a better kinetic in crystallization process, a higher talc amount has to be considered (5% loading), in combination with a relatively high mould temperature.

5400 — 4300 — 4100 — 3900 — 3700 — Neat PLA

HTP1c

HTPultra5c

NTT05

Fig. 4: Flexural modulus (according to ISO 178) of PLA modiﬁed with different loadings of micronized talc. Specimens were annealed 3h @110°C before testing

By: Piergiovanni Ercoli Malacari Product and application development IMI Fabi, Milan, Italy

bioplastics MAGAZINE [03/14] Vol. 9

The modification of PLA with talc allows to achieve higher rigidity (without compromising the impact resistance) and, thanks to the nucleation, better service temperature. In order to achieve reliable results in PLA modification, it is necessary to use micronized talc characterized by high degree in purity, by tight particle size distribution and by high lamellarity such as the three talc products examined in this experimental work. In particular, the right selection of talc becomes very important when relatively high talc loadings are considered (i.e. 5%) and the other mechanical properties can be significantly affected by the type of talc. To summarize, for a cost-effective PLA modification, talc HTP1 offers the most attractive set of properties, while for outstanding final mechanical properties, talc NTT05 can record the best-in-class properties still remaining, in terms of costs, as an extender for PLA.

Materials

New high heat resistance grade

fter BIOPLAST 500, their first resin for film applications reaching 51% of biobased carbon according to ASTM D6866, BIOTEC GmbH & Co. KG (Emmerich, Germany) is now achieving new performances with the launch of BIOPLAST 900. Biotec launched the new injection moulding and thermoforming grade at interpack, Düsseldorf in early May 2014. “Products made of BIOPLAST 900 can, unlike some other bioplastics, withstand boiling temperatures without losing their shape, functionality and efficiency. Even at high filling temperatures, the taste of liquids/food is not affected.” says Harald Schmidt, Director of Innovation & New Technology of Biotec. This makes Bioplast 900 perfectly suitable for numerous food applications: coffee capsules, cups for cold as well as for hot drinks or the hot-filling of yoghurt or pudding products. Heat resistance combined with biodegradability - Bioplast 900 shows undisputable environmental advantages, e.g. organic recyclability. For instance, used coffee capsules or other products made of Bioplast 900 are perfectly suitable for industrial composting. The GMO-free product is 69% biobased (potato starch, PLA and other ingredients)

High deﬁnition moulding and short cycle times “Bioplast 900 processability allows moulding of extremely precise and complicated shapes. This innovative bioplastic resin exhibits moulding properties similar to conventional plastics, such as PP and PS.” adds Harald Schmidt.

For example “With a cycle time of 5 seconds for the coffee capsule application, Bioplast 900 meets the challenging cycle time of conventional plastics” states Peter Brunk, Managing Director of Biotec.

Technical data Bioplast 900 is designed for the following applications: injection moulded articles (e.g. cutlery, medical devices, clips, cups for hot and cold drinks) semi-ﬁnished products thermoformed products (e.g. food trays) blend partner in combination with other Bioplast materials (e.g. BIOPLAST GF 106/02)

Products made of Bioplast 900

are applicable for hot ﬁlling (e.g. beverages) are biodegradable according to EN 13432 are recyclable are printable by ﬂexographic and offset printing without pretreatment can be coloured with masterbatches are sealable (hot, RF, ultra sonic) www.biotec.de

interpack - review

bioplastics MAGAZINE [03/14] Vol. 9

Materials

Green biocomposites Green thermoset biocomposites Green biocomposites are composed of natural fibres and biobased matrices. Bio-based matrices and industrial natural fibres composition, including hemp, jute and flax, etc. leads mostly to product price increases, hence generating green thermoset biocomposite market limitations. The option of choosing cheaper available fibres from another natural fibres resource, as in the case of agro-fibres (i.e. agricultural plant fibre residues) is here suggested and applied. The main key that can provide attractive products for architectural applications using available thermoset biocomposites’ production techniques is the innovative product designs that can offer different innovative solutions for modern architectural spaces.

Agro-fibre thermoset biocomposites Commercially, thermoset biocomposites are still not widely available. In spite of this, high interest in such composites is pushing up demand due to the known higher material performance of the thermoset composites than that of the thermoplastic ones. Manufacturing techniques as found in the conventional thermoset composite industry, include both open mould d (e.g. hand lay-up and spray-up) and closed mould techniques (e.g. resin transfer moulding, vacuum infusion and compression moulding). Limitations in the case of agrofibres are their relative short fibre-lengths, while most of the compounding techniques are directed mainly for the usage of

long fibres, fleece and fabrics. In case of bioresins appliance (i.e. biobased thermoset resins), a high curing temperature – one of the most currently available ones in the contemporary market - is another limitation to the whole process. In the following product design case-studies, agro-fibres and bioresins of different types were applied using different thermoset composite techniques. Product designs concepts differed according to the desired architectural outcome, between the form, surface texture, natural fibre’s coloureffect, pigments, glowing additives and others.

Green biocomposites for architecture case studies The following case studies are products designed and manufactured by the author and students of the Faculty of Architecture - University of Stuttgart, Germany within the framework of educational courses. The products are composed up to 70% by weight of agro-fibre contents that were from different origins. The general criteria for designing the green biocomposites here is the appropriate material selection including the agro-fibre and the bioresin as well as the processing techniques. This influenced the designed product outcome as illustrated in Fig. 1.

Fig. 1 By:

Materials and processing interaction with the product design concept

Hanaa Dahy ITKE - (Institute for Building Structures and Structural Design) University of Stuttgart, Germany

Composite form: sandwich panel, particle board, …etc Geometry: Freeform, ﬂat, proﬁled,…etc Color Texture Transparency …

Design + Application

Concept

Materials

Processes

Natural Fibre + Matrix

bioplastics MAGAZINE [03/14] Vol. 9

Physical Processing: Fibre chopping Mold manufacturing Press molding techniques with vacuum assistance Fibre-spray techniques

Natural ﬁbre from Agricultural residues

Bio-resin

Inner Cladding Partitions False-ceiling tiles …

Processing

Chemical Processing: chemical reaction activities combining resin components within molding with the agro-ﬁbres

Materials

for architectural applications Case study – 1: TRAshell Product description Free-form interior and exterior architectural cladding screens made from cereal straw short ﬁbres and plantbased epoxy resin (TRAshell) processed by press-moulding (cold process).

Materials, design and production description Cereal straw, coconut of a reddish brown colour and black coal ash were here applied in their original colours. Agroﬁbres were chopped then combined with a linseed-oil based epoxy resin based on two components that hardened after mixing at room temperature within ~ 24 to 48 hours. The free-form panels were designed in two modules (A) and (B), as illustrated to provide through their combination a desired 3D physical curvature when the patterns are combined as illustrated. The moulds were carved using a robot machine at the faculty of architecture-University of Stuttgart, Germany, and the mixtures were moulded in the forms using different natural ﬁbres and glowing pigments, as illustrated in Fig. 2 and 3.

Fig. 2. TRAshell product design and application simulation as architectural cladding panels in an experimental pavilion, EcoPavilion in the foyer of the faculty of Architecture-University of Stuttgart Pavilion (Photo: B.Milklautsch)

Case study – 2: BiOrnament Product description Coloured laser-cut ﬂat panels (BiOrnament), processed by hand using the lay-up open moulding technique (hot process), for interior and exterior architectural cladding screens.

Materials, design and production description The design sketch illustrates the idea of the pattern that was applied and repeated depending on using both the positive and negative cutting models that would result from the laser cutting procedures after the flat panels were separately manufactured. The product theme depended on the rhythm and diversity within unity using a repetitive pattern with different colourings whether positive or negative cut modules. Therefore, the mixtures were pigmented according to the most suitable product design. Cereal straw fibres were bonded with a biobased epoxy thermoset polymer, composed of three components. Plant oil based (e.g. linseed) epoxidized triglycerides are combined with polycarboxylic acid anhydrides (based on bio-ethanol) and an initiator. This compound was only activated by heat to polymerize. Therefore, the mould was composed of flat metal plates. Fig. 4. Illustration of the ornamental pattern design according to which the developed biocomposite panels were laser cut. Right (Photo: B.Miklautsch)

Fig. 3. TRAshell with glowing glass particles and cereal straw, with coconut ﬁbres, plus raw straw and black coal ash respectively. Photo credit: B.Milklautsch

bioplastics MAGAZINE [03/14] Vol. 9

Materials Conclusions

Case Study-3: Light-24 Product description Pigmented proﬁled panels (Light-24), processed by hand lay-up open moulding technique (cold process) for interior and exterior architectural cladding systems.

Materials, design and production description Palm-fibres were applied in their long natural form, without chopping after being combined in a mat-form, with a bioresin of two components that hardened at room temperature in 24 hours. This bioresin is a vacuum moulding low-viscosity resin prepared from sunflower esters and caprolactones with various additives. Black light pigment was mixed in a ratio of 2% to the total bioresin mixture. Then by hand lay-up technique, the fibres were impregnated with the resin and pressed in several layers and finally pressed as one thick layer.

-The manufactured green biocomposites were tested for weathering conditions (according to Free Weathering TestDIN EN ISO 877) for 24 months as well as mechanically tested. The results were satisfactory and have shown high stability of the material against UV rays and weathering conditions. Mechanical testing showed comparable stiffness values with existing non-structural materials available in local markets that are applied in different architectural applications. This reveals the potential of replacing existing conventional materials with renewable resourced products based on cheap natural ﬁbres and bioresins. Further experimentations and designs should be proceeded by architects, designers and material engineers to reveal more attractive ecological biocomposite products for eco-architecture. - Using agro-ﬁbres and applying them in the form of biocomposites, utilizing biobased matrices based on renewable resources, can offer the opportunity to open a new market for green biocomposite materials with lower prices and acceptable performances, reducing resources consumption and providing more sustainability aspects.

Fig. 5. Illustration of the Light-24 product, during manufacturing and after fabrication. Photo credit: Dahy, H.

3 rd

mistry.eu www.co2-che CO2 as Chemical feedstock – a challenge for sustainable chemistry

1st Day (2 December 2014, 10 am – 7 pm): Political framework and vision: 2nd Day (3 December 2014, 9 am – 7 pm): Chemicals and energy from CO2:

y ye

Entrance Fee s

nue

y (2

Undergraduate and PhD students can attend the conference with a 50 % discount.

Dominik Vogt

bioplastics MAGAZINE [03/14] Vol. 9

Venue

nova-Institute

Materials

Bioplastic from shrimp shell (Photo: Harvard‘s Wyss Institute)

esearchers at Harvard‘s Wyss Institute (Boston, Massachussetts, USA) have developed a bioplastic from chitosan, a form of chitin, which is a powerful player in the world of natural polymers and the second most abundant organic material on Earth. Chitin is a long-chain polysaccharide that is responsible for the hardy shells of shrimps and other crustaceans, the exoskeleton of many insects, tough fungal cell walls — and flexible butterfly wings. The majority of available chitin in the world comes from discarded shrimp shells, and is either thrown away or used in fertilizers, cosmetics, or dietary supplements, for example. However, engineering successes have been limited to fabricate complex three-dimensional shapes using chitinbased materials — until now. The Wyss Institute team, led by Javier Fernandez and Founding Director Don Ingber, developed a new way to process the material so that it can be used to fabricate large objects with complex shapes using traditional casting or injection molding manufacturing techniques. What‘s more, their chitosan bioplastic is biodegradable in appropriate environments and it releases rich nutrients that efficiently support plant growth. “There is an urgent need in many industries for sustainable materials that can be mass produced,“ Ingber said. Ingber is also the Judah Folkman Professor of Vascular Biology at Boston Children‘s Hospital and Harvard Medical School, and Professor of Bioengineering at the Harvard School of Engineering and Applied Sciences. “Our scalable manufacturing method shows that chitosan, which is readily available and inexpensive, can serve as a viable bioplastic that could potentially be used instead of conventional plastics for numerous industrial applications.“ It turns out the small stuff really mattered, Fernandez said. After subjecting chitosan to a battery of tests, he learned that the molecular geometry of chitosan is very sensitive to the method used to formulate it. The goal, therefore, was to fabricate the chitosan in a way that preserves the integrity of its natural molecular structure, thus maintaining its strong mechanical properties.

“Depending on the fabrication method, you either get a chitosan material that is brittle and opaque, and therefore not usable, or tough and transparent, which is what we were after,“ said Fernandez. After fully characterizing in detail how factors like temperature and concentration affect the mechanical properties of chitosan on a molecular level, Fernandez and Ingber honed in on a method that produced a pliable liquid crystal material that was just right for use in large-scale manufacturing methods, such as casting and injection molding. Significantly, they also found a way to combat the problem of shrinkage whereby the chitosan polymer fails to maintain its original shape after the injection molding process. Adding wood flour, a waste product from wood processing, solved this problem. “You can make virtually any shape with impressive precision from this type of chitosan,“ said Fernandez, who molded a series of chess pieces to illustrate the point. The material can also be modified for use in water and also easily dyed by changing the acidity of the chitosan solution. And the dyes can be collected again and reused when the material is recycled. The next challenge is for the team to continue to refine their chitosan fabrication methods so that they can take them out of the laboratory, and move them into a commercial manufacturing facility with an industrial partner. MT

bioplastics MAGAZINE [03/14] Vol. 9

Materials

PHA Modiﬁers for

etabolix (Cambridge, Massachusetts, USA) recently introduced newly developed polyhydroxyalkanoate (PHA) copolymer technology. This development has extended the range of Metabolix’s PHA portfolio with crystallinity ranging from 0% or 60% (Fig.1) to include fully amorphous products. The glass transition temperature (Tg °C) of these PHAs now extends from +5°C down to ~-30°C. Like the more crystalline products in its portfolio, these amorphous PHA products are 100% renewable and widely biodegradable in most environments where microbial activity is present. Metabolix sees exciting opportunities for using these new copolymers to modify and improve the performance of PLA and thereby expand the market potential of PLA fibers and filaments. At Natureworks’ 2014 ITR conference, Metabolix showed early results for modifying PLA using these new PHA copolymers. Metabolix is grateful to Natureworks for their support in this development effort. This work focused on the ability to improve PLA ductility (Fig.2) without negatively impacting the PLA Tg (a common problem with using miscible plasticizers). Metabolix then demonstrated this effectiveness in PLA films by developing a much softer PLA blown film with flex modulus and toughness approaching HDPE. By varying modifier loads, flexibility and toughness in PLA blown and cast film can be adjusted across the range spanning from paper to HDPE. A series of these film prototypes were highlighted by Metabolix at Interpack 2014.

Fig. 4.

Soft PLA monoﬁlaments modiﬁed by Metabolix PHA

PLA

PHA Modiﬁed

More recently, Metabolix is excited by very interesting results in improving PLA ﬁbers using with these new PHA modiﬁers. These developments were also highlighted at the 3rd PLA World Congress in Munich.

Beneﬁts of Modifying PLA ﬁbers with PHA

Fig. 3.

Ductility; Drape

Improving PLA Nonwovens with PHA Modiﬁers

Improved touch and feel; Hand & Elongation Reduced Boiling Water Shrinkage

3500 —

0—

— 60

3000 —

PLA, Paper

-10 10 —

— 50

2500 —

Cups, Lids

-20 20 —

— 40

2000 —

Blister, Cards

-30 30 —

— 30

1500 —

HDPE

Amorphous Range

-40 40 — -50 —

— 20 — 10 —0

-60 — 0

100

Flexural exural Modulus lus (M (MPa)

— 70

Crystallinity [%]

Tg (C)

PLA Ductility Improvement 10 —

1000 —

LDPE

500 — 0— 0

mole % Comonomer

% PHP Copolymer

Fig. 1.

Fig. 2.

Metabolix extended PHA Copolymer technology range

Modifying PLA Flex Modulus with PHA

bioplastics MAGAZINE [03/14] Vol. 9

PLA Fiber The ductility improvement that characterized PHA modified PLA films is also clearly seen in PHA modified PLA fibers. Textile and nonwoven applications for skin contact require a gentle touch and feel. With only a very d of the PLA fibers low loading (< 5%) of PHA the Hand was reduced by 60% (Fig. 3). A soft, silky feel was imparted into the PLA fibers by modulus reduction as well as improved elongation leading to finer filaments and to improved Drape. Furthermore, after drawing and heat set, the PHA enabled hot water shrinkage to be significantly reduced and tenacity improved. By improving the softness characteristics of PLA nonwovens, expanded potential is possible in medical, personal hygiene (where skin contact comfort is important) and home care applications where single use is expected. The PHA modifier doesn’t compromise the 100% renewable makeup of these non-woven single-use materials. In textiles, touch and feel comparable to PET is also an important aesthetic factor for success and PHA copolymer modifiers can enable this softness in PLA filaments (Fig. 4). Furthermore, being polyesters in their backbone chemistry, PHA modifiers are compatible with typical fiber treatments for dying and sizing.

DRIVING A RESOURCE EFFICIENT EUROPE

Distinct Advantages of PHA modifiers in PLA fibers Efficient improvement of touch and feel Compatibility with fiber treatments 100% Renewable (bio-based) Fully Compostable Metabolix is prototyping these PHA modifiers on a pilot scale in nonwoven and monofilament applications and expects to launch several modifier Masterbatches this year and into 2015 when expanded production of the new PHA copolymer products is expected to be available. These products will take advantage of the extended range of PHA copolymer technology that Metabolix has developed and a variety of PLA base resins to provide solutions for expanding the market potential of PLA fibers.

By: Bob Engle VP BioPlastics Metabolix, Inc., Cambridge, MA USA

interpack - review

Save the date! 2/ 3 December 2014 The Square Meeting Centre Brussels More information at: www.european-bioplastics.org

www.metabolix.com

www.conference.european-bioplastics.org bioplastics MAGAZINE [03/14] Vol. 9

Thermoset

Co-creation makes bio-resins work lthough biobased materials are increasingly used in composites, they only represent a small portion of the total market volume. As still biobased d tends to be more expensive than fossil-based, customers are reluctant to pay a price premium just for having a better environmental conscience. This situation is now changing with the introduction of the biobased Beyone™ 201-A-01 resin in highly demanding wind energy applications. Composite systems with this resin provide simultaneously a great end-use performance, cost savings through easier processing, and on top they bring improved sustainability.

In line with these market demands DSM has been introducing several synthetic resins based on renewable resources in the past few years. Objective is to secure future supply of raw materials, decreasing our dependency on fossilbased raw material sources. This will help to ensure security of supply down the value chain. Also, with these renewable raw materials becoming available in larger quantities, we expect to reduce the eco-footprint of our resins and we will be able to pass on that ‘eco advantage’ to our customers.

Composites materials solutions are well established in today’s society as they bring numerous beneﬁts to consumers. Cars can have unique shapes and great aerodynamics, while the low weight of composite parts contributes to lower energy consumption and reduced CO2 emissions. The great corrosion resistance of composites pipes enables continued operation and minimal maintenance in water treatment plants. When renovation of sewer networks is required, open roads and trafﬁc disruption can be avoided by using relining solutions based on composites.

An example of these developments is the introduction of the Synolite™ 7524-N-1 FC resin for artiﬁcial stone. This new DSM material is a biobased unsaturated polyester resin, has a bio-content of 45%, and is produced in line with Good Manufacturing Practice (GMP), the well accepted standard for making products used in contact with food. With this resin the company Compac (Spain) was able to create a new range of stone products suitable for kitchen work surface applications with great aesthetics.

Meanwhile, consumers want more for less: better quality of life, more functionality of the products they buy, and preferably at a lower price. They have become increasingly conscious about the impact they have on the environment, and are looking for ways to reduce their ecological footprint. Consequently, the demand for solutions based on renewable raw materials has been increasing. Obviously this represents a great challenge for the companies they buy from, and for the entire supply chain.

bioplastics MAGAZINE [03/14] Vol. 9

Biobased materials for food contact

Innovation in infrastructure A completely different example of the use of biobased material is the application of Synolite™ 7500-N-1 structural resin for a bio-bridge, installed by FiberCore (Netherlands). Composite bridges can be easily installed because of their low weight. This reduces installation time and potential disruption to trafﬁc and people. Also the lower weight requires lighter foundations compared to bridges made in pure steel or concrete. Because of their very nature, composite materials resist well water, heat and chemicals. Therefore these bridges

Thermoset

only require limited maintenance, while again the impact on the environment and trafﬁc is minimized. The novel Synolite 7500-N-1 resin of DSM is a high strength structural resin (UP) partly based on renewable raw materials (~50 %). The resin can be easily converted through vacuum infusion manufacturing processes into composite components.

Peace-of-mind on cost and the environment While the usage of biobased raw materials is increasing and the bio-feature is said to be highly appreciated by consumers and endcustomers, it is also clear that the market is reluctant to pay a signiﬁcant price premium for bio-solutions. Yet because of the scale of production of biobased raw materials (typically made in lower volumes and still in sub-optimized manufacturing plants) and the availability of biobased sources to make the biobased raw materials, it can be expected they remain more expensive than the fossilbased raw materials for the foreseeable future.

Compac has used DSM’s Synolite 7524-N-1 FC GMP-compliant resin, which features a high content of bio raw materials, to create a new range of artiﬁcial stone products called the Bio Technological Quartz Collection™

Easy installation of composite bridges, based DSM’s novel Synolite 7500-N-1 resin with 50 % biobased raw materials

The introduction of DSM’s novel Beyone 201-A-01 resin for making wind turbine blades may well represent a major change. The current material systems used for making wind turbine blades are mainly based on epoxy resins. While they bring resistance to fatigue, these resins are more sensitive to process variations, and require a time-consuming post-cure for reaching optimum physical properties. Systems based on polyester resins are easier to process but lack the high strength and fatigue resistance required for this demanding application. Moreover, blade manufacturers prefer to use resin systems without styrene, in order to have the best working environment for their operators.

Beyone 201-A-01 vs. WTB Epoxy reference

1,0

1,3

Excellent resistance to fatigue for long live blade performance.

0,3

0,7

Tensile fatigue performance (S-N Curve) of Beyone 201-A-01 glass reinforced composites compared to standard epoxy systems for wind turbine blades

WTB Epoxy reference + SE2020 Standard UPR resins + Standard Glass

Beyone 201-A-01 + SE3030 1,E+01

1,E+02

1,E+03

1,E+04

1,E+05

1,E+06

1,E+07

Numbe er of cycles

bioplastics MAGAZINE [03/14] Vol. 9

Thermoset Reduced Eco-footprint of Beyone 201-A-01 resins vs. epoxy resin reference

Co-creation works

ECO-footprint is the sum of all environmental impacts from an LCA (including e.g. CO2 footprint, toxicity, waste, resource consumption, land use) Eco Footprint (points) Beyone 1

Epoxy system

0,575

0,72

DSM has proposed an all-new composite system for making wind turbine blades, together with its partners 3B-the ﬁbreglass company, Siemens Wind Power and DTU Wind Energy, featuring easy blade manufacturing, low weight, high stiffness, and excellent resistance to fatigue. The system is based on DSM’s Beyone 201-A-01, a resin that is styrenefree, cobalt-free (based on BluCure™ Technology, www. BluCure.com), and 40 % biobased. It has been demonstrated that this system can be used for making long blades at a record speed (through faster resin infusion and short postcure), giving an increased output per mold and an outlook for excellent process consistency. The bio-ingredients in the product formulations introduced in this article are derived from a mix of corn and corn waste material (the so-called generation 1.5 5). DSM wants to demonstrate that high performance levels can be achieved through using bio-ingredients (hence the introduction of these three resins). At the same time, DSM has increased its efforts to investigate routes for making the required raw materials from secondary organic sources (i.e. not competing with the food chain). DSM already has a track record of introducing new biobased products, supported by its strong roots in Life Sciences and biotechnology.

In order to commercialize new technologies that have the potential to revolutionize the manufacturing of wind turbine blades, it was necessary to think out of the box and form a strong channel partnership. DSM, 3B, Siemens Wind Power and DTU were able to demonstrate that through cocreation, a complex technology can be evaluated at record speed and prepared for live application in line with market requirements. Presently, the material system is under evaluation by Siemens Wind Power for its next-generation wind turbine blades. The development of Beyone 201-A-01 may turn out to be a game-changer not only for its performance in wind energy but also for the general application of biobased composite resins. Through the combination of great end-use performance, cost savings through easier processing, and improved sustainability the introduction of this material can be truly called a green revolution.

Together for a brighter future with composites Building on its unique position as Life Sciences & Materials Sciences company, DSM is the leading global innovator of high performance, sustainable composite solutions. Through DSM’s Bright Science and market leadership across a number of industries including transportation, construction, infrastructure and industrial the company creates value by enhancing performance, improving health & safety, and minimizing environmental footprint.

By: Thomas Wegman Marketing Manager DSM Composite Resins Zwolle, The Netherlands

Great outlook for use of biobased materials in wind energy applications

bioplastics MAGAZINE [03/14] Vol. 9

www.dsmcompositeresins.com www.blucure.com

Thermoset

Biobased Epoxy Epichlorohydrin from glycerin enables biobased epoxy resins is marketed under the brand name Epicerol®. In contrast to some other ECH producers, Solvay is not downstream integrated and does not produce epoxy resins.

he possible ways of producing epoxy resins are very different and complex. The most common and important class of epoxy resins is derived from epichlorohydrin (ECH) and bisphenol A (BPA), a bivalent alcohol.

“Epicerol revolutionized the way of ECH production,” Thibaud Caulier, Senior Business Development Manager at Solvay explains to bioplastics MAGAZINE. “Epicerol not only uses 100% renewable carbon and reduces the carbon footprint of ECH production,” he says. “It is environmentally friendly in many other respects.” The whole production process consumes less energy and chlorine. The chemical reactions involved are more selective than in the propylenebased process, which signiﬁcantly reduces the generation of chlorinated by-products. Another distinctive feature of Epicerol is that it does not release liquid efﬂuents in the environment.

BPA is exclusively produced from fossil feedstock. However, health and safety concerns about the use of this chemical in food contact applications have led to the development of BPA substitutes, some of which being bio-based (e.g. lignin derivatives). Epichlorohydrin has been produced from oil-based propylene for decades, but it can also be obtained from biobased glycerin, a by-product from biodiesel and oleochemicals production. Thanks to identical physicochemical properties, biobased ECH can be used as a drop in substitute for fossil ECH.

In 2013, AkzoNobel and Solvay signed a three-year agreement whereby AkzoNobel will progressively increase the use in their coatings of bio-based epoxy resins produced with Epicerol, aiming to reach by 2016 20% of their equivalent ECH demand as bio-based material.

The world market for epichlorohydrin is about 1.5 million tonnes, 87% of which being used for the production of epoxy resins (in Asia and especially China, this share exceeds 90%). The main use of epoxy resins is for the production of protective coatings (corrosion proof) for the marine, automotive and industrial markets. The second biggest application area for epoxy resins is the manufacture of electronic components such as printed circuit boards and encapsulated semiconductors. In third position is the ﬁeld of composites, mainly for public transportation (aerospace, automotive,…) and wind-power generation.

In March 2014, a joint panel was organized at the World Biomarkets conference in Amsterdam, with Kukdo Chemical (epoxy supplier of AkzoNobel) and EY besides Solvay and AkzoNobel. Kukdo is committed to develop bio-based epoxy resins based on Epicerol. EY is bringing its competencies in order to implement a chain of custody that keeps track along the chain of the use of Epicerol in AkzoNobel coatings.

Belgian multinational Solvay is a major supplier of ECH and the world’s biggest producer of bio-based epichlorohydrin, made from glycerin. The diversiﬁed chemicals group entered the ECH market in the early 1960s, growing its annual ECH production capacity to 210,000 tonnes nowadays. Solvay produces propylene-based ECH at its plant in Rheinberg/ Germany and a mix of propylene and bio-based ECH in Tavaux/France. Its plant in MapTa Phut/Thailand is entirely dedicated to biobased epichlorohydrin (100,000 t/a) which

Chemistry of epichlorohydrin manufacturing (simpliﬁed)

Solvay is actively seeking to establish further supply chain partnerships in other epichlorohydrin market segments. Besides thermoset resins, Epicerol can also be used for rubber products. This shall be covered in a separate issue of bioplastics MAGAZINE. MT www.solvay.com

CI2 CI HCI

Propylene

HCIO CI

NaOH O

Allyl Chloride CI

HCI

OH HO

OH CI Dichloropropanol

Brine

Epichorohydrin

Bio sourced Glycerine

H 2O

bioplastics MAGAZINE [03/14] Vol. 9

From Science & Research

Supercritical Fluid assisted injection moulding A New Paradigm for Process-friendly Fabrication of Bioplastics

espite increasing interests and outstanding environmental beneﬁts, the application of certain bioplastics in areas, which are currently dominated by petroleum based plastics, such as structural, electrical and other consumer products are limited. This is due to the fact that those bioplastics possess inferior material properties and are relatively expensive. In addition, bioplastics possess narrow processing windows, which makes them vulnerable for thermal degradation while also limiting widespread processability including composites formulation.

The material- and processing- challenges of such bioplastics can be overcome by using a unique supercritical ﬂuid (SCF) assisted fabrication technology. SCF is a state of gas (such as CO2 or N2) above its critical pressure and temperature (Fig. 1). At an SCF state, the gas will have both gas-like and liquid-like properties. Both the properties direct the mixing of SCF with the polymer [1]. SCF effectively swells and plasticizes glassy polymers thereby leveraging low-temperature processing of plastics, which is highly desirable for moisture- and heat-sensitive bioplastics. The plasticization effect by SCF is triggered by increased polymer interchain distance that results in enhanced mobility of polymer segments, a phenomenon similar to plasticizing effect by conventional solvents or additives. A desiring feature of SCF plasticization as opposed to liquid or additive plasticizers is easy removal of the plasticizers from the processed bioplastics. This will aid in nontransformative processing of bioplastics. Moreover, SCFs are environmentally friendly yet being cost-effective. The SCF processing of bioplastics also results in the development of microcellular foams, which possess superior material properties at reduced densities aka material consumption, a feature highly desired for expensive bioplastics. For these outstanding beneﬁts, SCF technology is currently employed

for a host of conventional plastics processing technologies such as extrusion, injection moulding, blow moulding, etc. This article focuses on SCF injection moulding (IM) process.

SCF Assisted Injection Moulding Technology The SCF technology was commercialized as MuCell® technology in 1995 [2, 3]. A schematic of the microcellular injection moulding process with microstructure is shown in Fig. 2. In addition to lower temperature processing, reduced material consumption, and improved properties such as toughness, damping ability, etc., the SCF injection moulding technology aids in enhanced moulding thermodynamics which results in quicker cycle time which is highly desired for high-speed production lines. Moreover, the SCF IM process is run at lower pressures which results in stress-free and reduced warped parts [1]. Unlike conventional foams, the SCF IM processed microcellular foams yield reduced cell sizes and enhanced cell densities, typically on the order of 10μm or less and 109 cells/cm3 or more, respectively. These micron-sized cells may serve as crack arrestors by blunting crack tips, thereby enhancing part toughness [4], impact strength [5], and fatigue life [6]. The microcellular injection moulding process takes place in three steps: nucleation, cell growth, and cell stabilization. First, SCF is dissolved into a polymer melt to form a singlephase polymer–gas solution, that is, the polymer melt is super-saturated with the blowing agent. Then, the pressure is suddenly lowered to a value below the saturation pressure triggering a thermodynamic instability and inducing cell nucleation. Cell growth is controlled by the gas diffusion rate and the stiffness of the polymer–gas solution. In general, cell growth is affected by the following factors: (a) time allowed for cells to grow; (b) state of supersaturation;

Fig. 1:

Fig. 2:

Diagram of material phases (reproduced from [2])

Schematic of the SCF injection molding process.

Liquid

SCF

Pcr

Solid Critical C rittica al po point ointt

Pressure >

Gas

Tcr

bioplastics MAGAZINE [03/14] Vol. 9

Cavity Cross Section

Supercritical N2 or CO2 Higher Back Pressure (80 - 200 bar)

Rapid Pressure Drop in Nozzle Triggers Cell Nucleation

Single-Phase Polymer-Gas Solution

Special Reciprocating Screw

From Science & Research (c) hydrostatic pressure applied to the polymer; (d) temperature of the system; and (e) viscoelastic properties of the single-phase polymer–gas solution. Other than processing parameters, materials formulations such as fillers and polymer blends also have strong influence on cell nucleation and growth. Especially, addition of fillers, which act as nucleating agents, leads to heterogeneous cell nucleation. They provide a large number of nucleation sites leading to higher cell densities and smaller cell sizes. Thus, increased adoption of bioplastics, specifically with new formulation designs comprising biobased blends and green composites, will benefit significantly from the SCF IM process.

Polylactic Acid-Hyperbranched Polyester-Nanoclay Bionanocomposite Foams This study conducted by the authors exempliﬁes structure, morphology and properties of polylactic acid (PLA)hyperbranched polyester (HBP)nanoclay composite foams processed via SCF IM technology [7]. Poly (maleic anhydride-alt-1-octadecene) (PA) was used as a cross-linking agent for the HBP. As shown in Table-1, PLA was combined with PA, HBP, and nanoclay into a variety of formulations using a twin-screw extruder. Table-2 presents the processing conditions for the SCF IM process. For comparison, samples were also fabricated without SCF. NonSCF samples are herein after termed as ‘solid’ and SCF samples are termed as ‘microcellular’. As can be observed, using SCF process, a 5ºC reduction in processing temperature was achieved which is due to the plasticizing effect of the SCF. This testiﬁes the enhanced processability of SCF assisted technology. Fig. 3:

Representative SEM images of the fracture surfaces of solid and microcellular PLA and PLA-HBP blends: (a) Pure PLA (Solid), (b) Pure PLA (Microcellular), (c) PLA-6%(H2004+PA) (Solid), (d) PLA-6%(H2004+PA) (Microcellular), (e) PLA-12%(H2004+PA) (Solid), (f) PLA-12%(H2004+PA) (Microcellular), (g) PLA-12%(H2004+PA)-2%Nanoclay (Solid), (h) PLA-12%(H2004+PA)-2%Nanoclay (Microcellular), (i) PLA-12%(H20+PA) (Solid), (j) PLA-12%(H20+PA) (Microcellular)

bioplastics MAGAZINE [03/14] Vol. 9

From Science & Research Fig. 4:

Solid

Tensile properties of solid and microcellular PLA and PLA-HBP blends: (a) Specific toughness, (b) Strain–at–break, (c) Specific modulus, (d) Specific tensile strength.

Microcellular

Speciﬁc Toughness [MPa/(Kg/m3)]

Strain-at-break [%]

Speciﬁc Modulus [MPa/(Kg/m3)]

Speciﬁc Tensiles Strenght [MPa/(Kg/m3)]

0 0.005 0.01 0.015 0.02

PLA

PLA - 6% (H2004 + PA)

PLA - 12% (H2004 + PA)

PLA - 12% (H2004 + PA) -2% NC

PLA - 12% (H20 + PA)

PLA - 12% (H2004 + PA)

Fig. 3 shows the morphology of the solid and microcellular samples. The cell morphology of the microcellular foams showed that the addition of HBPs and nanoclay decreased the average cell size while increasing the cell density. Moreover, among all the solid and microcellular PLA–HBP blends, PLA–12%(H2004+PA)–2%nanoclay composites exhibited the highest specific toughness and strain-at-break followed by PLA–12%(H2004+PA) and PLA–6%(H2004+PA) (Fig. 4). On the other hand, PLA–12%(H20+PA) had a similar specific toughness and strainat-break values as the pure PLA for both solid and microcellular samples. Furthermore, the addition of HBPs+PA and HBP–nanoclay caused a slight reduction in specific modulus and a considerable reduction in specific strength compared with pure PLA in all solid and microcellular PLA–HBP blends. Overall, using SCF process, a weight reduction of 10–16% was achieved which testifies reduced materials consumption.

15 30 40 60

0.4 0.8 1.2 1.6

0.02

0.04

0.06

Conclusions The advocacy of certain bioplastics specifically in areas currently dominated by conventional plastics will be realized only after sustained alleviation in the process and materials properties limitations of such bioplastics. In this regard, SCF assisted injection moulding technology plays a vital role specifically in lowering the viscosity of these bioplastics thereby lessening its processing temperature or widening the processing window, reducing the materials consumption through the development of low density foams without compromising on the specific materials properties, promoting the impact resistance of the materials, inducing stress-free and thus reduced warped parts, high throughout production, etc. Despite these extraordinary benefits, the science of SCF aided bioplastics is at a nascent state. Thus, significant innovations need to be created to pioneer and establish this technology within the commercial space.

By: Srikanth Pilla* Clemson University, South Carolina, USA Shaoqin Gong University of Wisconsin-Madison, USA *: Corresponding author: spilla@clemson.edu

References 1. J. Xu, Microcellular Injection Moulding, Chapter 1, p. 15, 2010. 2. N. P. Suh, Innovation in Polymer Processing, Ed. J. F. Stevenson, Chapter 3, p. 93, 1996. 3. J. Xu, and D. Pierick, J. Injection Moulding Technol., Vol. 5, p. 152, 2001. 4. D.F. Baldwin, N.P. Suh, SPE ANTEC Tech. Papers, Vol. p. 1503, 1992. 5. J.E. Martini, F.A. Waldman, N.P. Suh, SPE ANTEC Tech. Papers, Vol. 40, p. 674, 1982. 6. K.A. Seeler, V. Kumar, Cell. Polym., Vol. 38, p. 93, 1992. 7. S. Pilla, A. Kramschuster, J. Lee, S. Gong and L-S. Turng, J. Materials Sci., Vol. 45, p. 2732, 2010.

Table-2:

Injection-moulding conditions used to mould the tensile bars (S-Solid; M-Microcellular) S

Mould Temp (ºC)

Nozzle Temp (ºC)

175

170

Injection Speed (cm3/sec)

Wt% SCF Content

n/a

0.56

Pack Pressure (bar)

795

Pack Time (sec)

7.5

280

Table-1:

Percent composition of the materials compounded Experiment Sample

1 2

PLA-6%(H2004+PA)

99.6 93.6

0.0 1.5

HBP

0 4.5

Naugard-10 Naugard-524 (0.2wt% total (0.2wt% total formulation) formulation) 0.2 0.2

0.2 0.2

Cloisite® 30B

PLA-12%(H2004+PA)

87.6

3.0

9.0

0.2

Screw Recovery Speed (RPM)

PLA-12%(H2004+PA)-2%NC 85.6

3.0

9.0

0.2

Cooling Time (sec)

Microcellular Process Pressure (bar)

n/a

190

PLA

PLA-12%(H20+PA)

bioplastics MAGAZINE [03/14] Vol. 9

87.6

7.4

4.6

0.2

Materials he stars of today’s bioplastics industry are polymers like PLA or PBS. However, in a growth market like bioplastics, other substances are coming to market all the time. One such compound is 5-hydroxymethylfurfural (5-HMF), named by the US Department of Energy as one of the most versatile and promising renewable platform chemicals.

Renewable 5-HMF

Since February 2014, 5-HMF has been produced commercially by AVA Biochem, a Swiss-based company who recently developed a technological breakthrough in the continuous, automated and highly-scalable production of 5-HMF by means of modiﬁed hydrothermal carbonisation (HTC). Located in Switzerland, AVA Biochem’s plant produces 20 tonnes of 5-HMF per year, at purities of up to 99.9%. Currently, 5-HMF is being produced using fructose sourced in Europe. The modiﬁed HTC technology however, will allow for the use of several different biomass streams in the future, including waste biomass.

Biobased platform chemical presents opportunities for bioplastics sector

The scale-up potential of the AVA Biochem process means bulk 5-HMF prices should be possible in the near future. If co-located with an efficient feedstock supply and at a suitable scale, 5-HMF could achieve cost parity with petro-based chemicals soon and therefore become cheaper to use in bioplastics applications. Capacity at the plant could be increased to 40 tonnes/year through process improvements and efficiency gains. Scale-up, together with bulk 5-HMF prices, will have significant consequences, opening new opportunities and potentially revolutionising the bioplastics industry.

Figure 1:

Production route for bio-based 5-HMF

Renewable 5-HMF can already replace petrobased 5-HMF as a drop-in in many applications, such as adhesives used as plasticisers. One of the most promising routes is 2,5 furandicarboxylic acid (FDCA), produced as an intermediate when 5-HMF is oxidised. It can substitute terephthalic acid in polyester, especially polyethylene terephthalate (PET). Global PET output in 2009 was 49.2 million tonnes and PET ﬁbre accounted for about two-thirds. PET for packaging and ﬁlms accounted for 34%.

Figure 2:

Potential applications for 5-HMF

Other increasingly significant markets are biopolyamides and resins, where 5-HMF derivatives caprolactam and 2,5-Bishydroxymethylfuran (2,5BHF) play an important part. By conducting technical, lifecycle and market analyses, clearly defining end-product specifications and potential applications, the bio-based industries can help strengthen market pull for bioplastics. Application development done in conjunction with partners is also key to bringing more bioplastics technologies to market. Discussions between AVA Biochem and potential industry partners have begun and the company is optimistic that cooperation will help further develop the downstream chemistry pathways. The industrialscale production of 5-HMF has the potential to open the door to more innovative and highly interesting applications – in bioplastics and beyond. MT

O N H Caprolactam

O Caprolactone

OH 1,6-Hexanediol

5-Alkoxymethylfurfural

O O

HO OH

2,5-Furandicarboxylic acid

O Adipic acid

O O

5-HMF

O Levulinic acid

5-Hydroxymethylfuroic acid

OH H

5-Hydroxymethylfuroic acid

O O

O H

Bis(5-methylfurfurly)ether

http://www.ava-biochem.com 2,5-Dimethylfuran

bioplastics MAGAZINE [03/14] Vol. 9

Market

European and Global Markets 2012 and Future Trends Wood-Plastic Composites (WPC) and Natural Fibre Composites (NFC)

n the European Union about 352,000 tonnes of Wood- and Natural Fibre Composites were produced in 2012. The most important application sectors are construction (decking, siding and fencing) and automotive interior parts. About 15% of the total European composite market is covered by WoodPlastic Composites (WPC) and Natural Fibre Composites (NFC). A comprehensive market study was conducted by the nova-Institute (Germany) in cooperation with Asta Eder Composites Consulting (Austria/ Finland) to give a detailed picture of the use and amount such biocomposites in the European biobased economy. The analysis covers composites in extrusion, injection and compression moulding in different sectors and for different applications.

Total production of biocomposites

Table 1: Production of biocomposites (WPC and NFC) in the European Union in 2012 (in tonnes) (nova 2014)

100% 352,000 Total Volume Biocomposites

Table 1 summarises the results of the survey, showing all WoodPlastic Composites and Natural Fibre Composites produced in the European Union, including all

sectors, applications and processing technologies. Decking and automotive are the most important application sectors for WPC, followed by siding and fencing. Only the automotive sector is relevant for Natural Fibre Composites (NFC) today. The share of WPC and NFC in the total composite market â&#x20AC;&#x201C; including glass, carbon, wood and Natural Fibre Composites â&#x20AC;&#x201C; is already an impressive 15%. Even higher shares are to be expected in the future: NFC are starting to enter other markets than just the automotive industry. WPC granulates for injection moulding are now produced and offered by global players and are becoming more attractive for clients that manufacture consumer goods, automotive and technical parts. With increasing polymer prices and expected incentives for bio-based products (the bio-based economyy is one of the lead markets in Europe) this trend will go from strength to strength, resulting in two-digit growth and increasing market shares over the coming decade.

74%

26%

260,000

92,000

Wood-Plastic Composites

Natural Fibre Composites 90,000 2,000

15 % Share

2.4 Million Composite Production in European Union total volume (Glass, Carbon, WPC and NFC)

bioplastics MAGAZINE [02/14] Vol. 9

(Photo: hammerkauf.de)

(Photo: nova)

Automotive Others

Market Global Production of WPC in 2010 and 2012 and Forecast for 2015

110,000

65,000

40,000

55,000

40,000

30,000

2015

Fig. 2:

Use of wood and natural ﬁbres for composites in the European automotive industry in 2012, including cotton and wood. Others are mainly jute, coir, sisal and abaca (nova 2014)

others

hemp 5% kenaf

38% wood

19% ﬂax

cotton

25%

80,000

TOTAL

Interior parts for the automotive industry is by far the most dominant use of Natural Fibre Composites – other sectors such as consumer goods are still at a very early stage. In the automotive sector, Natural Fibre Composites have a clear focus on interior trims for highvalue doors and dashboards. WoodPlastic Composites are mainly used for rear shelves and trims for trunks and spare wheels, as well as in interior trims for doors. Figure 2 shows the total volume of 80,000 tonnes of different wood and

2012

300,000

WPC and NFC in the automotive industry

2010

70,000

25,000

5,000

40,000

20,000

10,000

The report also gives an overview of the latest market developments in North-America, Asia and Russia, and provides an overview of, and a forecast for, the global WPC market. Worldwide WPC production will rise from 2.43 million tonnes in 2012 to 3.83 million tonnes in 2015. Although North America is still the world’s leading production region with 1.1 million tonnes, ahead of China (900,000 t) and Europe (260,000 t), it is expected that China (with 1.8 million t by then) will have overtaken North America (1.4 million t) by 2015. European production will grow by around 10% per year and reach 350,000 tonnes in 2015.

Fig 1.

VOLUME

The typical production process in Europe is extrusion of a decking proﬁle based on a PVC or PE matrix followed by PP. Increasing market penetration by WPC has meant that WPC volumes have risen strongly and Europe is now a mature WPC market. However, WPC is increasingly used for applications beyond the traditional ones like decking or automotive parts. This includes for example, furniture, technical parts, consumer goods and household electronics, using injection moulding and other non-extrusion processes. Also, new production methods are being developed for the extrusion of broad WPC boards. In the face of rising plastic prices, WPC granulates are getting more and more attractive for injection moulding. Three big paper companies released cellulose-based PP granulates for injection moulding between 2012 and 2013. They use a PP matrix with cellulose and have ﬁbre contents between 20 and 50% for new and interesting applications such as furniture, consumer goods and automotive parts.

350,000

260,000

Wood-Plastic Composites – Decking still dominant, but technical applications and consumer goods rising

2015

2012

2010

50,000

20,000

10,000

2015

2012

2010

220,000

900,000

1,100,000

1,350,000

1,800,000

bioplastics MAGAZINE [04/14] Vol. 9

Market

Production in 2012

Forecast production in 2020

Biocomposites

without ... with strong ...

WPC

190,000 t

400,000 t 450,000 t

Construction, extrusion

60,000 t

15,000 t

NFC

... incentives for bio-based products

90,000 t

Automotive, press moulding & extrusion/thermoforming

80,000 t 300,000 t

Granulates, injection moulding

100,000 t > 200,000 t

120,000 t

Automotive, press moulding

2,000 t

Granulates, injection moulding

350,000 t 10,000 t > 20,000 t

Table 2: Production of biocomposites (WPC and NFC) in the European Union in 2012 and forecast 2020 (in tonnes) (nova 2014)

natural fibres used in the 150,000 tonnes of composites for passenger cars and lorries that were produced in Europe in 2012 (90,000 tonnes of Natural Fibre Composites and 60,000 tonnes of WPC). Recycled cotton fibre composites are mainly used for the driver cabins of lorries. Process-wise, compression moulding of wood and Natural Fibre Composites are an established and proven technique for the production of extensive, lightweight and high-class interior parts for mid-range and luxury cars. The advantages (lightweight construction, crash behaviour, deformation resistance, lamination ability and, depending on the overall concept, price) and disadvantages (limited shape and design forming, scraps, cost disadvantages in case of high part integration in construction parts) are well known. Process optimisations are in progress in order to reduce certain problems such as scraps and to recycle wastage. Since 2009, new improved compression- moulded parts have shown impressive weight- reduction characteristics. This goes some way to explaining the growing interest in new car models. Using the newest technology, it is now possible to get area weight down to 1,500 g/ m2 (with thermoplastics) or even 1,000 g/m2 (with thermosets), which are outstanding properties when compared to pure plastics or glass fibre composites.

bioplastics MAGAZINE [02/14] Vol. 9

Still small in volume but also strong in innovation: PP and cellulose-based granulates for injected- moulded parts were recently introduced onto the automotive market by big paper companies in Europe and the USA.

Outlook for WPC and NFC production in the EU until 2020 The production and use of 150,000 tonnes biocomposites (using 80,000 tonnes of wood and natural ﬁbres) in the automotive sector in 2012 could expand to over 600,000 tonnes of biocomposites in 2020, using 150,000 tonnes of wood and natural ﬁbres each along with some recycled cotton. Yet this fast development will not take place if there are no major political incentives to increase the bio-based share of the materials used in cars. Without incentives the authors forecast that production will only increase to 200,000 tonnes. With improved technical properties, lower prices and bigger suppliers, huge percentage increases can also be expected for WPC and NFC granulates used in injection moulding for all kind of technical and consumer goods. Extruded WPC is now well established as a material for decking, fencing and facade elements. Its market share is still growing and should reach and surpass the level of tropical wood in most of the European countries by 2020.

By: Michael Carus, Lara Dammer Lena Scholz, Roland Essel, Elke Breitmayer nova-Institute,Hürth, Germany Asta Eder Asta Eder Composites Consulting, Austria / Finland Hans Korte PHK Polymertechnik GmbH, Wismar, Germany

A more comprehensive summary is available for free at www.bio-based.eu/markets The full report can be ordered for 1,000 € plus VAT at www.bio-based.eu/markets

Microplastic

Microplastics in the Environment

total mass in million tonnes

Sources, Consequences, Solutions

350 1950

1970

1990

300 250

2010

Plastic waste in the oceans

Diameter

Typical dimensions Typical dimensions of aquatic creatures of industrial plastics

Macroplastic

> 25 mm

Fish, shellﬁsh, mussels, etc.

Mesoplastic

5 – 25 mm

production of plastic granules /pellets

Global plastic production 200 150 100

Ingress of plastic waste into the oceans estimations by: UNEP 2006 Wright et al. 2013

Large microplastic 1 – 5 mm particle Small microplastic < 1mm particle

Plankton

Application of microplastic in cosmetics

Tabelle 1 50 0

Table 1: Classiﬁcation of marine plastic debris on the basis of size (Source: own representation based on JRC 2013, STAP 2011)

Figure 1: Global plastics production in the period from 1950 to 2012 und estimated volume of discharge of plastics into the oceans (Source: own representation based on PlasticsEurope 2013, UNEP 2006, Wright et al. 2013)

cientific studies have shown that plastics make a huge contribution to the littering g of the seas. In marine protection, plastic particles with a diameter of less than 5 mm are referred to as microplastics. These can be fragments created by the breaking up of larger pieces of plastic such as packaging, or as fibres are washed out of textiles. They can also be primary plastic particles, produced in microscopic sizes. These include granulates used in cosmetics, washing powders, cleaning agents and in other applications. The following article describes the source of microplastics, the effects they have on the ecosystem and on people, and discusses potential solutions. For the first time, on July 1st 2014, a conference will be dedicated to this topic in Germany.

plastic bottles or bags, steadily increasing amounts of plastic microparticles – commonly known as microplasticss – are being observed in ocean gyres, sediments, and on beaches, as well as being found in marine organisms. The term microplastics, however, is not used consistently. In the cosmetics industry, it is used to describe plastic granulates that in many cases are much smaller than 1 mm in diameter. In marine protection, in contrast, plastic particles with a diameter of less than 5 mm are considered microplastics (Arthur et al. 2009). On the other hand, Browne et al. (2011) use the term for plastic particles with a diameter of less than 1mm. Neither source gives a lower value for the diameter of particles, meaning that the term microplastics also includes signiﬁcantly smaller particles (Leslie et al. 2011). Microplasticss can therefore be considered an umbrella term for various plastic particles determined solely on the basis of size (cf. Table 1).

Waste in the oceans and inland waters is dominated by plastics (Barnes et al. 2009). The United Nations Environment Programme (UNEP) assumes coverage of up to 18,000 pieces of plastic for every square kilometre of ocean (UNEP 2006). It can take centuries for plastic to be broken down in the oceans In accordance with this deﬁnition, in the text that follows, by physical, chemical, and biological decomposition processes all plastic particles with a diameter smaller than 5mm are (UBA 2010). Along with larger waste items such as termed microplastics.

bioplastics MAGAZINE [02/14] Vol. 9

Microplastic

pollutants can attach to and accumulate on plastic microparticles. If marine organisms consume these particles, The most commonly used polymers in cosmetics are these contaminants can enter the food chain (Teuten et al. polyethylene (PE), polypropylene (PP) and polyamide (PA). A 2007) and ultimately cause harm to humans. whole series of other polymers are also in use (Leslie et al. Can bioplastics be a solution? 2012).

Sources of microplastics

Primary microparticles from cosmetics make up only a Manufacturers add synthetic polymers to cosmetics for a number of reasons: some possess film-forming and viscosity- small part of the plastics in the oceans in absolute terms. g of regulating properties, others act as abrasives. They are Strategies designed to reduce the ever-increasing littering the world’s seas should therefore not focus solely on the use designed to remove impurities from the skin or to clean teeth. of these microparticles, but should apply to all kinds of plastic Along with their use in the cosmetics industry, there are waste. other applications for plastic microparticles. They are used Cosmetics manufacturers can, however, eliminate longas abrasive beads in detergents and cleaning fluids, and as a blasting abrasive in, for example, the surface cleaning of lasting plastic microparticles from their products, or replace stainless steel. They are use as lubricants, separating agents, them with microparticles produced from other materials. or as carriers for pigments, or to adjust the viscosity of hot Many of these companies are currently on the lookout for melt adhesives. Water softeners can also contain plastic alternatives. Chemicals producers and traders already offer a selection (cellulose, wood chip, minerals). microparticles. As well as microplastics produced directly in microscopic sizes to be used in cosmetics and other products, microparticles in many cases are secondary fragments produced by the breakdown of larger pieces of plastic. Plastic microparticles can originate, for example, from plastic packaging dumped in the environment, such as bags or boxes, or from plastic fibres from textiles, or particles released by tyre wear. The production and recycling of plastics also generates particles. Ryan et al. (2010) also record direct macroplastic pollution from ship waste. Although the sources of microplastics are largely documented, until now no reliable data has been produced on the amounts of microplastics from cosmetics and other implementations, and other sources, actually enter the environment. The United Nations Environment Programme refers to the estimate made in 1997 that in the 1990s, around 6.4 million tonnes of plastic debris entered the oceans annually, of which just short of 5.6 million tonnes came from shipping (UNEP 2006). Wright et al. 2013 estimate that, in total, around ten per cent of global plastics production will find its way into the ocean at some point. It follows that of the 288 million tonnes of plastic produced worldwide in 2012 (according to PlasticsEurope estimates), just short of 30 million tonnes will sooner or later enter the marine environment and serve as a potential source of microplastics (cf. Figure 1).

Consequences of microplastics The presence of microplastics in the environment has a number of negative consequences for humans and the natural environment. If animals ingest pieces of plastic, large or small, mistaking them for food, a permanent feeling of satiety can result – and they starve to death. In experiments feeding mussels with microplastics, researchers demonstrated that plastic particles could penetrate the stomach lining and enter the bloodstream. Many plastic parts contain chemicals like softeners or ﬂame retardants. Some of these additives are harmful to fertility or imitate natural hormones. They are only weakly bound into the plastic matrix, and can easily leach out and impact plant and animal life. Long-lasting hydrophobic

Whether or not biodegradable polymers can be an option is an exciting and important question. Their use would be of interest above all because the existing production chain could be kept in use largely unaltered, and the functioning of the microparticles would also be a very close match for the plastics previously in use. Polyhydroxyalkanoates (PHA), and polybutylene succinate (PBS), are potential candidates, as are polylactic acid (PLA) produced from maize starch, chitosan from chitin or casein from animal protein. Current studies suggest that PLA is probably not the best solution, whereas PHAs have real future potential (CalRecycle 2012). PHAs are natural thermoplastics, which degrade quickly in almost any environment (including in the sea). The greatest challenges lie in ensuring that breakdown occurs only after the product has been used, and in developing mass production.

e plastics are no In contrast, so-called oxo-(bio)degradable solution – in fact, they’re part of the problem. These plastics aren’t actually biodegradable. They contain predetermined breaking points that cause the polymers to fragment i.e. produce microparticles. Up to 80 % of the content (in terms of the original weight of the product) remains in the environment and can produce toxic effects (Narayan 2009).

Conclusions The availability of precise numbers on the amount of plastic microparticles used in cosmetics and other products is unsatisfactory. Due to the lack of data, it is difﬁcult to establish the volumes in which these particles enter the environment, and what the predominant transport and release mechanisms are. Their accumulation in the oceans, on the seaﬂoor, on beaches worldwide, and in numerous organisms (and the resulting adverse effects for both humans and nature) is receiving ever more public attention, and demands solutions. Fragments from plastic debris that has entered the sea are a far greater source of damage. This means that if we want to decrease the amount of microplastics in the environment, and above all in the world’s oceans, it is not enough to focus on microplastics in cosmetics. Instead, measures need to

bioplastics MAGAZINE [04/14] Vol. 9

be taken to drastically reduce the amount of plastic waste entering the environment in general – not just in Germany or the EU, but worldwide. The EU is pointing us in the right direction with its ﬁve-step waste hierarchy: reuse – reduce, recycle, incinerate (waste to energy) – (avoid) landﬁll.

By: Roland Essel Head of Sustainability Department nova-Institute Hürth, Germany

The nova-Institute is organising a conference entitled “Microplastics in the Environment – Sources, Consequences, Solutions” to take place on July 1st between 9am and 6pm at the Maternushaus conference centre in Cologne, Germany. Further information about the conference can be found at: www.bio-based.eu/mikroplastik

References Arthur, C.; Baker, J. & H. Bamford (2009): Proceedings of the international Research Workshop on the Occurrence, Effects and Fate of Microplastic Marine Debris. Sept 9-11, 2008. NOAA Technical Memorandum NOSQR&R-30. Barnes, D.K.A.; Galgani, F.; Thompson, R. C. & M. Barlaz (2009): Accumulation and fragmentation of plastic debris in global environment. In: Philosophical Transaction of the Royal Society B (biological sciences) 364: 1985-1998 Browne, M.A.; Crump, P.; Niven, S.J.; Teuten, E.; Tonkin, A.; Galloway, T. & R. Thompson (2011): Accumulation of Microplastic on Shorelines Worldwide: Sources and Sinks. In: Environmental Science & Technology 45: 9175-9179 CalRecycle – California Department of Resources Recycling and Recovery (2012): PLA and PHA Biodegradation in the Marine Environment. State of California, Department of Resources Recycling and Recovery, Sacramento, California Gouin, T.; Roche, N.; Lohmann, R. & G. Hodges (2011): A thermodynamic approach for assessing the environmental exposure of chemicals absorbed to microplastic. In: Environmental Science & Technology 45: 1466-1472 JRC – Joint Research Centre (2013): Guidance on Monitoring of Marine Litter in European Seas – A guidance document within the Common Implementation Strategy fort he Marine Strategy Framework Directive. MSFD Technical Subgroup on Marine Litter. European Union, 2013 Leslie, H.; van der Meulen, M. D.; Kleissen, F. M. & A. D. Vethaak (2011): Microplastic Litter in the Dutch Marine Environment – Providing facts and analysis for Dutch policymakers concerned with marine microplastic litter. Deltares, the Netherlands Narayan, R. (2009): Biodegradability... In: bioplastics MAGAZINE [01/09] Vol. 4: 28-31 PlasticsEurope – Association of Plastics Manufacturers (2013): Plastics – the Facts 2013. An analysis of European latest plastics production, demand and waste data. PlasticsEurope, Brussels Ryan, P.G.; Moore, C.J.; van Franeker, J.A. & C.L. Moloney (2010): Monitoring the abundance of plastic depbris in the marine environment. In: Philpsophical Transactions of the Royal Society B 364, pp: 1999 - 2012 STAP – Scientiﬁc and Technical Advisory Panel (2011): Marine Debris as a Global Environmental Problem: Introducing a solutions based framework focused on plastics. Global Environment Facility, Washington, DC. Teuten, E.L., Rowland, S.J., Galloway, T.S. & Richard C. Thompson (2007): Potential for plastics to transport hydrophobic contaminants. In Environmental Science and Technology 41, 7759-7764 Thompson, Richard C. (2014): The challenge: Plastics in the marine Environment. Environmental Toxicology and Chemistry 33: 6-8 UBA - Umweltbundesamt (2010): Abfälle im Meer – ein gravierendes ökologisches, ökonomisches und ästhetisches Problem. Umweltbundesamt, Dessau-Roßlau UNEP – United Nations Environment Programme (2006): Ecosystems and Biodiversity in Deep Waters and High Seas. UNEP Regional Seas Reports and Studies No. 178. UNEP /IUCN, Switzerland Wright, S. L.; Thompson, R. & T. S. Galloway (2013): The physical impacts of microplastics on marine organisms: A review. In: Environmental Pollution 177: 483-492

bioplastics MAGAZINE [02/14] Vol. 9

Basics

Injection Moulding

njection moulding is a plastics processing technique for the fully automated production of plastic parts with complex geometries. Almost all sizes and shapes of plastic parts can be made by injection moulding. About 60% of all plastics processing machines are injection moulding machines [1]. Injection moulded parts range from a few milligrams (e.g. cogwheels in Swatch® whatches) up to many kilograms (e.g. dashboards or bumpers for automobiles). The possible applications for injection moulding are almost endless. Some examples are ball-point pens, rulers and other ofﬁce accessories, disposable cutlery, garden furniture, beverage crates, knobs and handles, small mechanical parts, and lots more.

The process In the injection moulding process molten plastic material is injected into a mould. The granular plastic raw material for the part is fed by gravity from a hopper into a heated barrel. In this barrel the plastic material is transported forward by a turning screw. During this process the plastic is melted, mixed and homogenized. At the same time the crew slowly moves backward during the melting process to enable a shot of melted plastic to build up in front of the screw tip (Fig. 1). Once the quantity needed for one shot is reached the screw moves forward and presses the melt through a pre-heated nozzle and under pressure through the feed channel to the cavity of the cold mould, the so-called tooll. The plastic now cools down in the tool and is ejected as a ﬁnished moulded part [1].

Injection moulding of bioplastics [4] In contrast to blown ﬁlm production, which uses existing machinery that has already proved to be effective, some reservations still exist in terms of the injection moulding of bioplastics.

The most important requirement for successfully injection moulding bioplastics is the compatibility of existing production equipment. Frankly, existing machinery and production tools that are designed for common plastics such as PP, PS or ABS are perfectly suitable for the processing bioplastics (such as FKuR’s BIO-FLEX® or BIOGRADE®) However, a small investment may be necessary concerning the hot runner system and the clearances within existing tools. One key to success is to reduce the residence time of the material. When compared with PS, for example, there are some bioplastics that can be processed with a reduction of 30% of the whole cycle time while others, such as PLA need longer cooling times due to the crystallisation process. While the mass temperature should not fall outside the defined temperature profile the processor should be informed, through recommended processing conditions, that the injection pressure and speed can be modified to fill the mould properly. The small processing window of bioplastics in terms of the temperature profile may result in the need for a new hot runner system. Commonly hot runner systems do not have a constant temperature along the whole length. This, along with the tendency of the materials to either freeze immediately or to burn if the temperature goes outside the processing window, can cause problems if improper hot runner systems are used. After resolving the issues of the hot runner by applying a suitable system then the only thing that the machine operator needs is a bioplastic grade designed for injection moulding (pre-dried if necessary) as well as a little practice with the new materials. Some examples of successful products made from FKuR’s bioplastics in both multi and single cavity tools with hot and cold runners are consumer electronics, office equipment and catering articles. MT References: [1]: Stitz, S.; Keller, W.: Spritzgießtechnik, Carl Hanser Publishers, 2001

Fig 1: The injection moulding process (picture: according to www.fenster-wiki.de)

[2]: Thielen,M.: Bioplastics - Basics. Applications. Markets, Polymedia Publisher, 2012 cooling

heating

screw

[3]: Wikipedia

granules

plasticizing

mould

melt

[4]: Lohr, C.: Bioplastics Designed for rigid parts, bioplastics MAGAZINE (Vol. 5) Issue 03/2010

d ve drive

injection, cool cooling ng with after-pressure

demoulding

Injection moulding machine (picture: Ferromatik Milacron)

bioplastics MAGAZINE [03/14] Vol. 9

Events

Event Calendar

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Biochemicals & Bioplastics 2014 10.06.2014 - 11.06.2014 - Duesseldorf, Germany Renaissance Hotel http://ci43.actonsoftware.com/acton/ct/ 6204/s-005c-1403/Bct/l-0051/l-0051:587/ct0_0/1

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10.06.2014 - 12.06.2014 - Amsterdam, The Netherlands Amsterdam RAI Convention Centre

4th Biobased Performance Materials Symposium 12.06.2014 - Wageningen, Netherlands Hotel De Wageningsche Berg

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ﬁp solution plastique 17.06.2014 - 18.06.2014 - Lyon, France Lyon Euroexpo, France www.f-i-p.com

Biobased Materials 24.06.2014 - 25.06.2014 - Stuttgart, Germany 10th Congress for Biobased Materials, Natural Fibres and WPC www.biobased-materials.com

Mikroplastik in der Umwelt – Quellen, Folgen und Lösungen2nd International

ISSN 1862

-5258

01.07.2014 – Cologne, Germany Maternushaus May/Jun

03 | 2014

http://bio-based.eu/mikroplastik

Conference Bio-based Polymers and Composites 24.08.2014 - 28.08.2014 - Visegrád, Hungary

Highligh ts Injection Moulding | 10 Thermose t | 34

www.bipoco2014.hu

Bio-based Global Summit 2014 09.09.2014 - 10.09.2014 - Brussels, Belgien Thon EU Hotel Brussels www.biobased-global-summit.com

International Symposium on BioPolymers - ISBP2014 Vol. 9

29.09.2014 - 01.10.2014 - Santos, Brazil

MAGAZIN

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BioEnvironmental Polymer Society 14.10.2014 - 17.10.2014 - Kansas City, USA Kauffman Foundation Conference Center ... is read in 91 countrie

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Forum Kunststoffgeschichte 2014 „Plastics Heritage“ 22.10.2014 - 24.10.2014 - Berlin, Germany Hochschule für Technik und Wirtschaft HTW in Berlin

www.forum-kunststoffgeschichte.de

Ecochem The Global Sustainable Chemistry & Engineering Event 11.11.2014 - 13.11.2014 - Switzerland, Germany Congress Center Basel http://ecochemex.com

Mention the promotion code ‘watch‘ or ‘book‘ and you will get our watch or the book3) Bioplastics Basics. Applications. Markets. for free 1) Offer valid until 31 July 2014

3rd Conference on Carbon Dioxide as Feedstock for Chemistry and Polymers 02.12.2014 - 03.12.2014 - Essen, Germany Haus der Technik www.co2-chemistry.eu/registration

9th European Bioplastics 02.12.2014 - 03.12.2014 - Brussels, Belgien The Square, Brussels www.european-bioplastics.org

3) Gratis-Buch in Deutschland nicht möglich, no free book in Germany

You can meet us! Please contact us in advance by e-mail.

Suppliers Guide 1. Raw Materials

AGRANA Starch Thermoplastics Conrathstrasse 7 A-3950 Gmuend, Austria Tel: +43 676 8926 19374 lukas.raschbauer@agrana.com www.agrana.com

Shandong Fuwin New Material Co., Ltd. Econorm® Biodegradable & Compostable Resin North of Baoshan Road, Zibo City, Shandong Province P.R. China. Phone: +86 533 7986016 Fax: +86 533 6201788 Mobile: +86-13953357190 CNMHELEN@GMAIL.COM www.sdfuwin.com

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

Simply contact: Tel.: +49 2161 6884467 suppguide@bioplasticsmagazine.com Stay permanently listed in the Suppliers Guide with your company logo and contact information. For only 6,– EUR per mm, per issue you can be present among top suppliers in the ﬁeld of bioplastics.

39 mm

For Example:

Dammer Str. 112 41066 Mönchengladbach Germany Tel. +49 2161 664864 Fax +49 2161 631045 info@bioplasticsmagazine.com www.bioplasticsmagazine.com

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

GRAFE-Group Waldecker Straße 21, 99444 Blankenhain, Germany Tel. +49 36459 45 0 www.grafe.com

Jincheng, Lin‘an, Hangzhou, Zhejiang 311300, P.R. China China contact: Grace Jin mobile: 0086 135 7578 9843 Grace@xinfupharm.com Europe contact(Belgium): Susan Zhang mobile: 0032 478 991619 zxh0612@hotmail.com Natur-Tec® - Northern Technologies DuPont de Nemours International S.A. www.xinfupharm.com 4201 Woodland Road 2 chemin du Pavillon Circle Pines, MN 55014 USA 1218 - Le Grand Saconnex Tel. +1 763.225.6600 1.1 bio based monomers Switzerland Fax +1 763.225.6645 Tel.: +41 22 171 51 11 info@natur-tec.com Fax: +41 22 580 22 45 www.natur-tec.com plastics@dupont.com www.renewable.dupont.com www.plastics.dupont.com Corbion Purac Arkelsedijk 46, P.O. Box 21 4200 AA Gorinchem The Netherlands Tel.: +31 (0)183 695 695 PolyOne Fax: +31 (0)183 695 604 Avenue Melville Wilson, 2 www.corbion.com/bioplastics Zoning de la Fagne bioplastics@corbion.com 5330 Assesse Tel: +86 351-8689356 Fax: +86 351-8689718 www.ecoworld.jinhuigroup.com jinhuibio@126.com

1.2 compounds

Belgium Tel.: + 32 83 660 211 www.polyone.com

Sample Charge: 39mm x 6,00 € = 234,00 € per entry/per issue

Sample Charge for one year: 6 issues x 234,00 EUR = 1,404.00 € The entry in our Suppliers Guide is bookable for one year (6 issues) and extends automatically if it’s not canceled three month before expiry.

Evonik Industries AG Paul Baumann Straße 1 45772 Marl, Germany Tel +49 2365 49-4717 evonik-hp@evonik.com www.vestamid-terra.com www.evonik.com

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

WinGram Industry CO., LTD Great River(Qin Xin) Plastic Manufacturer CO., LTD Mobile (China): +86-13113833156 Mobile (Hong Kong): +852-63078857 Fax: +852-3184 8934 Email: Benson@wingram.hk 1.3 PLA

www.facebook.com www.issuu.com www.twitter.com

Natureplast 11 rue François Arago 14123 Ifs – France Tel. +33 2 31 83 50 87 www.natureplast.eu t.lefevre@natureplast.eu

Kingfa Sci. & Tech. Co., Ltd. No.33 Kefeng Rd, Sc. City, Guangzhou Hi-Tech Ind. Development Zone, Guangdong, P.R. China. 510663 Tel: +86 (0)20 6622 1696 info@ecopond.com.cn www.ecopond.com.cn FLEX-162 Biodeg. Blown Film Resin! Bio-873 4-Star Inj. Bio-Based Resin!

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

www.youtube.com

bioplastics MAGAZINE [03/14] Vol. 9

Suppliers Guide 1.4 starch-based bioplastics

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

6. Equipment

Metabolix, Inc. Bio-based and biodegradable resins and performance additives 21 Erie Street Cambridge, MA 02139, USA US +1-617-583-1700 DE +49 (0) 221 / 88 88 94 00 www.metabolix.com info@metabolix.com

6.1 Machinery & Molds 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

1.6 masterbatches

BIOTEC Biologische Naturverpackungen Werner-Heisenberg-Strasse 32 46446 Emmerich/Germany Tel.: +49 (0) 2822 – 92510 info@biotec.de www.biotec.de

GRAFE-Group Waldecker Straße 21, 99444 Blankenhain, Germany Tel. +49 36459 45 0 www.grafe.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 4. Bioplastics products

62 136 LESTREM, FRANCE 00 33 (0) 3 21 63 36 00 www.gaialene.com www.roquette.com

Grabio Greentech Corporation Tel: +886-3-598-6496 No. 91, Guangfu N. Rd., Hsinchu Industrial Park,Hukou Township, Hsinchu County 30351, Taiwan sales@grabio.com.tw www.grabio.com.tw

PSM Bioplastic HK Room 1901B,19/F, Allied Kajima Buil- ding 138 Gloucester Road, Wanchai, Hongkong Tel: +852-31767566 Fax: +852-31767567 support@psm.com.cn www.psm.com.cn

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

3. Semi ﬁnished products 3.1 ﬁlms

1.5 PHA

TianAn Biopolymer 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 52

bioplastics MAGAZINE [03/14] Vol. 9

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

ProTec Polymer Processing GmbH Stubenwald-Allee 9 64625 Bensheim, Deutschland Tel. +49 6251 77061 0 Fax +49 6251 77061 500 info@sp-protec.com www.sp-protec.com 6.2 Laboratory Equipment

Minima Technology Co., Ltd. Esmy Huang, Marketing Manager No.33. Yichang E. Rd., Taipin City, 2. Additives/Secondary raw materials 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 GRAFE-Group Waldecker Straße 21, 99444 Blankenhain, Germany Tel. +49 36459 45 0 www.grafe.com

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

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

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

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

MODA: Biodegradability Analyzer SAIDA FDS INC. 143-10 Isshiki, Yaizu, Shizuoka,Japan Tel:+81-54-624-6260 Info2@moda.vg www.saidagroup.jp 7. Plant engineering

EREMA Engineering Recycling Maschinen und Anlagen GmbH Unterfeldstrasse 3 4052 Ansfelden, AUSTRIA Phone: +43 (0) 732 / 3190-0 Fax: +43 (0) 732 / 3190-23 erema@erema.at www.erema.at

Uhde Inventa-Fischer GmbH Holzhauser Strasse 157–159 D-13509 Berlin Tel. +49 30 43 567 5 Fax +49 30 43 567 699 sales.de@uhde-inventa-fischer.com Uhde Inventa-Fischer AG Via Innovativa 31 CH-7013 Domat/Ems Tel. +41 81 632 63 11 Fax +41 81 632 74 03 sales.ch@uhde-inventa-fischer.com www.uhde-inventa-fischer.com

Suppliers Guide 9. Services

11 rue François Arago 14123 Ifs – France Tel. +33 2 31 83 50 87 www. biopolynov.com t.lefevre@natureplast.eu

10.2 Universities

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

UL International TTC GmbH Rheinuferstrasse 7-9, Geb. R33 47829 Krefeld-Uerdingen, Germany Tel.: +49 (0) 2151 5370-370 Fax: +49 (0) 2151 5370-371 ttc@ul.com www.ulttc.com 10. Institutions

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

nova-Institut GmbH Chemiepark Knapsack Industriestrasse 300 50354 Huerth, Germany Tel.: +49(0)2233-48-14 40 E-Mail: contact@nova-institut.de www.biobased.eu

10.1 Associations

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

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

IfBB – Institute for Bioplastics and Biocomposites University of Applied Sciences and Arts Hanover Faculty II – Mechanical and Bioprocess Engineering Heisterbergallee 12 30453 Hannover, Germany Tel.: +49 5 11 / 92 96 - 22 69 Fax: +49 5 11 / 92 96 - 99 - 22 69 lisa.mundzeck@fh-hannover.de http://www.ifbb-hannover.de/

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

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

‘Basics‘ book on bioplastics This book, created and published by Polymedia Publisher, maker of bioplastics MAGAis available in English and German language.

ZINE

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 or 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 blow-moulding 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

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

Or subscribe and get it as a free gift (see page 69 for details, outside German y only) bioplastics MAGAZINE [03/14] Vol. 9

Companies in this issue Company

Editorial Advert

Agrana

Company

AIMPLAS

API

Company

Editorial Advert

Hydal Biotech

President Packaging

IMI Fabi

ProTec

Inst. F.Bioplastics & Biocomposites

PTT

Asta Eder Composites Consulting

Institut f.Kunststofftechnik

Reverdia

AVA Biochem

Interbros

RheinChemie

BASF

ITKE (Univ. Stuttgart)

RIKEN

Biomer

Jiangsu Clean Environmental

Biopolynov

Bioserie

Biotec

BPI

Roquette

Jinhui Zhaolong

Sabic

Kingfa

Saida

Shandong Fuwin

Limagrain Cereales Ingredients

Megatech

19 32

51 48, 50

Shanghai Disoxidation

Braskem

Metabolix

Shenzhen Esun Industrial

Clemson Univ

Michigan State Univ.

Showa Denko

Compac

Minima Technology

Sidaplax

Corbion

CTAG

DSM

17, 34 35

DuPont

Siemens Wind Power

Mohawk

Spolvay

Nanobiomatters

Sprint

Suzhou Cleanet

Tahghleef Industries

narocon 50

Natureplast

Erema

NatureWorks

European Bioplastics

Naturtec

51, 55

Ferromatik Milacron

FiberCore

FKuR Kunststoff

2, 51

Fraunhofer UMSICHT

Godfrey Hirst Carpets

Grabio Greentzech

Grupo Antolin

Hallinnk

HBC Bulckaert

Huhtamaki

Editorial Planner

Toyota

UL Thermoplastics

Univ. Madison Wisconsin

22 42, 46

Univ. Minho

30, 52

Universiti Sains Malaysia

50, 51

UPM

Pallmann Maschinenfabrik

VTT Tech. Research Ctr.

PHK Polymertechnik

Wacker Chemie

PIEP

WinGram

plasticker

Wuhan Huali

Plastic Suppliers

Wyss Institute (Harvard)

polymediaconsult

Xinfu Pharm

PolyOne

50 48, 51 31 50

50, 51

2014

Issue

Month

Publ.-Date

edit/ad/ Deadline

04/2014

Jul/Aug

04.08.14

05/2014

Sept/Oct

06/2014

Nov/Dec

Editorial Focus (1)

Editorial Focus (2)

Basics

04.07.14

Bottles / Blow Moulding

Fibre Reinforced Composites

PET

06.10.14

06.09.14

Fiber / Textile / Nonwoven

Toys

Building Blocks

01.12.14

01.11.14

Films / Flexibles / Bags

Consumer Electronics

Sustainability

www.bioplasticsmagazine.com

bioplastics MAGAZINE [03/14] Vol. 9

51 11

Newlight Technologies

Novamont

50, 51

Tianan Biopolymer

NBM

nova-Institute

Grafe

14, 17, 22, 32

Nomacorc

19, 23, 49

Mitsubishi Chemical

Fair Specials Subject to changes

DTU Wind Energie

Evonik

Editorial Advert

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