bioplasticsMAGAZINE_1403
bioplasticsMAGAZINE_1403
bioplasticsMAGAZINE_1403
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ISSN 1862-5258<br />
May/June<br />
03 | 2014<br />
Highlights<br />
Injection Moulding | 10<br />
Thermoset | 34<br />
bioplastics MAGAZINE Vol. 9<br />
... is read in 91 countries
Sustainable Packaging<br />
for future generations<br />
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bioplastics. By using Green PE fully biobased<br />
solutions can be created, whereas the Bio-Flex ® product<br />
line enables fully biodegradable product solutions.<br />
<br />
<br />
product, SCA can guarantee a secure long term supply<br />
of truly sustainable packaging.<br />
Paper packaging extrusion-coated with Green PE<br />
For more information visit
Editorial<br />
dear<br />
readers<br />
Busy days – these days! … After Chinaplas, interpack and quite a number<br />
of conferences even our 3 rd PLA World Congress will be over when<br />
you read this.<br />
For this issue we promised a comprehensive review for both Chinaplas<br />
and interpack. However, as Chinaplas did not show very much breaking<br />
news apart from what we covered in the show preview, we just have a<br />
small review for this event. All in all it could be noticed that an increasing<br />
number of Chinese companies (suppliers as well as visitors/buyers)<br />
are more and more interested in the biobased origin of raw materials<br />
and are not so much focused only on the biodegradability any more.<br />
Suppliers of PBAT for example are looking for biobased 1,4-BDO …<br />
For interpack there is no review at all. It turned out that the preview<br />
already covered most news. The few items that are related to interpack<br />
in this issue are marked with a small interpack icon.<br />
ISSN 1862-5258<br />
May/June<br />
03 | 2014<br />
The other editorial focus topics in this issue are thermoset and<br />
injection moulding.<br />
Some recent news and reports raise new questions and will certainly<br />
be discussed in our upcoming issues. These are the news about “renewable<br />
polyolefins” and other conventional thermoplastics by applying a<br />
mass balance approach. Please read my comment on page 6 and stay<br />
tuned…<br />
As usual this issue is once again rounded off by a number of industry<br />
and applications news…<br />
We hope you enjoy reading bioplastics MAGAZINE<br />
Sincerely yours<br />
Michael Thielen<br />
bioplastics MAGAZINE Vol. 9<br />
Highlights<br />
Injection Moulding | 10<br />
Thermoset | 34<br />
... is read in 91 countries<br />
Follow us on twitter!<br />
www.twitter.com/bioplasticsmag<br />
Like us on Facebook!<br />
www.facebook.com/bioplasticsmagazine<br />
bioplastics MAGAZINE [03/14] Vol.9 3
Content<br />
03|2014 May/June<br />
Injection Moulding<br />
Injection moulding of PTT ............................10<br />
The blend makes the difference .......................14<br />
From Science & Research<br />
New biocomposites for car interior ....................18<br />
PHA from sunlight ..................................20<br />
Editorial ............................. 3<br />
News ............................. 5 - 7<br />
Application News ..................... 22<br />
Event Calendar ....................... 53<br />
Suppliers Guide ...................... 50<br />
Companies in this issue ............... 54<br />
Events<br />
Biobased packaging 2015 ............... 8<br />
Biobased materials for automotive ....... 8<br />
applications 2015<br />
Chinaplas 2014 - Review ............... 17<br />
Talc filled PLA ......................................24<br />
Supercritical Fluid assisted injection moulding ...........38<br />
Applications<br />
White teeth – Naturally! ..............................23<br />
Materials<br />
New high heat resistance grade .......................27<br />
Green biocomposites for architects. ....................28<br />
PHA Modifiers for PLA Fiber ..........................21<br />
Renewable 5-HMF ..................................41<br />
Thermoset<br />
Co-creation makes bio-resins work ....................34<br />
Biobased Epoxy .....................................37<br />
Market<br />
European and Global Markets 2012 and Future Trends. ....42<br />
Microplastic<br />
Microplastics in the Environment ......................46<br />
Basics<br />
Injection Moulding ..................................49<br />
Imprint<br />
Publisher / Editorial<br />
Dr. Michael Thielen (MT)<br />
Samuel Brangenberg (SB)<br />
contributing editor: Karen Laird (KL)<br />
Layout/Production<br />
Mark Speckenbach<br />
Julia Hunold<br />
Head Office<br />
Polymedia Publisher GmbH<br />
Dammer Str. 112<br />
41066 Mönchengladbach, Germany<br />
phone: +49 (0)2161 6884469<br />
fax: +49 (0)2161 6884468<br />
info@bioplasticsmagazine.com<br />
www.bioplasticsmagazine.com<br />
Media Adviser<br />
Elke Hoffmann, Caroline Motyka<br />
phone: +49(0)2161-6884467<br />
fax: +49(0)2161 6884468<br />
eh@bioplasticsmagazine.com<br />
Print<br />
Kössinger AG (7,500 copies)<br />
84069 Schierling/Opf., Germany<br />
Total print run: 3,400 copies<br />
bioplastics MAGAZINE<br />
ISSN 1862-5258<br />
bM is published 6 times a year.<br />
This publication is sent to qualified<br />
subscribers (149 Euro for 6 issues).<br />
bioplastics MAGAZINE is printed on<br />
chlorine-free FSC certified paper.<br />
bioplastics MAGAZINE is read in 91 countries.<br />
Not to be reproduced in any form<br />
without permission from the publisher.<br />
The fact that product names may not be<br />
identified in our editorial as trade marks is<br />
not an indication that such names are not<br />
registered trade marks.<br />
bioplastics MAGAZINE tries to use British<br />
spelling. However, in articles based on<br />
information from the USA, American<br />
spelling may also be used.<br />
Editorial contributions are always welcome.<br />
Please contact the editorial office via<br />
mt@bioplasticsmagazine.com.<br />
Envelopes<br />
A part of this print run is mailed to the<br />
readers wrapped in BoPLA envelopes<br />
sponsored by Taghleef Industries, S.p.A.<br />
Maropack GmbH & Co. KG, and<br />
SFV Verpackungen<br />
Cover<br />
Cover: Monika Gniot (Shutterstock)<br />
4 bioplastics MAGAZINE [02/14] Vol. 9<br />
Follow us on twitter:<br />
http://twitter.com/bioplasticsmag<br />
Like us on Facebook:<br />
http://www.facebook.com/pages/bioplastics-MAGAZINE/103745406344904
News<br />
Biofore Concept Car uses biomaterials<br />
The Biofore Concept Car, presented at the Geneva<br />
International Motor Show 2014, showcases the use of<br />
UPM’s (Helsinki, Finland) innovative biomaterials in the<br />
automotive industry. The majority of parts traditionally<br />
made from plastics are replaced with high quality, safe and<br />
durable biomaterials, UPM Formi and UPM Grada, which can<br />
significantly improve the overall environmental performance<br />
of car manufacturing. The Biofore Concept Car is designed<br />
and manufactured by students from the Helsinki Metropolia<br />
University of Applied Sciences.<br />
Parts made of UPM Grada thermoformable wood material<br />
are the passenger compartment floor, centre console,<br />
display panel cover and door panels. Grada technology<br />
revitalises the forming of wood with heat and pressure, and<br />
opens up new opportunities for designs not achievable with<br />
traditional methods. UPM Grada’s unique forming properties<br />
enable high quality ecological designs which are also visually<br />
appealing.<br />
Parts made of UPM Formi biocomposite include front<br />
mask, side skirts, dashboard, door panels and interior<br />
panels. UPM Formi is a durable, high quality biocomposite for<br />
injection moulding, extrusion and thermoforming production.<br />
Consisting of renewable fibres and plastic, the material is<br />
non-toxic, odourless and uniform in quality. UPM Formi is<br />
ideal both for industrial and consumer applications. UPM‘s<br />
responsible supply chain combined with use of renewable<br />
raw materials ensure a small carbon footprint.<br />
“Sustainability is a major subject globally. We were<br />
excited to be able to design and build a vehicle that would<br />
demonstrate that already today we have biomaterials that are<br />
a real alternative to traditional oil-based materials. During<br />
the past four years of building the Biofore Concept Car, our<br />
students have come to see that these biomaterials are of high<br />
quality, durable and also offer new design opportunities,”<br />
says Pekka Hautala, Project Director from Metropolia.<br />
“The Biofore Concept Car showcases the potential of<br />
UPM’s biomaterials. Not only for the automotive industry, but<br />
also for various other end-uses including design, acoustics<br />
- a wide range of industrial and consumer applications. The<br />
possibilities are endless,” says Elisa Nilsson, Vice President<br />
of Brand and Communications at UPM.<br />
“According to our Biofore strategy, we create value from<br />
renewable raw material - wood from responsibly managed<br />
forests - and strive for a more resource efficient future.<br />
The Biofore Concept Car is a fine manifestation of this. We<br />
are proud of the cooperation with Metropolia’s automotive<br />
engineering and industrial design students, and what we<br />
have achieved together,” Nilsson concludes.<br />
bioplastics MAGAZINE will report in more detail about the<br />
biomaterials in upcoming issues.<br />
www.bioforeconceptcar.upm.com<br />
Bio-succinic acid market volume<br />
is expected to reach 710,000 tonnes<br />
Allied Market Research recently published a new market<br />
research report titled “Bio-succinic Acid Market - Size, Share,<br />
Trends, Opportunities, Global Demand, Insights, Analysis,<br />
Research, Report, Company Profiles, Segmentation and<br />
Forecast, 2013 - 2020.” As per the study, the global bio-succinic<br />
acid market volume is expected to grow at a CAGR of 45.6%<br />
between 2013 and 2020. The market revenue was estimated<br />
to be $115.2 million in 2013 and is expected to grow to $1.1<br />
billion by 2020. Increase in demand of bio-based chemicals<br />
is the major driver for this market. In addition, rising crude<br />
oil prices, adoption in newer industrial applications namely,<br />
1,4-Butanediol (BDO), PBS, polyester polyols (polyurethane),<br />
and plasticizers will enable faster growth of the market<br />
“The potential for bio-succinic acid market is in the<br />
replacement of existing succinic acid and adoption in newer<br />
industrial application areas, namely, 1,4-butanediol (BDO), PBS,<br />
polyesterpolyols (polyurethane), alkyd resins and plasticizers.<br />
These factors together will provide faster growth thrust to the<br />
market” states Allied Market Research analyst Sarah Clark.<br />
“Presently, price of bio-succinic acid may hinder market growth<br />
as it costs higher than petroleum based succinic acid. However,<br />
mass production and improvement in production techniques<br />
will quickly address the cost viability issue of the bio-succinic<br />
acid market” adds Ms. Clark. Moreover, lower volatility of<br />
feedstock prices will add to its stable adoption in various<br />
application segments.<br />
www.alliedmarketresearch.com/bio-succinic-acid-market<br />
bioplastics MAGAZINE [03/14] Vol. 9 5
News<br />
SABIC launches<br />
renewable polyolefins<br />
BASF presents<br />
biobased Ultramid<br />
SABIC (headquartered in Saudi Arabia) recently announced<br />
that it will launch its first portfolio of certified renewable<br />
polyolefins, certified under the ISCC Plus certification scheme,<br />
which involves strict traceability and requires a chain of custody<br />
based on a mass balance system. The portfolio, which includes<br />
renewable polyethylenes (PE) and polypropylenes (PP), responds<br />
to the increasing demand for sustainable materials from SABIC’s<br />
customers, most notably in the packaging industry, and is<br />
applicable for all its polyolefins grades, potentially for all market<br />
applications.<br />
SABIC is the first petrochemicals company to be able to<br />
produce renewable second generation PP & PE. SABIC has a<br />
unique position in Europe to be able to crack heavy renewable<br />
feedstocks made from waste fats and oils in its assets.<br />
SABIC worked closely with the International Sustainability and<br />
Carbon Certification (ISCC) organization to prove the sustainability<br />
of the new feedstock. Independent third party auditors checked<br />
and ensured the reliable use of the mass balance system within<br />
SABIC.<br />
In addition, SABIC worked closely with the Dutch Ministry<br />
of Economic Affairs under a Green Deal, on the concept of<br />
‘sustainability certificates’, with the ultimate objective to<br />
encourage the production and use of bio-based polyolefins within<br />
the industry.<br />
The ISCC Plus certified polypropylene (PP) and polyethylene<br />
(PE) materials will be produced initially at SABIC’s production<br />
facilities at Geleen in the Netherlands. MT<br />
www.sabic.com<br />
BASF now offers high performance Ultramid ®<br />
(polyamide), which is derived from renewable raw<br />
materials. BASF uses an innovative approach that replaces<br />
up to 100% of the fossil resources used at the beginning of<br />
the integrated production process with certified biomass.<br />
The share of renewable raw materials in the sales product<br />
is then indicated in the respective quantity. A third-party<br />
certification confirms to customers that BASF has used the<br />
required quantities of renewable raw materials which the<br />
customer has ordered in the value chain.<br />
The resulting Ultramid, which is produced according to<br />
the so called mass balance approach, is identical in terms<br />
of formulation and quality but associated with lower green<br />
house gas emissions and saving of fossil resources. Also,<br />
existing plants and technologies along the value chain can<br />
continue to be used without changes.<br />
“Consumer demand for products made of renewable raw<br />
materials continues to rise,” says Joachim Queisser, Senior<br />
Vice President of the Polyamides and Precursors Europe<br />
regional business unit. “This offering opens excellent<br />
possibilities for packaging film manufacturers to market<br />
their products accordingly.” MT<br />
www.basf.com<br />
interpack - review<br />
Editor‘s note on these two news<br />
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?<br />
The idea is to throw a biobased carbon source (from oil crops or even from used oils and fats) into a cracker, which typically<br />
stands at the beginning of a complex chemical site with many outlets and inter-connections. Whilst usually running on fossil oil<br />
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<br />
assigned to a respective output, here an amount of produced renewable plastic. This is completely independent from whether a<br />
scientist would detect or not any biobased carbon in the respective product when applying the radio carbon method. At least no<br />
one can tell how much biobased content is actually in the end product. The claims however inform about “renewable polyolefin”<br />
or a product “Derived from up to 100% renewable feedstock”. It’s all done by calculation. Think about the competitive product,<br />
which might be a biobased carbon containing product. Is it OK to call a Mass Balance calculated product renewable polymer?<br />
What do you think needs to be the legitimation for such claims? You may be aware about the CEN TC 411 standardisation which<br />
is ongoing and which tries to answer such questions through science and broad stakeholder and expert agreements.<br />
The whole approach seems like a huge black box: there is (biobased) input on one end and there is assigned biobased<br />
plastics as output on the other end. It is comparable to 100% renewable electricity. I do buy 100% renewable electricity, knowing<br />
well that the power coming from my outlet is being produced by a nearby coal power station... is this OK?<br />
This new approach poses a lot of questions. Let this editor’s note be food for thought and let’s discuss these questions in<br />
detail in the upcoming issues of bioplastics MAGAZINE. Michael Thielen<br />
6 bioplastics MAGAZINE [03/14] Vol. 9
News<br />
New online platform at bioplasticsmagazine.com<br />
Tap into the online resources of the new bioplastics MAGAZINE news platform!<br />
On our website bioplasticsmagazine.com we used to have a News-section, that was, however, not well maintained.<br />
This is has changed now. A new platform at<br />
news.bioplasticsmagazine.com now offers a new online<br />
resource targeted at readers seeking a medium that answers<br />
the need for reliable news and informative content with<br />
immediate appeal. Visitors will find new news-items every<br />
day now. Together with the printed bioplastics MAGAZINE, and<br />
the new, biweekly bioplastics MAGAZINE newsletter, it offers<br />
a platform for professionals in the industry to reach out to<br />
prospective partners, suppliers and customers across the<br />
globe.<br />
The bioplastics MAGAZINE newsletter reaches a<br />
targeted audience of some 7000 international bioplastics<br />
professionals across all continents. The platform offers<br />
readers up-to-date news and advertisers the power to<br />
create integrated campaigns, built on interaction between<br />
the different media channels and taking advantage of the<br />
different strengths of each. For advertisers, a perfect means<br />
to add value to opportunity.<br />
Visit news.bioplasticsmagazine.com (without www) every day to stay up-to-date.<br />
Newlight Technologies sprints ahead<br />
US telecom giant Sprint takes pride in its reputation for<br />
bringing sustainable options to market. The company, just<br />
recently announced that it is becoming one of the first to<br />
use AirCarbon, a new carbon-negative PHA made from<br />
greenhouse gas to create plastic products.<br />
The material will be used to produce cell phone cases for the<br />
iPhone 5 and iPhone 5s. Sprint is the first telecommunications<br />
company in the world to launch a carbon-negative product<br />
using AirCarbon.<br />
AirCarbon is manufactured by California-based<br />
sustainable materials producer NewlightTechnologies,<br />
using a proprietary carbon capture process to convert air<br />
and greenhouse gases (GHGs) into a plastic that has similar<br />
durability and performance characteristics to petroleumbased<br />
plastics. The conversion technology can synthesize<br />
high-performance thermoplastics from a wide range of<br />
sources, including methane and/or carbon dioxide from<br />
agricultural operations, water treatment plants, landfills,<br />
anaerobic digesters, or energy facilities. The PHA material<br />
has wide applications, as it can then be formed and moulded<br />
into almost any given design.<br />
Newlight announced on January 1st of this year that it had<br />
achieved successful commercial scale-up of its technology.<br />
Today, its commercial site is a four-story operation with a<br />
multi-million pound per year nameplate production capacity,<br />
using air and captured methane-based carbon emissions<br />
from a farm to produce AirCarbon.<br />
“AirCarbon offers a new paradigm in which products we<br />
use every day, like cellphone cases, become part of the<br />
environmental solution,” said Mark Herrema, Newlight<br />
Technologies co-founder and CEO. “Newlight’s mission is<br />
to replace petroleum-based plastics with greenhouse gasbased<br />
plastics on a commodity scale by out-competing on<br />
price and performance – harnessing the power of our choices<br />
as consumers to make change. We’re thankful for companies<br />
like Sprint, which are helping us realize our founding vision of<br />
taking greenhouse gases and turning them into commercially<br />
useful products that generate both an environmental and<br />
economic benefit.”<br />
As Herrema pointed out: “We have spent over a decade<br />
optimizing our technology. Today, we have a four-story plant<br />
capturing carbon that would otherwise go into the air, using<br />
that carbon to make products that would otherwise be made<br />
from oil. As a result, our efforts have shifted from technology<br />
development to commercial expansion.” KL<br />
www.newlight.com<br />
bioplastics MAGAZINE [03/14] Vol. 9 7
io PAC<br />
Biobased<br />
packaging<br />
conference<br />
may 2015<br />
amsterdam<br />
bio CAR<br />
Biobased materials for<br />
automotive applications<br />
conference<br />
fall 2015<br />
» Packaging is necessary.<br />
» Packaging protects the precious goods<br />
during transport and storage.<br />
» Packaging conveys important messages<br />
to the consumer.<br />
» Good packaging helps to increase<br />
the shelf life.<br />
BUT:<br />
Packaging does not necessarily need to be made<br />
from petroleum based plastics.<br />
biobased packaging<br />
» is packaging made from mother nature‘s gifts.<br />
» is packaging made from renewable resources.<br />
» is packaging made from biobased plastics, from<br />
plant residues such as palm leaves or bagasse.<br />
» The amount of plastics in modern cars<br />
is constantly increasing.<br />
» Plastics and composites help achieving<br />
light-weighting targets.<br />
» Plastics offer enormous design opportunities.<br />
» Plastics are important for the touch-and-feel<br />
and the safety of cars.<br />
BUT:<br />
consumers, suppliers in the automotive industry and<br />
OEMs are more and more looking for biobased<br />
alternatives to petroleum based materials.<br />
That‘s why bioplastics MAGAZINE is organizing this new<br />
conference on biobased materials for the automotive<br />
industry.<br />
» offers incredible opportunities.<br />
www.bio-pac.info<br />
www.bio-car.info
PRESENTS<br />
2014<br />
THE NINTH ANNUAL GLOBAL AWARD FOR<br />
DEVELOPERS, MANUFACTURERS AND USERS OF<br />
BIO-BASED PLASTICS.<br />
Call for proposals<br />
Enter your own product, service or development, or nominate<br />
your favourite example from another organisation<br />
Please let us know until August 31st:<br />
1. What the product, service or development is and does<br />
2. Why you think this product, service or development should win an award<br />
3. What your (or the proposed) company or organisation does<br />
Your entry should not exceed 500 words (approx 1 page) and may also<br />
be supported with photographs, samples, marketing brochures and/or<br />
technical documentation (cannot be sent back). The 5 nominees must be<br />
prepared to provide a 30 second videoclip<br />
More details and an entry form can be downloaded from<br />
www.bioplasticsmagazine.de/award<br />
The Bioplastics Award will be presented during the<br />
9 th European Bioplastics Conference<br />
December 2013, Brussels, Belgium<br />
supported by<br />
Sponsors welcome, please contact mt@bioplasticsmagazine.com<br />
bioplastics MAGAZINE [04/13] Vol. 8 9
Injection Moulding<br />
Injection moulding of PTT<br />
Combining the benefits of renewability with<br />
processing and performance advantages<br />
As the demand for bio-based polymers with renewable<br />
materials content, smaller carbon footprint and reduced<br />
dependence on fossil fuels continues to grow, the<br />
challenge for advanced polymer producers is to offer these<br />
environmentally friendly attributes without compromising<br />
processing and end-use performance.<br />
DuPont took up the challenge in developing a new biobased<br />
engineering thermoplastic —Sorona ® EP PTT (poly<br />
trimethylene terephthalate) — working closely with plastics<br />
processors and parts manufacturers to prove several key<br />
processing and finished part benefits versus PBT (polybutylene<br />
terephthalate), PET (polyethylene terephthalate) and PC/<br />
ABS (polycarbonate/acrylonitrile butadiene styrene) in developmental<br />
and commercial programs.<br />
With Sorona EP, DuPont achieved a new combination of<br />
advantages in one product – a renewably sourced engineering<br />
plastic that can be processed in the same way as PBT<br />
and PET, and also offers very low shrinkage and warpage,<br />
plus enhanced surface finish, gloss, and scratch resistance<br />
in finished parts.<br />
The DuPont PTT contains 20% to 37% renewable content<br />
made from starch, using proprietary fermentation and chemical<br />
processes, resulting in high-performance resins suitable<br />
for engineering applications. A DuPont cradle-to-gate<br />
study indicates that the bio-based Sorona EP has a smaller<br />
carbon footprint than the traditional fossil route used to<br />
make the same polymer. Using bio-feedstock makes Sorona<br />
EP less dependent on fossil fuels, yet the performance of<br />
these products more than competes with conventional PBT,<br />
PET and PC/ABS.<br />
Renewably sourced Sorona was one of the bio-based polymers<br />
independently certified to meet the United States<br />
Department of Agriculture (USDA) BioPreferred program<br />
standards for biobased content. In addition to replacing<br />
petrochemical based ingredients with those made with renewable<br />
resources, the DuPont PTT also provides a 30% reduction<br />
in energy use and a 63% reduction in carbon dioxide<br />
emissions compared to incumbent materials such as nylon 6.<br />
Grades and properties<br />
Sorona EP is currently available in a selection of grades<br />
including unreinforced, medium toughened, and15%, 30%<br />
and 45% glass-fiber reinforced grades. Table 1. shows grade<br />
properties, and comparison with equivalent glass-reinforced<br />
PBT and PET polymers.<br />
Toyota chose DuPont Sorona EP for instrument panel<br />
vent louvre vanes on the Prius hybrid electric car to ensure<br />
scratch resistance and excellent surface appearance<br />
Diagram 1:<br />
Drying curve of 15% glassreinforced<br />
Sorona EP at 120°C<br />
Moisture Content (%)<br />
0 0.05 0.10 0.15 0.20<br />
0 1 2 2 2 5<br />
During at 120 °C, -40 °C Dew Point<br />
DuPont Sorona 3015G NC010 [Melt Temperature / Residence Time]<br />
10 bioplastics MAGAZINE [03/14] Vol. 9
ISO Sorona 3301<br />
Unreinforces<br />
Sorona<br />
3015G<br />
PBT-GF15<br />
Sorona<br />
3030G<br />
PBT-GF30 PET-GF30 Sorona<br />
2045G<br />
Stress at Break, MPa 60* 125 109 165 140 158 180<br />
Strain at Break, % 15 3 3.5 2.5 2.7 2.5 1.6<br />
Tensile Modulus, MPa 2,400 6,500 5,800 11,000 10,000 11,000 16,000<br />
Notched Charpy, kJ/m 2 4 5.5 7 9 11 11 9<br />
Melting Temperature, °C 228 227 225 227 225 252 227<br />
Density, g/cm 3 1.3 1.4 1.4 1.56 1.53 1.56 1.7<br />
Parallel 1.3 0.2 0.4 0.2 0.3 0.2 0.2<br />
Mold Shrinkage, 2 mm, %<br />
Normal 1.4 0.7 1.1 0.7 1.1 0.8 0.5<br />
Table 1:<br />
Properties of currently<br />
available Sorona EP<br />
grades, and comparison<br />
with equivalent<br />
glass-reinforced PBT<br />
and PET polymers<br />
* Stress at Yield<br />
Commercial successes<br />
“The end-use advantages of Sorona EP — higher strength<br />
and stiffness at elevated temperatures, lower warpage and<br />
shrinkage, and improved scratch resistance and surface appearance<br />
— are already being seen in successful commercial<br />
programs,” said Thomas Werner, Business Development Manager,<br />
DuPont Performance Polymers.<br />
“These attributes make Sorona EP an excellent choice for<br />
many precision molded industrial and consumer products,<br />
including automotive parts such as instrument panel air conditioning<br />
vent louvers — chosen by Toyota for the Prius —<br />
electrical/electronic components like connectors, switches,<br />
plugs, mobile phone housings, and for furniture.”<br />
In its renewably sourced fiber form, Sorona is already widely<br />
used in residential and commercial carpets, apparel and<br />
automotive mats and carpets. Mohawk Group, the worlds largest<br />
flooring manufacturer, HBC Bulckaert and Godfrey Hirst<br />
Carpets, specify the DuPont biopolymer for durability and<br />
stain resistance. In automotive, the Toyota SAI ® has ceiling<br />
surface skin, sun visor and pillar garnish of Sorona, complementing<br />
the car’s eco-friendly design.<br />
Processing characteristics and recommendations<br />
Material preparation<br />
Like PET polyester, pellets of Sorona EP must be dried to<br />
a moisture content below 0.02%, using a dehumidifier drier<br />
with direct material transfer in a closed hopper, to ensure<br />
that optimum mechanical properties are achieved. The dew<br />
point of the drier must remain below -20°C.<br />
A drying temperature of 120°C is recommended, allowing 4<br />
hours drying for a newly opened bag, and 6-8 hours for a bag<br />
that has been opened for more than 1 week.<br />
Flow length<br />
Sorona EP exhibits good flow properties, allowing parts<br />
with long flow paths and narrow wall thicknesses to be molded<br />
easily. Good flow also contributes to generating a high<br />
surface finish and glossy appearance, even with glass-fiber<br />
reinforced grades.<br />
Using a standard 1mm thickness spiral flow test, Sorona<br />
EP exhibited 20% greater flow than standard PBT, allowing:<br />
Diagram 2:<br />
Strain at break of Sorona EP as a function<br />
of melt temperature and residence time<br />
Diagram 3:<br />
Recommended cylinder temperature<br />
setting as a function of residence time<br />
ain at Bre<br />
5 10 15 20 25<br />
0 10 20<br />
250 °C / 6 min<br />
250 °C / 10 min<br />
250 °C / 15 min<br />
270 °C / 6 min<br />
275 °C / 10 min<br />
Temperat<br />
ture<br />
230 240 250 260 270 280<br />
270 °C<br />
250 °C<br />
235 °C<br />
90 °C<br />
5 min<br />
Residence<br />
Time<br />
Molding Settings<br />
[Melt Temperature / Residence Time]<br />
Front<br />
Center<br />
Rear<br />
bioplastics MAGAZINE [03/14] Vol. 9 11
improved filling of longer cavities<br />
reduced part thickness<br />
reduced melt temperatures to fill the<br />
same cavity, enabling shorter molding<br />
cycle time<br />
gating simplification.<br />
Melt stability - mechanical properties<br />
Sorona EP exhibits good melt stability<br />
without significant change in mechanical<br />
properties up to a residence<br />
time of 10 minutes, when dried to below<br />
0.02% moisture content and molded at<br />
a recommended melt temperature of<br />
250°C. The melting point of Sorona EP<br />
is 227°C, close to PBT at 225°C.<br />
Melt stability - cylinder profile<br />
When molding semi-crystalline polymers<br />
such as PBT and Sorona EP PTT,<br />
the cylinder temperature profile should<br />
be adjusted as a function of residence<br />
time to minimize degradation, maintain<br />
stability, and achieve an optimum balance<br />
of homogeneity while maintaining<br />
the high molecular weight of the molten<br />
material.<br />
Effect of mold temperature on<br />
aesthetics<br />
Superior surface quality and a high<br />
gloss effect require a minimum temperature<br />
of 80°C in a polished mold. Increasing<br />
the mold temperature to 90°C will<br />
further improve the excellent scratch<br />
resistant properties of the DuPont PTT.<br />
This has been demonstrated in Erichsen<br />
scratch hardness testing showing that<br />
increasing the mold temperature from<br />
70°C to 90°C increases the scratching<br />
force by up to 8N.<br />
Effect of mold temperature on<br />
shrinkage and warpage<br />
Shrinkage is caused by thermal contraction<br />
and crystallisation of the polymer<br />
during the hold pressure and cool<br />
down phase. Uneven wall thickness and<br />
anisotropic fillers will reinforce a tendency<br />
to deform.<br />
Non-reinforced Sorona EP exhibits<br />
approximately 0.4 to 0.5% lower shrinkage<br />
than standard PBT, while parts<br />
molded in glass-reinforced Sorona EP<br />
have shown less warpage versus standard<br />
glass-reinforced PBT. To produce<br />
molded parts of Sorona EP with optimum<br />
characteristics and low postshrinkage<br />
requires a sufficient degree<br />
of crystallization. This is influenced to a<br />
large extent by mold temperature.<br />
A mold temperature of 80°C is sufficient<br />
to produce parts with low postshrinkage.<br />
Higher mold temperatures<br />
(>85°C) contribute to reduced dimensional<br />
changes caused by post-crystallization<br />
(post-shrinkage).<br />
Meeting growing demand for<br />
bio-based polymers<br />
With Sorona EP, DuPont has developed<br />
a PTT polymer that meets the growing<br />
demand for a sustainable bio-based<br />
Photo 1: excellent high gloss finish of<br />
unreinforced Sorona EP pigmented using<br />
a masterbatch<br />
engineering plastic with in-use performance<br />
equivalent to, or better than,<br />
PBT, PET or PC/ABS polymers.<br />
It also exhibits a molding behavior<br />
similar to high-performance PBT in<br />
conventional injection molding equipment.<br />
Processing conditions are essentially<br />
the same with some minor adjustments,<br />
following DuPont processing<br />
recommendations.<br />
Compared to PBT, glass-fiber reinforced<br />
Sorona EP exhibits better mechanical<br />
properties at elevated temperatures<br />
including enhanced strength<br />
and dimensional stability, stiffness, lower<br />
warpage and shrinkage, and improved<br />
surface appearance.<br />
The new backbone chemistry of PTT<br />
provides new functionality to a PBT-like<br />
polymer. A skilled molder with PBT expertise<br />
should have no concerns about<br />
testing Sorona EP. The reward will be in<br />
the added value of higher quality finished<br />
components. <br />
www.dupont.com<br />
Diagram 5:<br />
Backbone chemistry of Sorona EP PTT<br />
Diagram 4:<br />
Shrinkage and post-shrinkage of Sorona EP PTT polymers<br />
Annealing conditions: 1 hour in an oven at 120°C<br />
HO<br />
C<br />
C<br />
C<br />
OH<br />
1,3 Propanediol<br />
(PDO)<br />
+<br />
HO<br />
O<br />
C<br />
O<br />
C<br />
OH<br />
Terephthalic Acid<br />
O<br />
O<br />
O C O<br />
C C C C C C C<br />
O C O<br />
O<br />
O<br />
Polytrimenthylene terephtalate<br />
S hrinkage<br />
(%)<br />
0.80 1.00 1.20 1.40 1.60 1.80<br />
Standard PBT after annealing<br />
Standard PBT<br />
DuPont Sorona 3301 NC010<br />
after annealing<br />
DuPont Sorona 3301 NC010<br />
40 60 90 110<br />
Melt Temperature (°C)<br />
12 bioplastics MAGAZINE [03/14] Vol. 9
9th & 10th September 2014<br />
Thon EU Hotel, Brussels<br />
Bioeconomy in Action –<br />
from Rhetoric to Reality<br />
e Bio-based Global Summit will inform decision<br />
akers from the Bio Chemical, Plastic, Polymer<br />
d Packaging markets of the real potential<br />
d viability of the Bio economy – in terms of<br />
emicals, plastics and fuels.<br />
Speaking at the Bio-based Global Summit will be:<br />
Maira Magnani, Ford Research & Advanced<br />
Engineering Europe<br />
esse Putzel, Senior Sustainability Manager, BAM<br />
(Packaging Design Agency)<br />
Dr John Williams, Group Technical Director,<br />
Sinvestec<br />
Rulande Henderson, PhD, Commercial Director,<br />
Econic Technologies<br />
and many more<br />
Book your place now<br />
delegates rates are:<br />
ore 23rd June 2014 – Early bird delegate rate of €895<br />
elgian VAT<br />
or after 23rd June 2014 – Normal delegate rate of €1,000<br />
elgian VAT<br />
can book online at:<br />
www.biobased-global-summit.com<br />
Organised by Supported by Media partners
Injection Moulding<br />
The blend<br />
makes<br />
the difference<br />
Selectively optimizing the<br />
material properties of bioplastics<br />
PLA used:<br />
Ingeo 4043 D by Nature Works LLC;<br />
PBS used:<br />
GS Pla FZ 91 PD by Mitsubishi Chemical;<br />
binder used:<br />
Vinnex 2504 and Vinnex 2510 by Wacker Chemie AG<br />
With the exception of niche applications, bioplastics<br />
have so far failed to make a breakthrough on mass<br />
markets – often due to their unsatisfactory material<br />
properties or the lack of cost-effective production processes.<br />
Using sophisticated chemical techniques, the Munich (Germany)<br />
based chemical company WACKER has developed a<br />
solution for eliminating the inherent weaknesses of bioplastics.<br />
The improved physical properties of these materials<br />
mean they can now be processed like standard thermoplastics,<br />
using methods such as injection molding, extrusion or<br />
thermoforming.<br />
New Polymers Must Be Compatible with<br />
Polymer Industry Processes<br />
In order to expand their potential, bioplastics must possess<br />
properties that justify their use over traditional plastics. In<br />
addition to that requirement, however, bioplastics also have to<br />
be compatible with processes commonly used in the polymer<br />
industry, such as injection molding. A material that meets<br />
some of these requirements is polylactic acid (PLA), which<br />
is similar to traditional thermoplastics, and can easily be<br />
processed in existing plants. An inherent disadvantage of pure<br />
PLA, however, is that it is very rigid and its impact strength<br />
is low. Attempts have already been made to compensate this<br />
drawback through the use of suitable blends. One US patent,<br />
for instance, identifies a variety of aliphatic polyesters that<br />
can be blended with PLA to increase the impact strength of<br />
the material or make it more flexible [1].<br />
Vicat A [°C]<br />
0 10 20 30 40 50 60 70 80 90<br />
PLA<br />
PBS<br />
PBS / PLA / VINNEX<br />
PBS / PLA / VINNEX / Talc<br />
Fig. 1:<br />
Thermostability<br />
of PBS/PLA/Vinnex blends<br />
compared to PLA and PBS<br />
Tensile Strength [MPa]<br />
Elongation [%]<br />
Vicat A [°C]<br />
15,84<br />
Fig. 2:<br />
Long-term stability of the thermal<br />
and mechanical properties of a<br />
PBS/PLA/Vinnex blend<br />
3,78<br />
99,6<br />
15,63<br />
3,55<br />
99,3<br />
16,78<br />
3,75<br />
98,3<br />
0 10 20 30 40 50 60 70 80 90 100<br />
0 4 weeks 8 weeks<br />
14 bioplastics MAGAZINE [02/14] Vol. 9
Injection Moulding<br />
Another disadvantage of PLA is its poor resistance to<br />
heat, as amorphous PLA begins to soften at temperatures<br />
of approximately +60°C, making the material unsuitable for<br />
wide range of applications<br />
Crystallization generally improves PLA‘s thermostability.<br />
However, crystallization results in long processing times,<br />
which reduce the cost-effectiveness of the process. Therefore,<br />
the goal of development was to avoid costly thermal posttreatment.<br />
Eliminating Poor Heat Resistance and<br />
the Miscibility Gap<br />
Wacker developers discovered that the heat resistance<br />
of PLA increases from +58°C to +65°C when blended with<br />
polybutylene succinate (PBS). Further research at Mitsubishi<br />
Chemicals (an important PBS manufacturer) demonstrated<br />
that this effect can be magnified – increasing heat resistance<br />
to +100°C – through the use of a different grade of PBS (see<br />
Fig. 1).<br />
Making use of this effect, however, meant overcoming yet<br />
another hurdle. One study showed that PLA/PBS miscibility<br />
is limited and that a miscibility gap arises when PBS is<br />
blended with PLA at a concentration of 20% [2]. Researchers<br />
also found that the amount of PBS required to produce the<br />
desired properties falls within that miscibility gap.<br />
A solution to this problem is provided by VINNEX ® , a<br />
Wacker binder system based on polyvinyl acetate. Studies<br />
have demonstrated that Vinnex is compatible with both PLA<br />
and PBS, and that the addition of 15 to 20% Vinnex eliminates<br />
the miscibility gap. This results in visibly homogeneous<br />
polymer blends in which both polymers can be combined in<br />
any mixing ratio and essentially adjusted to the application at<br />
hand. The resulting blend combines the advantages of both<br />
components.<br />
Also, a partially crystalline PBS grade was used with a<br />
largely amorphous grade of PLA, which meant that another<br />
issue had to be resolved: long-term stability. Studies showed<br />
that the properties of PLA/PBS blends containing Vinnex had<br />
not changed within eight weeks, and that Vinnex apparently<br />
suppresses effectively post-crystallization of the PBS portion<br />
of the blend (see Fig. 2).<br />
Unlike PLA, PBS is not yet available on the market in large<br />
quantities, consequently making it expensive. That situation<br />
is set to change in the near future, however. The PTT Public<br />
Company Limited of Thailand and Mitsubishi Chemicals are<br />
already planning a joint venture (PTT MCC) involving the<br />
construction of a production facility in southeast Asia for<br />
manufacturing PBS from renewable raw materials.<br />
Improving Cost-Effectiveness with<br />
the Right Fillers<br />
In order to optimize the cost-effectiveness of the process,<br />
studies were performed with the aim of maximizing the<br />
PLA content of blends without affecting the thermostability<br />
achieved with PBS. One other project involved diluting costs<br />
by adding fillers such as calcium carbonate (chalk) or talc<br />
[N/mm 2 ]<br />
0 500 1000 1500 2000 2500 3000 3500 4000 4500<br />
0% Filler<br />
10% CaCO3<br />
20% CaCO3<br />
30% CaCO3<br />
10% Talc<br />
20% Talc<br />
30% Talc<br />
Fig. 3a:<br />
Effects of chalk and talc<br />
on the elastic modulus of<br />
PBS / PLA / Vinnex blends<br />
Fig. 3b:<br />
Effects of chalk and talc<br />
on the impact strength of<br />
PBS / PLA / Vinnex blends<br />
0% Filler<br />
10% CaCO3<br />
20% CaCO3<br />
30% CaCO3<br />
10% Talc<br />
20% Talc<br />
30% Talc<br />
0 10 20 30 40 50 60 70 80 90<br />
[kJ/m²]<br />
Tensile E-Modulus<br />
Charpy impact strength<br />
bioplastics MAGAZINE [04/14] Vol. 9 15
Injection Moulding<br />
in concentrations of up to 30%. Talc was found to be a particularly good fit, as<br />
it significantly increases both the elastic modulus (a measure of rigidity) and<br />
impact strength at concentrations of up to 20% (see Fig. 3a/b). Thanks to this<br />
effect, manufacturers can now achieve property profiles comparable to those of<br />
a number of standard plastics [3].<br />
The effect on processing was found to be similar: thanks to Vinnex, PLA/PBS<br />
polymer blends can easily be processed using traditional injection molding,<br />
thermoforming or extrusion equipment. And because Vinnex effectively<br />
suppresses recrystallization while improving melt strength, the polymer blend<br />
can be thermoformed to yield stable, three-dimensional structures.<br />
Thermoforming Opens the Door to Mass Markets<br />
With the aid of a series of prototypes, Wacker developers have now been able<br />
to demonstrate that blends of PLA and PBS can be thermoformed to create<br />
containers suitable for hot filling applications (see Fig. 4), opening up mass<br />
markets for products such as coffee cups and soup containers. Future consumer<br />
behavior may provide an additional tailwind as well: a recent study conducted<br />
by consulting firm Frost & Sullivan showed that food products represent the<br />
primary area where consumers demand biodegradable packaging. This requires<br />
food-contact approval for use in foods from the EU and the US Food and Drug<br />
Administration (FDA), which have already approved selected Vinnex grades. For<br />
PBS, food-grade approval in the US is still pending from the FDA, but this is<br />
expected in 2015 at the latest.<br />
Conclusion: Modular System for a Broad Range of Applications<br />
Polymers based on renewable resources may represent a sustainable<br />
alternative to petrochemicals. Until now, however, the properties and processing<br />
characteristics of pure biopolymers have often failed to match those of standard<br />
thermoplastics.<br />
Thanks to the Vinnex binder system, polymers based on renewable raw<br />
materials can now be processed just like conventional thermoplastics. The system<br />
improves the physical properties of the bioplastics and also makes the materials<br />
compatible with each other – the use of Vinnex for optimizing polymer blends is<br />
not limited to just the PLA/PBS system, after all. Quite the contrary: a variety of<br />
Vinnex grades can be combined with one or more biopolyesters and fillers. This<br />
modular concept makes it possible to combine polyhydroxyalkanoates (PHAs)<br />
with cellulose acetate (CA) or starch to create polymer blends that, depending<br />
on their composition and Vinnex content, exhibit better impact strength, melt<br />
strength and flexibility than conventional biopolymers.<br />
Vinnex thus opens up an expanding range of applications for bioplastics.<br />
For example, the new blends can be processed into food packaging materials,<br />
brochures, office supplies and promotional items, parts for electronic appliances<br />
or self-degradable gardening and agricultural containers. <br />
Fig. 4: Thermoformed parts made<br />
of PBS/PLA blends with Vinnex<br />
(right) and without Vinnex (left)<br />
Karl Weber<br />
Wacker Chemie AG<br />
References:<br />
[1] Li Shen, Juliane Haufe, Martin K. Patel:<br />
Product overview and market projection of<br />
emerging biobased plastics. PRO-BIP 2009,<br />
Final Report, June 2009.<br />
[2] McCarthy et. al, United States Patent<br />
5,883,199 (Mar. 16, 1999).<br />
[3] Bhatia, A, Gupta, R, Bhattacharya, S, and<br />
Choi, H 2007, “Compatibilty of biodegradable<br />
poly(lactic acid) (PLA) and poly(butylene<br />
succinate) (PBS) blends for packaging<br />
applications,” Korea-Australia Rheology<br />
Journal, vol. 19, no. 3, pp. 125-131.<br />
[4] Pfaadt, Marcus, Tangelder, Robert, European<br />
Patent EP 2 334 734 B1 of October 14, 2009.<br />
16 bioplastics MAGAZINE [02/14] Vol. 9
Show Review<br />
The booth of NatureWorks (Photo: Adsale)<br />
Chinaplas<br />
2014 -<br />
Review<br />
CHINAPLAS 2014, Asia’s largest plastics and rubber<br />
fair was running its 28th edition in Shanghai on 23-26<br />
April, setting a number of new records. The exhibition<br />
attracted 130,370 visitors during the 4-day show, up 14.26%<br />
as compared with last year in Guangzhou. It also sets a new<br />
record since its debut in 1983. With the exhibition becoming<br />
increasingly international, the number of overseas visitors<br />
soars by 19.73% to 36,841 which accounts for 28.26% of total<br />
visitors. They are coming from 143 countries and regions<br />
mainly from Hong Kong, India, Indonesia, Iran, Japan, Korea,<br />
Malaysia, Taiwan, Thailand, Russia, etc. The number of domestic<br />
visitors maintains a strong figure of 93,529 with an<br />
increment of 12.24%.<br />
Besides, CHINAPLAS also marks the new records in terms<br />
of exhibition scale and number of exhibitors participated.<br />
This year, over 3,000 exhibitors from 39 countries and<br />
regions participated in the show, of which over 400 are new<br />
to the show. In addition to occupying all 17 exhibition halls<br />
in Shanghai New International Expo Center (SNIEC), 13<br />
additional outdoor halls and 6 exhibition suites were also<br />
set up at the Central Square of SNIEC to cope with the ever<br />
increasing number of exhibitors, resulting in a total exhibition<br />
area over 220,000 sqm for this year.<br />
In a special Bioplastics Zone in hall N3 again more than<br />
30 companies were listed in the show catalogue to present<br />
their products and services in terms of biobased and/or<br />
biodegradable plastics. In contrast to previous years the<br />
number of companies offering traditional PE or PP filled with<br />
starch, straw or bamboo, as well as oxo-degradable additives<br />
and compounds was significantly smaller. On the contrary,<br />
it could be noticed, that the Chinese companies (suppliers<br />
as well as visitors/buyers) do no longer focus just on the<br />
biodegradability, but consider the biobased origin of raw<br />
materials as increasingly important. Suppliers of PBAT for<br />
example are looking for biobased 1,4-BDO …<br />
In addition to the Chinaplas Preview published in the last<br />
issue, you can find a few more highlights here.<br />
As a first time exhibitor at Chinaplas 2014, Reverdia (a JV<br />
between DSM and Roquette) demonstrated the benefits of<br />
Biosuccinium sustainable succinic acid with 100% bio-based<br />
content and lower environmental footprint. The company<br />
highlighted the value of partnership with the Chinese plastics<br />
industry. Biosuccinium enables the production of a biobased<br />
PBS (polybutylene succinate), a biodegradable polymer<br />
that can be used as a single polymer or in compounds for both<br />
durable and biodegradable applications. Other applications<br />
include polyols for polyurethanes, coating and composite<br />
resins and phthalate-free plasticizers. End products include<br />
footwear, packaging, paints and many more.<br />
Hydal Biotech is the first and only industrial technology for<br />
production of biopolymers in the world which uses waste, used<br />
cooking oil, as a source and doesn’t exhaust raw materials<br />
from the food chain. It also exhibits highest productivity and<br />
yield of the polymer thanks to patented know-how and used<br />
resources. Hydal Biotech is a Czech-Chinese Joint Venture<br />
founded by two partners that reached significant synergic<br />
effects. Its founders are Nafigate Corporation and Jiangsu<br />
Clean Environmental Technology Co., Ltd. Czech Company<br />
Nafigate Corporation, specialized in the transfer of high-tech<br />
technologies, has introduced its unique Hydal biotechnology<br />
to the Chinese market. Nafigate has partnered on this project<br />
with China-based Suzhou Cleanet, a company that collects<br />
and processes waste cooking oil at an increasing number of<br />
locations in China.<br />
Shanghai Disoxidation Enterprise Development Co., Ltd.,<br />
introduced a UV-stabilized grade of their PBAT based BSR<br />
09 material. Thus it is now perfectly suited for mulch film<br />
applications. Tests run in northern part of China showed<br />
very positive results. BSR 09 has been successfully produced<br />
since 2010, and acquired certificates of EN13432, ASTM<br />
D6400 and AS4736.MT<br />
www.chinaplasonline.com<br />
bioplastics MAGAZINE [06/13] Vol. 8 17
From Science & Research<br />
New biocomposites<br />
for car interior<br />
The development of novel biocomposites based on new<br />
biopolymers, reinforced with natural fibers, nanofillers<br />
and additives, for applications in automotive interior<br />
parts was the goal of the European Research Project<br />
ECOplast, which is now successfully nearly completed. The<br />
project consortium incorporates 13 partners coming from 5<br />
European countries and is led by the Spanish Galician Automotive<br />
Technological Centre (CTAG, (Porriño Pontevedra,<br />
Spain)<br />
Requirements for interior parts in automotive are manifold:<br />
mechanical stability, odor, fogging and temperature resistance<br />
are only a small sample of what the producers have to take<br />
care for. Bioplastics which are available nowadays do not<br />
meet the requirements of the automotive industry. Pablo Soto<br />
from Grupo Antolin, a Spanish automotive supplier who was a<br />
partner in the Ecoplast consortium, states: “We recognize that<br />
the automotive industry wants to use bio-based plastics and<br />
natural fibers on the condition that they pass the requirements<br />
for materials in interior parts that are really challenging, at<br />
a level of price similar to current materials“. Before Ecoplast<br />
started, the insufficient temperature resistance of PLA, for<br />
example, and the fogging behavior and volatile emissions of<br />
PHB prevented their use in car interiors.<br />
Improvements of PHB and PLA<br />
In the past, the odor and fogging of PHB limited its use<br />
in cars. Within the scope of the Ecoplast project, AIMPLAS<br />
(Paterna, València, Spain) studied the efficiency of<br />
supercritical CO 2<br />
(sc-CO 2<br />
) in the reduction of the volatiles. A<br />
significant reduction of the organic volatile substances by up<br />
to 80 % was achieved. However, the process was too expensive<br />
and instead of it a new formulation of PHB which reduces<br />
volatiles was developed. The components that lead to fogging<br />
or volatiles emissions were successfully identified and<br />
replaced by others. As a result BIOMER (Krailling, Germany)<br />
now offers a new formulation of PHB for car interior parts.<br />
Corbion (Gorinchem, The Netherlands) improved the<br />
temperature resistance of PLA by using PDLA nucleated<br />
PLLA materials, so-called nPLA. A separately developed high<br />
impact blend (n-PLAi) was used to overcome the low impact<br />
strength of PLA.<br />
Compatibilty of wood fibers<br />
The incompatibility of hydrophilic wood fibers and<br />
hydrophobic thermoplastic matrices causes weakness to<br />
composite material strength properties, especially impact<br />
strength. VTT (Espoo, Finland) modified the cellulose fiber<br />
surface to be more compatible with polymer matrix utilizing<br />
a new dry compacting method and reactive plasticizers<br />
or additives capable of forming bridges between fiber and<br />
polymer matrix. The resulted PLA-cellulose fiber composite<br />
material showed increased impact and tensile strength<br />
values. With rising amount of fibers the heat resistance, heat<br />
deflection temperature, HDT (A), of the composite material<br />
increases (see fig. 1).<br />
Fig. 1: Heat deflection temperature in dependence of fiber amount<br />
All in all, great improvements in the proprieties of the PLAcellulose<br />
fibre composites were achieved, just a few of the<br />
requirements for car interiors, as fogging or resistance to<br />
humidity, need further developments.<br />
PHB long natural fiber composites<br />
Compression molding appeared as the best option to<br />
reinforce PHB with fiber mats. The best results were<br />
achieved by Aimplas with impregnated flax mats. Using this<br />
process the PHB penetrates completely through the mats.<br />
The obtained samples show good mechanical properties and<br />
a nice appearance (see fig. 2). Values for unnotched Charpy<br />
impact reached more than 40 kJ/m 2 and the flexural modulus<br />
over 3 GPa.<br />
Fig. 2: PHB with flax mats<br />
18 bioplastics MAGAZINE [03/14] Vol. 9
From Science & Research<br />
Improvements using nanocellulose and nanoclays<br />
First trials with compounds of n-PLAi with nanocellulose<br />
indicated favourable results but the compound has to be<br />
optimized, which needs more research work. Preliminary<br />
tests of using nanocellulose as an additive in silk-elastin-like<br />
polymer matrices were promising, too.<br />
NBM has developed the first organomodified clays for the<br />
use in PLA compounds (see fig. 3). The preparation included<br />
the formulation, optimization and fabrication of the nanofillers<br />
according to proprietary purification and surface modification<br />
technology. A compound based on n-PLAi with 5 wt % of this<br />
new nanoadditive based on natural clays complies with all<br />
requirements defined in the project.<br />
New protein-based copolymer<br />
Basic research for the development of a new protein-based<br />
copolymer using silk-like crystalline and elastin-like flexible<br />
blocks (silk-elastin-like polymers, SELP), performed by the<br />
University of Minho, and for the scale-up of SELP production<br />
revealed good results. More details of this can be found in<br />
Casal et al. (2014). Additionally, the methodology and knowhow<br />
to produce biocomposites based on these novel polymers<br />
was developed within the Ecoplast project in collaboration with<br />
PIEP.<br />
New approaches to the biocomposites<br />
processing technologies<br />
PIEP addressed the possibility of processing the target<br />
biocomposites using a more energy efficient technology – iCIM:<br />
integrated twin screw extruder and in-line injection molding<br />
(see fig. 4) - and hence profit from the inherent advantages<br />
for this type of materials provided by iCIM: shorter residence<br />
times, lower shear stresses and superior maintenance of fiber<br />
morphology. For the studied n-PLA biocomposite it was possible<br />
to obtain, at least, the same level of mechanical performance,<br />
when compared to the results achieved with conventional<br />
technologies, sustaining the potential of this technology.<br />
Conclusion<br />
Ecoplast project results are very promising and may lead to<br />
the production of innovative completely bio-based composites<br />
which are validated for the automotive industry:<br />
Organomodified clays for PLA were developed. A compound<br />
based on n-PLAi with 5 wt % of this new nanoadditive<br />
complies with all requirements defined in the project.<br />
A great improvement of PHB properties was achieved,<br />
especially for PHB reinforced with short fibers which yielded<br />
results far better than expected. Additionally, of special<br />
importance is the development of a new PHB formulation<br />
that meets the automotive fogging requirements.<br />
PHB reinforced with mats shows interesting results.<br />
The materials can be used in different applications.<br />
For both materials under investigation in the Ecoplast<br />
project, n-PLA and PHB, the cycle times have been remarkably<br />
reduced during the project. Material prices are still high but are<br />
expected to be drastically reduced upon large-scale industrial<br />
commercialization of polymer production. Additionally, the<br />
reduction of processing costs has to be one of the principal<br />
lines of investigation in the near future.<br />
Fig. 3: TEM image of nanoclay in PLA matrix<br />
Fig. 4: iCIM: integrated twin screw extruder<br />
and in-line injection molding<br />
Literature:<br />
M. Casal, A. Cunha, R. Machado: „Future Trends for Recombinant<br />
Protein-Based Polymers: The Case Study of Development and<br />
Application of Silk-Elastin-Like Polymers“ in: Kabasci, S. (Ed.): Biobased<br />
Plastics: Materials and applications. (Wiley series in renewable<br />
resources, 11) Chichester: Wiley, 2014, S. 311; ISBN 978-1-119-99400-8.<br />
The partners involved in the project are:<br />
Centro Tecnológico de Automoción de Galicia<br />
(CTAG), Spain (coordinator)<br />
Asociación de Investigación de Materiales Plásticos<br />
y Conexas – AIMPLAS, Spain<br />
PIEP Associação sociação – Polo de Inovação em Engenharía<br />
de Polímeros, Portugal<br />
Biomer, Germany<br />
FKuR Kunststoff GmbH, Germany<br />
Fraunhofer-Institut für Umwelt-, Sicherheits- und<br />
Energietechnik UMSICHT, Germany<br />
Grupo Antolín – Ingeniería S.A., Spain<br />
Megatech ech Industries Amurrio S.L. (MEGATECH),<br />
Spain<br />
NanoBioMatters R&D (NMB), Spain<br />
Pallmann Maschinenfabrik GmbH & Co, Germany<br />
Corbion (Purac), Netherlands<br />
University of Minho (UMINHO), Portugal<br />
VTT–T<br />
Technical Research Centre of Finland, Finland<br />
www.ecoplastproject.com<br />
bioplastics MAGAZINE [03/14] Vol. 9 19
From Science & Research<br />
PHA from<br />
sunlight<br />
New route for bioplastics<br />
production in cyanobacteria<br />
via photosynthesis<br />
By:<br />
Minami Matsui<br />
RIKEN Center for Sustainable Resource Science<br />
Yokohama, Japan<br />
Photosynthesis<br />
PhaA<br />
Cupriavidus<br />
necator<br />
PhaB<br />
Cupriavidus<br />
necator<br />
PhaC<br />
Chromobacterium<br />
sp.<br />
Cyano<br />
bacteria<br />
Acetyl-CoA<br />
Acetoacetyl-CoA<br />
(R)-3-Hydroxybutyryl-CoA<br />
Polyhydroxyalkanoate (PHA)<br />
Heterotrophic<br />
bacteria<br />
Carbon source<br />
(sugars)<br />
Malonyl-CoA<br />
NphT7<br />
Streptomyces<br />
sp.<br />
Figure 1:<br />
Metabolic pathways for PHA production.<br />
For the production of PHA in cyanobacteria, the<br />
genes, phaA, phaB and phaC were introduced. The<br />
condensation reaction of two acetyl-CoA compounds to<br />
form acetoacetyl-CoA by PhaA was hypothesized to be<br />
thermodynamically unfavorable in cyanobacteria under<br />
photosynthetic conditions. Therefore, PhaA was replaced<br />
by NphT7 that catalyzes the irreversible condensation of<br />
acetyl-CoA and malonyl-CoA to give acetoacetyl-CoA.<br />
In the past few decades, among all of the bio-based polymers,<br />
polyhydroxyalkanoates (PHA) have gained significantly<br />
in interest since they were shown to be completely<br />
biodegradable in appropriate environments. Another attractive<br />
feature of PHAs, apart from their biodegradability, is that<br />
they can be synthesized from renewable resources, allowing<br />
a sustainable production on a large scale. PHA is a type of<br />
storage inclusion that is naturally synthesized by numerous<br />
micro-organisms under unfavorable growth conditions. However,<br />
the commercialization of PHA has been ongoing, but<br />
with limited success due to its high production cost. The use<br />
of heterotrophic bacteria for PHA production calls for culture<br />
requirements and the supply of carbon sources that contribute<br />
significantly to the cost of production.<br />
Cyanobacteria, endowed with a photosynthetic system to<br />
fix carbon dioxide in a reduced form, are an ideal biosynthetic<br />
machine for sustainable production of various industrially<br />
important products, such as PHA. The conversion of<br />
atmospheric carbon dioxide into a biopolymer by cyanobacteria<br />
eliminates the use of costly external carbon sources and helps<br />
to achieve a carbon neutral bioplastic production process.<br />
The current bottleneck for photosynthetic PHA production<br />
using plant and other photosynthetic micro-organisms is to<br />
achieve production at an economically viable level. Minami<br />
Matsui, Nyok Sean Lau and colleagues from the RIKEN<br />
Synthetic Genomics Research Team in collaboration with<br />
Sudesh Kumar at Universiti Sains Malaysia have genetically<br />
engineered a cyanobacterium to address the challenges in<br />
terms of cost and productivity.<br />
The genetically modified variant of the cyanobacterium,<br />
Synechocystis sp. strain 6803, synthesized an encouraging<br />
level of PHA as high as 14% of the dried cellular biomass.<br />
So far, this is the highest level achieved in completely<br />
photoautotrophic PHA production without the provision<br />
of any carbon source. The addition of a carbon source in a<br />
small amount (0.4% acetate) had improved PHA production<br />
to 41% of the dry weight. Although cyanobacteria have<br />
relatively simple nutrient requirements, the provision of<br />
exogenous carbon source was found to boost PHA production<br />
approximately three-fold. Nonetheless, the amount of carbon<br />
source provided was very much lower compared to that<br />
required by heterotrophic bacteria to achieve the same PHA<br />
production level. In this modified strain, the carbon flux to<br />
PHA biosynthetic pathway was enhanced by the introduction<br />
of acetoacetyl-CoA synthase from Streptomyces sp. CL190,<br />
an enzyme that catalyzes the irreversible condensation of<br />
acetyl-CoA and malonyl-CoA to give acetoacetyl-CoA. In<br />
addition, a highly active PHA polymerizing enzyme, PHA<br />
synthase from Chromobacterium sp., was also introduced to<br />
improve the strain’s production efficiency.<br />
To better understand the mechanism that leads to the<br />
enhanced photoautotrophic PHA production, gene expression<br />
in the PHA overproducer was compared with its unmodified<br />
counterpart. It is surprising to find that the activities of<br />
enzymes directly involved in PHA synthesis are not the<br />
critical factors responsible for the overproduction of PHA in<br />
20 bioplastics MAGAZINE [03/14] Vol. 9
From Science & Research<br />
Figure 2:<br />
Microscope image shows<br />
the likely accumulation of<br />
PHA in genetically modified<br />
cyanobacteria.<br />
Upper left: Image of cells after staining<br />
with nile-red pigment that shows lipid and<br />
polymer inclusions.<br />
Upper right: Image of cyanobacterial cells.<br />
Bottom: Merged image of upper two<br />
images. It shows that PHA is accumulating<br />
in cyanobacterias cells.<br />
the modified strain. On the other hand, genes<br />
encoding proteins involved in several aspects<br />
of photosynthetic activities were significantly<br />
upregulated in the PHA overproducer compared<br />
to the control strain. Results from this study<br />
suggest that cyanobacterial cells may utilize<br />
enhanced photosynthesis capability to drive<br />
the product formation. During PHA formation,<br />
the pool of carbon in cyanobacterial cells<br />
was constantly being used for the synthesis.<br />
In order to cope with the higher production<br />
demand, the cyanobacterial cells may increase<br />
the carbon fixing capacity to replenish the pool<br />
of carbon that was lost to PHA synthesis. At the<br />
same time, the flow of newly fixed carbon into<br />
cellular processes other than PHA (e.g. amino<br />
acids biosynthesis) was limited. Based on the<br />
findings of this study, future work can be done<br />
to engineer cyanobacteria for the production<br />
of various chemicals or biofuels and a similar<br />
approach can likely be extended to higher<br />
plants. It is hope that the development of a new<br />
route for the production of biopolymer only by<br />
solar energy will provide a platform for the shift<br />
of production process from petroleum-based to<br />
bio-based.<br />
Reference<br />
Lau, N.S., Foong, C.P., Kurihara, Y., Sudesh, K. & Matsui,<br />
M. RNA-Seq analysis provides insights for understanding<br />
photoautotrophic polyhydroxyalkanoate production in<br />
recombinant Synechocystis sp. PLoS One. 2014 Jan 22; 9(1):<br />
e86368. doi: 10.1371/journal.pone.0086368 (2014).<br />
<br />
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in Raw Materials,<br />
Machinery & Products<br />
Free of Charge<br />
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from the Industrial Sector<br />
and the Plastics Markets<br />
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Machinery & Equipment,<br />
Subcontractors<br />
and Services.<br />
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Executive Staff in the<br />
Plastics Industry<br />
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bioplastics MAGAZINE [03/14] Vol. 9 21
Application News<br />
Biobased cork –<br />
but not from bark<br />
Most bottles of wine savored by consumers today reach<br />
them in a standard format that was first adopted in the<br />
17th century: glass bottles and cork closures. However, in<br />
recent years debate has intensified on the ideal method<br />
for sealing bottles and the problems involving this type<br />
of cork.<br />
Cork is made from oak bark. The tree takes 25 years to<br />
give up its first harvest and then every nine years its cork<br />
bark can be harvested once again. The long production<br />
process and the presence of trichloroanisole (TCA), a<br />
fault of cork closures that imparts the aroma of mold<br />
(wine taint), has intensified the search for alternatives to<br />
ensure the longevity of the beverage, which has given rise<br />
to the use of engineered alternatives for bottle stoppers.<br />
Now wine lovers have a more sustainable option for<br />
their beverage. Nomacorc, the world’s leading producer<br />
of synthetic corks, has found an entirely new way to<br />
use Braskem’s sugarcane based polyethylene (Green<br />
PE) in its products. Called Select Bio, the closures are<br />
recyclable and feature the same oxygen-management<br />
performance as the conventional line, while also<br />
preventing deterioration and waste caused by processes<br />
such as oxidation and reduction.<br />
“The use of Braskem’s green polyethylene made from<br />
sugarcane gave us the materials we needed to offer our<br />
customers carbon-neutral corks, which not only helps<br />
guarantee the consistency and quality of the wines, but<br />
also supports the development of a more sustainable<br />
packaging solution,” explained dr. Olav Aagaard, Principal<br />
Scientist at Nomacorc.<br />
To Braskem, using Green Plastic helps strengthen<br />
environmental awareness around the world. “Choices<br />
such as Nomacorc’s attest to the high viability and<br />
excellent growth potential of this technology, which<br />
can be fully employed as a sustainable<br />
alternative to the use of fossil fuels,” said<br />
Marco Jansen, Renewable Chemicals<br />
Commercial Director at Braskem.<br />
interpack - review<br />
New toys for babies<br />
Bioserie (Hong Kong) is first to market with a line of toys that<br />
will provide health-conscious parents the safety they demand for<br />
their babies by using only plant based, renewable resources in<br />
their production.<br />
Toys and nursing aids is a significant milestone in Bioserie’s<br />
diversification into new consumer product markets and it marks a<br />
significant step in the availability of fully biobased toys and nursing<br />
aids for babies. For these products Bioserie is using Ingeo PLA<br />
by NatureWorks and a proprietary blend of biobased components.<br />
Even the coloring materials used are specially developed for<br />
biopolymers; they are based on sustainable raw materials and<br />
meet several global industry and composting standards, including<br />
EN 13432 (European Union), ASTM D6400 (USA), BPS GREENPLA<br />
(Japan).<br />
Stephanie Triau Samman, co-founder of Bioserie says “Most<br />
available toys are made of oil based plastics. As a parent, it’s<br />
very hard to know for sure that a product won’t have any negative<br />
health effects on your baby now or later. The information on toy<br />
packages are either inadequate, too technical for a normal person<br />
to understand or at times misleading. Bioserie puts an end to this<br />
with products derived from plants that are naturally free of any<br />
harmful substances associated with oil based plastic toys.”<br />
“We believe it is possible to enjoy technology without harming<br />
our children’s health and fragile ecosystems of our Earth,” says<br />
Kaya Kaplancali, Bioserie CEO. “We are exploring the cutting edge<br />
of bioplastics technology to develop products that allow consumers<br />
to enjoy life in a healthier, environmentally-responsible way.”<br />
Bioserie’s launch product line consists of a Rattle toy, a Stacker<br />
toy, a Teether and a Cutlery set.<br />
Since the launch of its first accessories for smartphones,<br />
starting with iPhone covers in 2010, Bioserie has won international<br />
recognition for its technological achievements in the field of<br />
bioplastics. It’s one of the first brands in the world to achieve<br />
100% biobased certification by USDA’s BioPreferred program.<br />
Bioserie was also nominated for bioplastics innovation awards in<br />
2013 in Germany by Nova Institut and in USA by SPI Bioplastics<br />
Council, for developing injection moulded bioplastic products with<br />
high durability and heat resistance. MT<br />
www.bioserie.com<br />
www.braskem.com<br />
www.nomacorc.com<br />
22 bioplastics MAGAZINE [02/14] Vol. 9
Applications<br />
White teeth –<br />
Naturally!<br />
Bio-polymers for high<br />
precision injection moulding<br />
AInterbros toothbrush are made primarily<br />
from renewable plastics. Furthermore,<br />
the packaging consists of a 100 % biobased<br />
plastic blister combined with a FSC certified<br />
carton board. This high value integrated product<br />
is the result of expert knowledge in a broad<br />
range of bioplastic materials and their processing<br />
on existing production equipment. As<br />
a result of its recently extended portfolio, FKuR<br />
Kunststoff GmbH, Germany, can now provide<br />
integrated material solutions fulfilling the requirements<br />
of even the most complex products.<br />
For many years Interbros GmbH from<br />
Schönau/Germany has been pursuing the<br />
strategy of developing an integrated toothbrush<br />
system made completely from bioplastics. The<br />
most important requirements were the use of<br />
the existing high end injection moulding and<br />
assembling lines while maintaining the quality<br />
of the toothbrushes. However, the fitting of the<br />
bristle filaments into the injection moulded<br />
handle would be a tough challenge for any new<br />
material as it has to be within a 10 µm tolerance.<br />
After successfully proving the processability<br />
of several biomaterials from FKuR’s portfolio for<br />
the injection moulding of the handles, Interbros<br />
decided on one of the transparent BIOGRADE ®<br />
materials as it is the best solution to demonstrate<br />
the performance of bioplastics for a<br />
toothbrush. This material offers a very good<br />
existing high performance lines with the bio<br />
based PA filaments produced by Hahl-Pedex,<br />
Germany, and packed into the transparent PLA<br />
blister and carton board. If customers require a<br />
more heat stable blister pack then a bio-based<br />
PET could be used for as a technically proven<br />
alternative.<br />
This toothbrush impressively demonstrates<br />
the success of a combination of several<br />
industrial scale plastics manufacturing<br />
processes to create an integrated solution<br />
from bioplastics. It is another success which<br />
proves that the tolerance and stability of FKuR’s<br />
materials’ is good enough for industrial scale<br />
processing and the injection moulding of very<br />
high precision fittings, even with state- of-theart<br />
hot-runner moulds. Furthermore, this added<br />
value toothbrush has been created without the<br />
need for any further investments in moulds or<br />
other expensive processing equipment.<br />
By:<br />
Christoph Lohr<br />
FKuR, Willich,Germany<br />
Hannes Hauser<br />
Sunstar-Interbros, Schönau, Germany<br />
www.sunstarinterbros.com<br />
www.hahl-pedex.com<br />
www.fkur.com<br />
bioplastics MAGAZINE [03/14] Vol. 9 23
From Science & Research<br />
Talc<br />
filled<br />
PLA<br />
Micronized talc:<br />
a functional filler<br />
for PLA nucleation<br />
The limited service temperature of standard PLA is narrowing the application<br />
opportunities in many disposable items (i.e. hot beverages cups) as well as<br />
in durable applications where service temperature is a relevant property. In<br />
general, for semi-crystalline polymers, by increasing the degree of crystallinity it<br />
is possible to improve the service temperature. Because of the limited crystallization<br />
kinetic of PLA, such polymer is not able to crystallise during standard shaping<br />
processes (such as in injection moulding). The usage of nucleating agent improves<br />
the crystallization speed, allowing PLA to enhance its properties.<br />
Highly micronized talc is a common nucleator for many semi-crystalline polymers<br />
(the most common one is polypropylene) and some properties of micronized talc as<br />
nucleator for PLA were investigated.<br />
Talc is a natural mineral and it can be identified as an hydrated magnesium sheet<br />
silicate. Talc is ranked as the softest mineral (Mohs scale) and it is hydrophobic and<br />
chemically inert. Thanks to its platy structure, talc is able to improve mechanical<br />
performances of polymers, offering quite high specific surface to better interact<br />
with the polymer. Because of its affinity with polymers, talc surface is a perfect<br />
substrate for crystal growth.<br />
Experimental<br />
Concerning PLA, the ability of different talc grades to enhance crystallization in<br />
such polymer was measured. The basic evaluation performed on PLA was related<br />
to differential scanning calorimeter (DSC) experiments. DSC is an easy method<br />
to evaluate crystallization, recording the exothermic peak, typically observed<br />
periment for most of semi-crystalline polymers. But when the<br />
cess is very slow, polymer chain structure re-organization can<br />
urther melting experiment.<br />
to neat PLA, once the polymer is in molten state and the<br />
history completely erased, if cooled under controlled conditions<br />
rystallization doesn’t take place. By melting the sample still<br />
olled conditions, it is possible to record an exothermic peak at<br />
°C, showing the PLA crystallization (Fig. 1).<br />
ntal evaluation, three different talc grades were considered: talc<br />
icronized talc), talc HTPultra5c (ultrafine talc) and talc NTT05<br />
nce talc). By modifying PLA with minor amounts of micronized<br />
sible to improve the crystallization behaviour, allowing modified<br />
hieve crystallization under cooling conditions. Two different talc<br />
rates were evaluated: 1% and 5%, by weight. Modification was<br />
rmed by dispersing talc in PLA via a 25mm twin screw extruder,<br />
ding talc upstream together with resin; also neat PLA was<br />
xtruded, as a reference for the process conditions.<br />
Table 1: half crystallization time for PLA<br />
modified with talc at different isothermal<br />
holding temperatures<br />
t 1/2<br />
@ 90°C [s] t 1/2<br />
@ 100°C [s] t @ 110°C [s]<br />
1/2<br />
Neat PLA 596 222 268<br />
PLA + 1% HTP1c 107 59 63<br />
PLA + 5% HTP1c
From Science & Research<br />
50 — Heat FlowEndo Up (mW)<br />
45 —<br />
Fig. 1:<br />
DSC curves of neat PLA<br />
In Fig. 2 it is possible to see the different DSC<br />
patterns for talc modified PLA at 1% talc HTP1c<br />
loading. In general all the three samples of talc<br />
gave same results in terms of crystallization<br />
temperature. By increasing the talc loading (5%),<br />
a higher crystallization temperature is recorded<br />
with no specific distinctions between the three<br />
talc samples. Talc loading plays a major role in<br />
PLA nucleation rather than the talc fineness.<br />
A relevant experiment, in order to better<br />
understand the crystallization conditions of<br />
talc modified PLA, is related to isothermal<br />
crystallization. Only talc HTP1c was considered<br />
as PLA modifier in this experiment. In DSC, the<br />
samples were heated up to 200°C at 10°C/min,<br />
held 5 min at 200°C and cooled rapidly (at<br />
100°C/min) down to the testing temperature,<br />
holding the specimen at testing temperature<br />
for a certain time, until crystallization takes<br />
place. Time was recorded and it quantifies the<br />
crystallization kinetic. Crystallization occurs<br />
at a temperature higher than glass transition<br />
temperature (Tg) because below Tg, molecular<br />
mobility is virtually zero, with no possibility<br />
of chain folding. PLA Tg is in the range of 60-<br />
70°C and experiments were performed from 90<br />
to 110°C as testing (hold) temperature for the<br />
isothermal crystallization on PLA modified with<br />
talc HTP1c at both 1% and 5% loading.<br />
In this experiment, the presence of talc<br />
significantly reduces the time to crystallization<br />
(generally expressed as time to achieve 50% of<br />
crystallization, t 1/2<br />
) allowing nucleated PLA to<br />
achieve crystallinity in a more reasonable time<br />
for practical process purposes. In Fig. 3, the<br />
behaviour of PLA modification with talc HTP1c at<br />
both 1% and 5% loading is shown. For each type<br />
of modification, three different temperatures<br />
were investigated. In table 1, the t 1/2<br />
values are<br />
summarized. The behaviour of the other two talc<br />
grades is basically similar to HTP1c. Talc loading<br />
plays a relevant role in shortening t 1/2<br />
.<br />
Based on such experiments, it appears that<br />
moulded PLA items must be kept at relatively<br />
high temperature for a certain time to develop<br />
the expected degree of crystallinity. Such<br />
process can be performed either from the melt<br />
of from quenched state, with a visible impact<br />
on production costs. The presence of a talc (as<br />
nucleator) in the resin helps to shorten such<br />
time improving the productivity. The reduction<br />
of crystallization time is also driven by the talc<br />
concentration. The minimum crystallization time<br />
is recorded at 100°C.<br />
40 —<br />
35 —<br />
30 —<br />
25 —<br />
20 —<br />
15 —<br />
10 —<br />
5 —<br />
0 —<br />
Crystallization<br />
Melting<br />
-50 -20 0 20 40 60 80 100 120 140 160 180 °C<br />
Fig. 2:<br />
DSC crystallization curves of talc modified PLA<br />
60 — Heat FlowEndo Up (mW)<br />
55 —<br />
50 —<br />
45 —<br />
40 —<br />
35 —<br />
30 —<br />
25 —<br />
20 —<br />
15 —<br />
10 —<br />
5 —<br />
0 —<br />
140 — Heat FlowEndo Up (mW)<br />
120 —<br />
100 —<br />
80 —<br />
60 —<br />
40 —<br />
20 —<br />
0 —<br />
neat PLA<br />
PLA + 1% HTP1c<br />
PLA + 5% HTP1c<br />
40 60 80 100 120 140 160 180 °C<br />
Fig. 3:<br />
Isothermal crystallyzation curves of talc modified<br />
PLA at different crystallization temperatures<br />
100°C<br />
110°C<br />
neat PLA<br />
PLA + 1% HTP1c<br />
PLA + 5% HTP1c<br />
0.2 1 2 3 4 5 6 7 8 9 min<br />
bioplastics MAGAZINE [03/14] Vol. 9 25
Market<br />
HDT A (@ 1.82 MPa) 1 % 5 %<br />
HDT B [°C]<br />
72 —<br />
71 —<br />
70 —<br />
69 —<br />
68 —<br />
67 —<br />
66 —<br />
Neat PLA HTP1c HTPultra5c NTT05<br />
Fig. 6:<br />
Heat Distortion Temperature (HDT A 1.82 MPa<br />
(according to ISO 75) of PLA modified with different<br />
loadings of micronized talc. Specimens were<br />
annealed 3h@110°C before testing<br />
Stiffness 1 % 5 %<br />
Flexural Modulus [Mpa]<br />
4900 —<br />
4700 —<br />
5400 —<br />
4300 —<br />
4100 —<br />
3900 —<br />
3700 —<br />
Impact notched 1 % 5 %<br />
Charpy notched @ 23 °C [kj/m 2 ]<br />
8 —<br />
7 —<br />
6 —<br />
5 —<br />
4 —<br />
3 —<br />
Neat PLA HTP1c HTPultra5c NTT05<br />
Fig. 5:<br />
Charpy noched (according to ISO 179/1eA) of PLA<br />
modified with different loadings of micronized<br />
talc. Specimens were annealed 3h@110°C before<br />
testing<br />
Neat PLA HTP1c HTPultra5c NTT05<br />
Fig. 4:<br />
Flexural modulus (according to ISO 178) of PLA<br />
modified with different loadings of micronized talc.<br />
Specimens were annealed 3h @110°C before testing<br />
By:<br />
Piergiovanni Ercoli Malacari<br />
Product and application development<br />
IMI Fabi, Milan, Italy<br />
For nucleation process the type of talc plays a minor role, while for both<br />
mechanical and thermal performances the situation is different and the<br />
three considered talc grades gave peculiar set of properties.<br />
In order to have comparable data, all specimens were injected by holding<br />
the mould at 30°C, to quench the molten polymer. In such condition, the<br />
crystallization didn’t take place in the mould. Specimens were annealed in<br />
oven at 110°C per 3 hours to post crystallize PLA.<br />
In terms of stiffness, the flexural modulus behaviour is shown in Fig. 4. The<br />
modification with 1% of talc didn’t affect PLA rigidity, while 5% talc loading<br />
recorded a visible improvement, up to 15% for talc NTT05 modification.<br />
Thanks to its platy structure, talc is able to improve PLA rigidity. Stiffness<br />
enhancement is generally linear with talc loading, but higher loading rates<br />
than 5% have not been investigated in this experimental work.<br />
The presence of a nucleator let the impact resistance improve versus the<br />
neat resin, because of better organized polymer structure. All the samples<br />
containing talc gave higher impact resistance than reference (Fig. 5). 1%<br />
talc loading is enough to record a significant improving in impact resistance.<br />
Ultrafine talc sample (HTPultra5c) shows better results thanks to its very<br />
tight particle size distribution.<br />
Concerning the evaluation of the service temperature, Heat Distortion<br />
Temperature (HDT) has been considered. HDT is the temperature at which<br />
a specimen, under a three point bending experiment at a specific load<br />
conditions, records a deflection of 0.25mm; it gives an easy indication about<br />
the service temperature.<br />
In Figure 6, HDT A (@ 1.82 MPa) data are listed. 1% talc modification doesn’t<br />
improve HDT of PLA, while the 5% talc modification offers a visible variation<br />
in service temperature. The modification with a high performing talc such<br />
as NTT05 allows to record a significant variation in HDT temperature versus<br />
the same loading of a highly micronized talc as HTP1c.<br />
Conclusions<br />
To allow PLA utilization in applications where service temperature<br />
plays the major role, the addition of highly micronized talc represents a<br />
good methodology for improving its thermal and mechanical properties,<br />
making such composites more interesting for technical applications. The<br />
incorporation of talc significantly accelerates the crystallization of PLA.<br />
From the experimental evidences, it appears that a small amount of talc<br />
(1%) is enough to achieve crystallization during molten PLA cooling process.<br />
In order to record a better kinetic in crystallization process, a higher talc<br />
amount has to be considered (5% loading), in combination with a relatively<br />
high mould temperature.<br />
The modification of PLA with talc allows to achieve higher rigidity (without<br />
compromising the impact resistance) and, thanks to the nucleation, better<br />
service temperature.<br />
In order to achieve reliable results in PLA modification, it is necessary to<br />
use micronized talc characterized by high degree in purity, by tight particle<br />
size distribution and by high lamellarity such as the three talc products<br />
examined in this experimental work. In particular, the right selection of talc<br />
becomes very important when relatively high talc loadings are considered<br />
(i.e. 5%) and the other mechanical properties can be significantly affected<br />
by the type of talc.<br />
To summarize, for a cost-effective PLA modification, talc HTP1 offers the<br />
most attractive set of properties, while for outstanding final mechanical<br />
properties, talc NTT05 can record the best-in-class properties still remaining,<br />
in terms of costs, as an extender for PLA. <br />
26 bioplastics MAGAZINE [03/14] Vol. 9
Materials<br />
New high heat resistance grade<br />
After BIOPLAST 500, their first resin for film applications<br />
reaching 51% of biobased carbon according to<br />
ASTM D6866, BIOTEC GmbH & Co. KG (Emmerich,<br />
Germany) is now achieving new performances with the<br />
launch of BIOPLAST 900. Biotec launched the new injection<br />
moulding and thermoforming grade at interpack, Düsseldorf<br />
in early May 2014.<br />
“Products made of BIOPLAST 900 can, unlike some other<br />
bioplastics, withstand boiling temperatures without losing<br />
their shape, functionality and efficiency. Even at high filling<br />
temperatures, the taste of liquids/food is not affected.” says<br />
Harald Schmidt, Director of Innovation & New Technology<br />
of Biotec. This makes Bioplast 900 perfectly suitable for<br />
numerous food applications: coffee capsules, cups for cold<br />
as well as for hot drinks or the hot-filling of yoghurt or<br />
pudding products.<br />
Heat resistance combined with biodegradability - Bioplast<br />
900 shows undisputable environmental advantages, e.g.<br />
organic recyclability. For instance, used coffee capsules or<br />
other products made of Bioplast 900 are perfectly suitable<br />
for industrial composting. The GMO-free product is 69%<br />
biobased (potato starch, PLA and other ingredients)<br />
High definition moulding and short cycle times<br />
“Bioplast 900 processability allows moulding of extremely<br />
precise and complicated shapes. This innovative bioplastic<br />
resin exhibits moulding properties similar to conventional<br />
plastics, such as PP and PS.” adds Harald Schmidt.<br />
For example “With a cycle time of 5 seconds for the coffee<br />
capsule application, Bioplast 900 meets the challenging cycle<br />
time of conventional plastics” states Peter Brunk, Managing<br />
Director of Biotec.<br />
Technical data<br />
Bioplast 900 is designed for the following applications:<br />
injection moulded articles (e.g. cutlery, medical devices,<br />
clips, cups for hot and cold drinks)<br />
semi-finished products<br />
thermoformed products (e.g. food trays)<br />
blend partner in combination with other Bioplast materials<br />
(e.g. BIOPLAST GF 106/02)<br />
Products made of Bioplast 900<br />
are applicable for hot filling (e.g. beverages)<br />
are biodegradable according to EN 13432<br />
are recyclable<br />
are printable by flexographic and offset printing without<br />
pretreatment<br />
can be coloured with masterbatches<br />
are sealable (hot, RF, ultra sonic)<br />
www.biotec.de<br />
interpack - review<br />
bioplastics MAGAZINE [03/14] Vol. 9 27
Materials<br />
Green biocomposites<br />
Green thermoset biocomposites<br />
Green biocomposites are composed of natural fibres and<br />
biobased matrices. Bio-based matrices and industrial natural<br />
fibres composition, including hemp, jute and flax, etc. leads<br />
mostly to product price increases, hence generating green<br />
thermoset biocomposite market limitations. The option<br />
of choosing cheaper available fibres from another natural<br />
fibres resource, as in the case of agro-fibres (i.e. agricultural<br />
plant fibre residues) is here suggested and applied. The main<br />
key that can provide attractive products for architectural<br />
applications using available thermoset biocomposites’<br />
production techniques is the innovative product designs<br />
that can offer different innovative solutions for modern<br />
architectural spaces.<br />
Agro-fibre thermoset biocomposites<br />
Commercially, thermoset biocomposites are still not widely<br />
available. In spite of this, high interest in such composites<br />
is pushing up demand due to the known higher material<br />
performance of the thermoset composites than that of the<br />
thermoplastic ones. Manufacturing techniques as found in<br />
the conventional thermoset composite industry, include both<br />
open mould (e.g. hand lay-up and spray-up) and closed mould<br />
techniques (e.g. resin transfer moulding, vacuum infusion<br />
and compression moulding). Limitations in the case of agrofibres<br />
are their relative short fibre-lengths, while most of the<br />
compounding techniques are directed mainly for the usage of<br />
long fibres, fleece and fabrics. In case of bioresins appliance<br />
(i.e. biobased thermoset resins), a high curing temperature –<br />
one of the most currently available ones in the contemporary<br />
market - is another limitation to the whole process.<br />
In the following product design case-studies, agro-fibres<br />
and bioresins of different types were applied using different<br />
thermoset composite techniques. Product designs concepts<br />
differed according to the desired architectural outcome,<br />
between the form, surface texture, natural fibre’s coloureffect,<br />
pigments, glowing additives and others.<br />
Green biocomposites for architecture -<br />
case studies<br />
The following case studies are products designed and<br />
manufactured by the author and students of the Faculty<br />
of Architecture - University of Stuttgart, Germany within<br />
the framework of educational courses. The products are<br />
composed up to 70% by weight of agro-fibre contents that<br />
were from different origins. The general criteria for designing<br />
the green biocomposites here is the appropriate material<br />
selection including the agro-fibre and the bioresin as well<br />
as the processing techniques. This influenced the designed<br />
product outcome as illustrated in Fig. 1.<br />
By:<br />
Hanaa Dahy<br />
ITKE - (Institute for Building Structures<br />
and Structural Design)<br />
University of Stuttgart, Germany<br />
Fig. 1<br />
Materials and processing interaction with the<br />
product design concept<br />
Composite form:<br />
sandwich panel,<br />
particle board, …etc<br />
Geometry: Freeform,<br />
flat, profiled,…etc<br />
Color<br />
Texture<br />
Transparency<br />
…<br />
Design +<br />
Application<br />
Concept<br />
Inner Cladding<br />
Partitions<br />
False-ceiling tiles<br />
…<br />
Natural fibre from<br />
Agricultural residues<br />
Materials<br />
Processes<br />
Physical Processing:<br />
Fibre chopping<br />
Mold manufacturing<br />
Press molding techniques<br />
with vacuum<br />
assistance<br />
Fibre-spray techniques<br />
Bio-resin<br />
Natural Fibre +<br />
Matrix<br />
Processing<br />
Chemical Processing:<br />
chemical reaction activities<br />
combining resin components<br />
within molding with<br />
the agro-fibres<br />
28 bioplastics MAGAZINE [03/14] Vol. 9
Materials<br />
for architectural applications<br />
Case study – 1: TRAshell<br />
Case study – 2: BiOrnament<br />
Product description<br />
Free-form interior and exterior architectural cladding<br />
screens made from cereal straw short fibres and plantbased<br />
epoxy resin (TRAshell) processed by press-moulding<br />
(cold process).<br />
Materials, design and production description<br />
Cereal straw, coconut of a reddish brown colour and black<br />
coal ash were here applied in their original colours. Agrofibres<br />
were chopped then combined with a linseed-oil based<br />
epoxy resin based on two components that hardened after<br />
mixing at room temperature within ~ 24 to 48 hours. The<br />
free-form panels were designed in two modules (A) and (B),<br />
as illustrated to provide through their combination a desired<br />
3D physical curvature when the patterns are combined as<br />
illustrated. The moulds were carved using a robot machine at<br />
the faculty of architecture-University of Stuttgart, Germany,<br />
and the mixtures were moulded in the forms using different<br />
natural fibres and glowing pigments, as illustrated in Fig. 2<br />
and 3.<br />
Fig. 2. TRAshell product design and application simulation as<br />
architectural cladding panels in an experimental pavilion, Eco-<br />
Pavilion in the foyer of the faculty of Architecture-University of<br />
Stuttgart Pavilion (Photo: B.Milklautsch)<br />
Product description<br />
Coloured laser-cut flat panels (BiOrnament), processed by<br />
hand using the lay-up open moulding technique (hot process),<br />
for interior and exterior architectural cladding screens.<br />
Materials, design and production description<br />
The design sketch illustrates the idea of the pattern<br />
that was applied and repeated depending on using both<br />
the positive and negative cutting models that would result<br />
from the laser cutting procedures after the flat panels were<br />
separately manufactured. The product theme depended on<br />
the rhythm and diversity within unity using a repetitive pattern<br />
with different colourings whether positive or negative cut<br />
modules. Therefore, the mixtures were pigmented according<br />
to the most suitable product design.<br />
Cereal straw fibres were bonded with a biobased epoxy<br />
thermoset polymer, composed of three components. Plant<br />
oil based (e.g. linseed) epoxidized triglycerides are combined<br />
with polycarboxylic acid anhydrides (based on bio-ethanol)<br />
and an initiator. This compound was only activated by heat to<br />
polymerize. Therefore, the mould was composed of flat metal<br />
plates.<br />
Fig. 4. Illustration of the ornamental pattern design according to<br />
which the developed biocomposite panels were laser cut. Right<br />
(Photo: B.Miklautsch)<br />
Fig. 3. TRAshell with glowing glass particles and cereal straw, with<br />
coconut fibres, plus raw straw and black coal ash respectively.<br />
Photo credit: B.Milklautsch<br />
bioplastics MAGAZINE [03/14] Vol. 9 29
Materials<br />
Case Study-3: Light-24<br />
Product description<br />
Pigmented profiled panels (Light-24), processed by hand<br />
lay-up open moulding technique (cold process) for interior<br />
and exterior architectural cladding systems.<br />
Materials, design and production description<br />
Palm-fibres were applied in their long natural form, without<br />
chopping after being combined in a mat-form, with a bioresin<br />
of two components that hardened at room temperature in<br />
24 hours. This bioresin is a vacuum moulding low-viscosity<br />
resin prepared from sunflower esters and caprolactones<br />
with various additives. Black light pigment was mixed in a<br />
ratio of 2% to the total bioresin mixture. Then by hand lay-up<br />
technique, the fibres were impregnated with the resin and<br />
pressed in several layers and finally pressed as one thick<br />
layer.<br />
Conclusions<br />
-The manufactured green biocomposites were tested for<br />
weathering conditions (according to Free Weathering Test-<br />
DIN EN ISO 877) for 24 months as well as mechanically tested.<br />
The results were satisfactory and have shown high stability<br />
of the material against UV rays and weathering conditions.<br />
Mechanical testing showed comparable stiffness values with<br />
existing non-structural materials available in local markets<br />
that are applied in different architectural applications. This<br />
reveals the potential of replacing existing conventional<br />
materials with renewable resourced products based on<br />
cheap natural fibres and bioresins. Further experimentations<br />
and designs should be proceeded by architects, designers<br />
and material engineers to reveal more attractive ecological<br />
biocomposite products for eco-architecture.<br />
- Using agro-fibres and applying them in the form of<br />
biocomposites, utilizing biobased matrices based on<br />
renewable resources, can offer the opportunity to open a<br />
new market for green biocomposite materials with lower<br />
prices and acceptable performances, reducing resources<br />
consumption and providing more sustainability aspects. <br />
Fig. 5. Illustration of the Light-24 product, during manufacturing<br />
and after fabrication. Photo credit: Dahy, H.<br />
www.co2-chemistry.eu<br />
CO 2 as Chemical feedstock –<br />
a challenge for sustainable chemistry<br />
3 rd<br />
1 st Day (2 December 2014, 10 am – 7 pm): Political framework and vision:<br />
2 nd Day (3 December 2014, 9 am – 7 pm): Chemicals and energy from CO 2 :<br />
Entrance Fee<br />
ye<br />
s<br />
y (2<br />
nue<br />
Undergraduate and PhD students can attend<br />
the conference with a 50 % discount.<br />
Dominik Vogt<br />
Venue<br />
nova-Institute<br />
30 bioplastics MAGAZINE [03/14] Vol. 9
Materials<br />
Bioplastic<br />
from<br />
shrimp shell<br />
(Photo: Harvard‘s Wyss Institute)<br />
Researchers at Harvard‘s Wyss Institute (Boston, Massachussetts,<br />
USA) have developed a bioplastic from<br />
chitosan, a form of chitin, which is a powerful player in<br />
the world of natural polymers and the second most abundant<br />
organic material on Earth. Chitin is a long-chain polysaccharide<br />
that is responsible for the hardy shells of shrimps and<br />
other crustaceans, the exoskeleton of many insects, tough<br />
fungal cell walls — and flexible butterfly wings.<br />
The majority of available chitin in the world comes from<br />
discarded shrimp shells, and is either thrown away or<br />
used in fertilizers, cosmetics, or dietary supplements, for<br />
example. However, engineering successes have been limited<br />
to fabricate complex three-dimensional shapes using chitinbased<br />
materials — until now.<br />
The Wyss Institute team, led by Javier Fernandez and<br />
Founding Director Don Ingber, developed a new way to<br />
process the material so that it can be used to fabricate large<br />
objects with complex shapes using traditional casting or<br />
injection molding manufacturing techniques. What‘s more,<br />
their chitosan bioplastic is biodegradable in appropriate<br />
environments and it releases rich nutrients that efficiently<br />
support plant growth.<br />
“There is an urgent need in many industries for sustainable<br />
materials that can be mass produced,“ Ingber said. Ingber<br />
is also the Judah Folkman Professor of Vascular Biology<br />
at Boston Children‘s Hospital and Harvard Medical School,<br />
and Professor of Bioengineering at the Harvard School<br />
of Engineering and Applied Sciences. “Our scalable<br />
manufacturing method shows that chitosan, which is readily<br />
available and inexpensive, can serve as a viable bioplastic<br />
that could potentially be used instead of conventional plastics<br />
for numerous industrial applications.“<br />
It turns out the small stuff really mattered, Fernandez said.<br />
After subjecting chitosan to a battery of tests, he learned<br />
that the molecular geometry of chitosan is very sensitive to<br />
the method used to formulate it. The goal, therefore, was to<br />
fabricate the chitosan in a way that preserves the integrity of<br />
its natural molecular structure, thus maintaining its strong<br />
mechanical properties.<br />
“Depending on the fabrication method, you either get a<br />
chitosan material that is brittle and opaque, and therefore<br />
not usable, or tough and transparent, which is what we were<br />
after,“ said Fernandez.<br />
After fully characterizing in detail how factors like<br />
temperature and concentration affect the mechanical<br />
properties of chitosan on a molecular level, Fernandez and<br />
Ingber honed in on a method that produced a pliable liquid<br />
crystal material that was just right for use in large-scale<br />
manufacturing methods, such as casting and injection<br />
molding.<br />
Significantly, they also found a way to combat the problem<br />
of shrinkage whereby the chitosan polymer fails to maintain<br />
its original shape after the injection molding process. Adding<br />
wood flour, a waste product from wood processing, solved<br />
this problem.<br />
“You can make virtually any shape with impressive<br />
precision from this type of chitosan,“ said Fernandez, who<br />
molded a series of chess pieces to illustrate the point. The<br />
material can also be modified for use in water and also easily<br />
dyed by changing the acidity of the chitosan solution. And the<br />
dyes can be collected again and reused when the material is<br />
recycled.<br />
The next challenge is for the team to continue to refine<br />
their chitosan fabrication methods so that they can take<br />
them out of the laboratory, and move them into a commercial<br />
manufacturing facility with an industrial partner. MT<br />
bioplastics MAGAZINE [03/14] Vol. 9 31
Materials<br />
PHA Modifiers for<br />
Fig. 4.<br />
Soft PLA monofilaments<br />
modified by Metabolix PHA<br />
Metabolix (Cambridge, Massachusetts, USA) recently introduced<br />
newly developed polyhydroxyalkanoate (PHA) copolymer technology.<br />
This development has extended the range of Metabolix’s<br />
PHA portfolio with crystallinity ranging from 0% or 60% (Fig.1) to include<br />
fully amorphous products. The glass transition temperature (Tg °C) of<br />
these PHAs now extends from +5°C down to ~-30°C. Like the more<br />
crystalline products in its portfolio, these amorphous PHA products are<br />
100% renewable and widely biodegradable in most environments where<br />
microbial activity is present. Metabolix sees exciting opportunities for<br />
using these new copolymers to modify and improve the performance<br />
of PLA and thereby expand the market potential of PLA fibers and filaments.<br />
At Natureworks’ 2014 ITR conference, Metabolix showed early results<br />
for modifying PLA using these new PHA copolymers. Metabolix is<br />
grateful to Natureworks for their support in this development effort.<br />
This work focused on the ability to improve PLA ductility (Fig.2) without<br />
negatively impacting the PLA Tg (a common problem with using miscible<br />
plasticizers). Metabolix then demonstrated this effectiveness in PLA<br />
films by developing a much softer PLA blown film with flex modulus and<br />
toughness approaching HDPE. By varying modifier loads, flexibility and<br />
toughness in PLA blown and cast film can be adjusted across the range<br />
spanning from paper to HDPE. A series of these film prototypes were<br />
highlighted by Metabolix at Interpack 2014.<br />
PLA<br />
20<br />
More recently, Metabolix is excited by very interesting results in<br />
improving PLA fibers using with these new PHA modifiers. These<br />
developments were also highlighted at the 3 rd PLA World Congress in<br />
Munich.<br />
PHA Modified<br />
8<br />
Benefits of Modifying PLA fibers with PHA<br />
Fig. 3.<br />
Improving PLA Nonwovens<br />
with PHA Modifiers<br />
Ductility; Drape<br />
Improved touch and feel; Hand & Elongation<br />
Reduced Boiling Water Shrinkage<br />
PLA Ductility Improvement<br />
10 —<br />
— 70<br />
3500 —<br />
0 —<br />
— 60<br />
3000 —<br />
PLA, Paper<br />
Tg (C)<br />
-10<br />
—<br />
-20 —<br />
-30<br />
—<br />
-40 —<br />
-50 —<br />
Amorphous<br />
Range<br />
— 50<br />
— 40<br />
— 30<br />
— 20<br />
— 10<br />
Crystallinity [%]<br />
Flexural Modulus (MPa)<br />
2500 —<br />
2000 —<br />
1500 —<br />
1000 —<br />
500 —<br />
Cups, Lids<br />
Blister, Cards<br />
HDPE<br />
LDPE<br />
-60 —<br />
— 0<br />
0 20 40 60 80 100<br />
mole % Comonomer<br />
Fig. 1.<br />
Metabolix extended PHA Copolymer technology range<br />
0 —<br />
0 10 20 30 40<br />
% PHP Copolymer<br />
Fig. 2.<br />
Modifying PLA Flex Modulus with PHA<br />
32 bioplastics MAGAZINE [03/14] Vol. 9
PLA Fiber<br />
The ductility improvement that characterized PHA<br />
modified PLA films is also clearly seen in PHA modified<br />
PLA fibers. Textile and nonwoven applications for skin<br />
contact require a gentle touch and feel. With only a very<br />
low loading (< 5%) of PHA the Hand of the PLA fibers<br />
was reduced by 60% (Fig. 3). A soft, silky feel was<br />
imparted into the PLA fibers by modulus reduction as<br />
well as improved elongation leading to finer filaments<br />
and to improved Drape. Furthermore, after drawing and<br />
heat set, the PHA enabled hot water shrinkage to be<br />
significantly reduced and tenacity improved.<br />
By improving the softness characteristics of PLA<br />
nonwovens, expanded potential is possible in medical,<br />
personal hygiene (where skin contact comfort is<br />
important) and home care applications where single use<br />
is expected. The PHA modifier doesn’t compromise the<br />
100% renewable makeup of these non-woven single-use<br />
materials.<br />
In textiles, touch and feel comparable to PET is also<br />
an important aesthetic factor for success and PHA<br />
copolymer modifiers can enable this softness in PLA<br />
filaments (Fig. 4). Furthermore, being polyesters in their<br />
backbone chemistry, PHA modifiers are compatible with<br />
typical fiber treatments for dying and sizing.<br />
DRIVING A<br />
RESOURCE<br />
EFFICIENT<br />
EUROPE<br />
Distinct Advantages of PHA modifiers in PLA fibers<br />
Efficient improvement of touch and feel<br />
Compatibility with fiber treatments<br />
100% Renewable (bio-based)<br />
Fully Compostable<br />
Metabolix is prototyping these PHA modifiers on a<br />
pilot scale in nonwoven and monofilament applications<br />
and expects to launch several modifier Masterbatches<br />
this year and into 2015 when expanded production of the<br />
new PHA copolymer products is expected to be available.<br />
These products will take advantage of the extended<br />
range of PHA copolymer technology that Metabolix has<br />
developed and a variety of PLA base resins to provide<br />
solutions for expanding the market potential of PLA<br />
fibers.<br />
By:<br />
Bob Engle<br />
VP BioPlastics<br />
Metabolix, Inc., Cambridge, MA USA<br />
interpack - review<br />
Save the date!<br />
2/3 December 2014<br />
The Square Meeting Centre<br />
Brussels<br />
More information at:<br />
www.european-bioplastics.org<br />
www.metabolix.com<br />
www.conference.european-bioplastics.org<br />
bioplastics MAGAZINE [03/14] Vol. 9 33
Thermoset<br />
Co-creation<br />
makes<br />
bio-resins work<br />
Although biobased materials are increasingly used in<br />
composites, they only represent a small portion of the<br />
total market volume. As still biobased tends to be more<br />
expensive than fossil-based, customers are reluctant to pay<br />
a price premium just for having a better environmental conscience.<br />
This situation is now changing with the introduction<br />
of the biobased Beyone 201-A-01 resin in highly demanding<br />
wind energy applications. Composite systems with this<br />
resin provide simultaneously a great end-use performance,<br />
cost savings through easier processing, and on top they bring<br />
improved sustainability.<br />
Composites materials solutions are well established in<br />
today’s society as they bring numerous benefits to consumers.<br />
Cars can have unique shapes and great aerodynamics, while<br />
the low weight of composite parts contributes to lower energy<br />
consumption and reduced CO 2<br />
emissions. The great corrosion<br />
resistance of composites pipes enables continued operation<br />
and minimal maintenance in water treatment plants. When<br />
renovation of sewer networks is required, open roads and<br />
traffic disruption can be avoided by using relining solutions<br />
based on composites.<br />
Meanwhile, consumers want more for less: better quality<br />
of life, more functionality of the products they buy, and<br />
preferably at a lower price. They have become increasingly<br />
conscious about the impact they have on the environment,<br />
and are looking for ways to reduce their ecological footprint.<br />
Consequently, the demand for solutions based on renewable<br />
raw materials has been increasing. Obviously this represents<br />
a great challenge for the companies they buy from, and for<br />
the entire supply chain.<br />
In line with these market demands DSM has been<br />
introducing several synthetic resins based on renewable<br />
resources in the past few years. Objective is to secure future<br />
supply of raw materials, decreasing our dependency on fossilbased<br />
raw material sources. This will help to ensure security<br />
of supply down the value chain. Also, with these renewable<br />
raw materials becoming available in larger quantities, we<br />
expect to reduce the eco-footprint of our resins and we will<br />
be able to pass on that ‘eco advantage’ to our customers.<br />
Biobased materials for food contact<br />
An example of these developments is the introduction of<br />
the Synolite 7524-N-1 FC resin for artificial stone. This<br />
new DSM material is a biobased unsaturated polyester resin,<br />
has a bio-content of 45%, and is produced in line with Good<br />
Manufacturing Practice (GMP), the well accepted standard for<br />
making products used in contact with food. With this resin the<br />
company Compac (Spain) was able to create a new range of<br />
stone products suitable for kitchen work surface applications<br />
with great aesthetics.<br />
Innovation in infrastructure<br />
A completely different example of the use of biobased<br />
material is the application of Synolite 7500-N-1 structural<br />
resin for a bio-bridge, installed by FiberCore (Netherlands).<br />
Composite bridges can be easily installed because of their low<br />
weight. This reduces installation time and potential disruption<br />
to traffic and people. Also the lower weight requires lighter<br />
foundations compared to bridges made in pure steel or<br />
concrete. Because of their very nature, composite materials<br />
resist well water, heat and chemicals. Therefore these bridges<br />
34 bioplastics MAGAZINE [03/14] Vol. 9
Thermoset<br />
only require limited maintenance, while again<br />
the impact on the environment and traffic is<br />
minimized.<br />
The novel Synolite 7500-N-1 resin of DSM<br />
is a high strength structural resin (UP) partly<br />
based on renewable raw materials (~50 %).<br />
The resin can be easily converted through<br />
vacuum infusion manufacturing processes<br />
into composite components.<br />
Peace-of-mind on cost and the<br />
environment<br />
While the usage of biobased raw materials<br />
is increasing and the bio-feature is said to be<br />
highly appreciated by consumers and endcustomers,<br />
it is also clear that the market is<br />
reluctant to pay a significant price premium<br />
for bio-solutions. Yet because of the scale<br />
of production of biobased raw materials<br />
(typically made in lower volumes and still in<br />
sub-optimized manufacturing plants) and the<br />
availability of biobased sources to make the<br />
biobased raw materials, it can be expected<br />
they remain more expensive than the fossilbased<br />
raw materials for the foreseeable<br />
future.<br />
The introduction of DSM’s novel Beyone<br />
201-A-01 resin for making wind turbine blades<br />
may well represent a major change. The<br />
current material systems used for making<br />
wind turbine blades are mainly based on epoxy<br />
resins. While they bring resistance to fatigue,<br />
these resins are more sensitive to process<br />
variations, and require a time-consuming<br />
post-cure for reaching optimum physical<br />
properties. Systems based on polyester<br />
resins are easier to process but lack the high<br />
strength and fatigue resistance required for<br />
this demanding application. Moreover, blade<br />
manufacturers prefer to use resin systems<br />
without styrene, in order to have the best<br />
working environment for their operators.<br />
Compac has used DSM’s Synolite 7524-N-1 FC GMP-compliant<br />
resin, which features a high content of bio raw materials, to create<br />
a new range of artificial stone products called the Bio Technological<br />
Quartz Collection<br />
Easy installation of composite bridges, based DSM’s novel<br />
Synolite 7500-N-1 resin with 50 % biobased raw materials<br />
0 0,3 0,7 1,0 1,3<br />
Beyone 201-A-01 vs. WTB Epoxy reference<br />
WTB Epoxy reference + SE2020<br />
Standard UPR resins + Standard Glass<br />
Beyone 201-A-01 + SE3030<br />
1,E+01 1,E+02 1,E+03 1,E+04 1,E+05 1,E+06 1,E+07<br />
Number of cycles<br />
Excellent resistance<br />
to fatigue for long live<br />
blade performance.<br />
Tensile fatigue performance (S-N<br />
Curve) of Beyone 201-A-01 glass<br />
reinforced composites compared<br />
to standard epoxy systems for wind<br />
turbine blades<br />
bioplastics MAGAZINE [03/14] Vol. 9 35
Thermoset<br />
Reduced Eco-footprint of Beyone 201-A-01<br />
resins vs. epoxy resin reference<br />
ECO-footprint is the sum of all environmental impacts<br />
from an LCA (including e.g. CO2 footprint, toxicity, waste,<br />
resource consumption, land use)<br />
Eco Footprint (points)<br />
Beyone 1<br />
Epoxy system<br />
0,575<br />
DSM has proposed an all-new composite system for<br />
making wind turbine blades, together with its partners<br />
3B-the fibreglass company, Siemens Wind Power and DTU<br />
Wind Energy, featuring easy blade manufacturing, low weight,<br />
high stiffness, and excellent resistance to fatigue. The system<br />
is based on DSM’s Beyone 201-A-01, a resin that is styrenefree,<br />
cobalt-free (based on BluCure Technology, www.<br />
BluCure.com), and 40 % biobased. It has been demonstrated<br />
that this system can be used for making long blades at a<br />
record speed (through faster resin infusion and short postcure),<br />
giving an increased output per mold and an outlook for<br />
excellent process consistency.<br />
The bio-ingredients in the product formulations introduced<br />
in this article are derived from a mix of corn and corn waste<br />
material (the so-called generation 1.5). DSM wants to<br />
demonstrate that high performance levels can be achieved<br />
through using bio-ingredients (hence the introduction of these<br />
three resins). At the same time, DSM has increased its efforts<br />
to investigate routes for making the required raw materials<br />
from secondary organic sources (i.e. not competing with the<br />
food chain). DSM already has a track record of introducing<br />
new biobased products, supported by its strong roots in Life<br />
Sciences and biotechnology.<br />
0,72<br />
Co-creation works<br />
In order to commercialize new technologies that have<br />
the potential to revolutionize the manufacturing of wind<br />
turbine blades, it was necessary to think out of the box and<br />
form a strong channel partnership. DSM, 3B, Siemens Wind<br />
Power and DTU were able to demonstrate that through cocreation,<br />
a complex technology can be evaluated at record<br />
speed and prepared for live application in line with market<br />
requirements. Presently, the material system is under<br />
evaluation by Siemens Wind Power for its next-generation<br />
wind turbine blades.<br />
The development of Beyone 201-A-01 may turn out to<br />
be a game-changer not only for its performance in wind<br />
energy but also for the general application of biobased<br />
composite resins. Through the combination of great end-use<br />
performance, cost savings through easier processing, and<br />
improved sustainability the introduction of this material can<br />
be truly called a green revolution.<br />
Together for a brighter future with composites<br />
Building on its unique position as Life Sciences & Materials<br />
Sciences company, DSM is the leading global innovator of<br />
high performance, sustainable composite solutions. Through<br />
DSM’s Bright Science and market leadership across a<br />
number of industries including transportation, construction,<br />
infrastructure and industrial the company creates value<br />
by enhancing performance, improving health & safety, and<br />
minimizing environmental footprint.<br />
By:<br />
Thomas Wegman<br />
Marketing Manager DSM Composite Resins<br />
Zwolle, The Netherlands<br />
www.dsmcompositeresins.com<br />
www.blucure.com<br />
Great outlook for use of<br />
biobased materials in wind<br />
energy applications<br />
36 bioplastics MAGAZINE [03/14] Vol. 9
Thermoset<br />
Biobased<br />
Epoxy<br />
Epichlorohydrin from glycerin<br />
enables biobased epoxy resins<br />
The possible ways of producing epoxy resins are very different<br />
and complex. The most common and important<br />
class of epoxy resins is derived from epichlorohydrin<br />
(ECH) and bisphenol A (BPA), a bivalent alcohol.<br />
BPA is exclusively produced from fossil feedstock. However,<br />
health and safety concerns about the use of this chemical<br />
in food contact applications have led to the development of<br />
BPA substitutes, some of which being bio-based (e.g. lignin<br />
derivatives).<br />
Epichlorohydrin has been produced from oil-based<br />
propylene for decades, but it can also be obtained from<br />
biobased glycerin, a by-product from biodiesel and<br />
oleochemicals production. Thanks to identical physicochemical<br />
properties, biobased ECH can be used as a drop in<br />
substitute for fossil ECH.<br />
The world market for epichlorohydrin is about 1.5 million<br />
tonnes, 87% of which being used for the production of epoxy<br />
resins (in Asia and especially China, this share exceeds<br />
90%). The main use of epoxy resins is for the production<br />
of protective coatings (corrosion proof) for the marine,<br />
automotive and industrial markets. The second biggest<br />
application area for epoxy resins is the manufacture of<br />
electronic components such as printed circuit boards and<br />
encapsulated semiconductors. In third position is the field<br />
of composites, mainly for public transportation (aerospace,<br />
automotive,…) and wind-power generation.<br />
Belgian multinational Solvay is a major supplier of ECH and<br />
the world’s biggest producer of bio-based epichlorohydrin,<br />
made from glycerin. The diversified chemicals group entered<br />
the ECH market in the early 1960s, growing its annual ECH<br />
production capacity to 210,000 tonnes nowadays. Solvay<br />
produces propylene-based ECH at its plant in Rheinberg/<br />
Germany and a mix of propylene and bio-based ECH in<br />
Tavaux/France. Its plant in MapTa Phut/Thailand is entirely<br />
dedicated to biobased epichlorohydrin (100,000 t/a) which<br />
is marketed under the brand name Epicerol ® . In contrast<br />
to some other ECH producers, Solvay is not downstream<br />
integrated and does not produce epoxy resins.<br />
“Epicerol revolutionized the way of ECH production,”<br />
Thibaud Caulier, Senior Business Development Manager<br />
at Solvay explains to bioplastics MAGAZINE. “Epicerol not<br />
only uses 100% renewable carbon and reduces the carbon<br />
footprint of ECH production,” he says. “It is environmentally<br />
friendly in many other respects.” The whole production<br />
process consumes less energy and chlorine. The chemical<br />
reactions involved are more selective than in the propylenebased<br />
process, which significantly reduces the generation<br />
of chlorinated by-products. Another distinctive feature of<br />
Epicerol is that it does not release liquid effluents in the<br />
environment.<br />
In 2013, AkzoNobel and Solvay signed a three-year<br />
agreement whereby AkzoNobel will progressively increase<br />
the use in their coatings of bio-based epoxy resins produced<br />
with Epicerol, aiming to reach by 2016 20% of their equivalent<br />
ECH demand as bio-based material.<br />
In March 2014, a joint panel was organized at the World<br />
Biomarkets conference in Amsterdam, with Kukdo Chemical<br />
(epoxy supplier of AkzoNobel) and EY besides Solvay and<br />
AkzoNobel. Kukdo is committed to develop bio-based epoxy<br />
resins based on Epicerol. EY is bringing its competencies in<br />
order to implement a chain of custody that keeps track along<br />
the chain of the use of Epicerol in AkzoNobel coatings.<br />
Solvay is actively seeking to establish further supply chain<br />
partnerships in other epichlorohydrin market segments.<br />
Besides thermoset resins, Epicerol can also be used for<br />
rubber products. This shall be covered in a separate issue of<br />
bioplastics MAGAZINE. MT<br />
www.solvay.com<br />
Chemistry of epichlorohydrin<br />
manufacturing (simplified)<br />
Propylene<br />
CI 2<br />
HCI<br />
OH<br />
HO OH<br />
Bio sourced<br />
Glycerine<br />
CI<br />
Allyl Chloride<br />
HCI<br />
HCIO<br />
NaOH<br />
CI OH<br />
CI<br />
Dichloropropanol Brine<br />
O<br />
Epichorohydrin<br />
CI<br />
H 2<br />
O<br />
bioplastics MAGAZINE [03/14] Vol. 9 37
From Science & Research<br />
Supercritical Fluid<br />
assisted injection moulding<br />
A New Paradigm for Process-friendly Fabrication of Bioplastics<br />
Despite increasing interests and outstanding environmental<br />
benefits, the application of certain bioplastics<br />
in areas, which are currently dominated by petroleum<br />
based plastics, such as structural, electrical and other consumer<br />
products are limited. This is due to the fact that those<br />
bioplastics possess inferior material properties and are relatively<br />
expensive. In addition, bioplastics possess narrow processing<br />
windows, which makes them vulnerable for thermal<br />
degradation while also limiting widespread processability including<br />
composites formulation.<br />
The material- and processing- challenges of such<br />
bioplastics can be overcome by using a unique supercritical<br />
fluid (SCF) assisted fabrication technology. SCF is a state<br />
of gas (such as CO 2<br />
or N 2<br />
) above its critical pressure and<br />
temperature (Fig. 1). At an SCF state, the gas will have both<br />
gas-like and liquid-like properties. Both the properties<br />
direct the mixing of SCF with the polymer [1]. SCF effectively<br />
swells and plasticizes glassy polymers thereby leveraging<br />
low-temperature processing of plastics, which is highly<br />
desirable for moisture- and heat-sensitive bioplastics.<br />
The plasticization effect by SCF is triggered by increased<br />
polymer interchain distance that results in enhanced<br />
mobility of polymer segments, a phenomenon similar to<br />
plasticizing effect by conventional solvents or additives. A<br />
desiring feature of SCF plasticization as opposed to liquid<br />
or additive plasticizers is easy removal of the plasticizers<br />
from the processed bioplastics. This will aid in nontransformative<br />
processing of bioplastics. Moreover, SCFs are<br />
environmentally friendly yet being cost-effective. The SCF<br />
processing of bioplastics also results in the development<br />
of microcellular foams, which possess superior material<br />
properties at reduced densities aka material consumption,<br />
a feature highly desired for expensive bioplastics. For these<br />
outstanding benefits, SCF technology is currently employed<br />
for a host of conventional plastics processing technologies<br />
such as extrusion, injection moulding, blow moulding, etc.<br />
This article focuses on SCF injection moulding (IM) process.<br />
SCF Assisted Injection Moulding Technology<br />
The SCF technology was commercialized as MuCell ®<br />
technology in 1995 [2, 3]. A schematic of the microcellular<br />
injection moulding process with microstructure is shown in<br />
Fig. 2. In addition to lower temperature processing, reduced<br />
material consumption, and improved properties such as<br />
toughness, damping ability, etc., the SCF injection moulding<br />
technology aids in enhanced moulding thermodynamics<br />
which results in quicker cycle time which is highly desired for<br />
high-speed production lines. Moreover, the SCF IM process<br />
is run at lower pressures which results in stress-free and<br />
reduced warped parts [1]. Unlike conventional foams, the<br />
SCF IM processed microcellular foams yield reduced cell<br />
sizes and enhanced cell densities, typically on the order of<br />
10μm or less and 109 cells/cm 3 or more, respectively. These<br />
micron-sized cells may serve as crack arrestors by blunting<br />
crack tips, thereby enhancing part toughness [4], impact<br />
strength [5], and fatigue life [6].<br />
The microcellular injection moulding process takes place<br />
in three steps: nucleation, cell growth, and cell stabilization.<br />
First, SCF is dissolved into a polymer melt to form a singlephase<br />
polymer–gas solution, that is, the polymer melt is<br />
super-saturated with the blowing agent. Then, the pressure<br />
is suddenly lowered to a value below the saturation pressure<br />
triggering a thermodynamic instability and inducing cell<br />
nucleation. Cell growth is controlled by the gas diffusion<br />
rate and the stiffness of the polymer–gas solution. In<br />
general, cell growth is affected by the following factors: (a)<br />
time allowed for cells to grow; (b) state of supersaturation;<br />
Fig. 1:<br />
Diagram of material phases (reproduced from [2])<br />
Fig. 2:<br />
Schematic of the SCF injection molding process.<br />
Liquid<br />
SCF<br />
P cr<br />
Solid<br />
Critical point<br />
Pressure ><br />
Gas<br />
Cavity Cross<br />
Section<br />
Supercritical<br />
N 2<br />
or CO 2<br />
Higher Back<br />
Pressure<br />
(80 - 200 bar)<br />
T cr<br />
Rapid Pressure Drop<br />
in Nozzle Triggers<br />
Cell Nucleation<br />
Single-Phase<br />
Polymer-Gas<br />
Solution<br />
Special<br />
Reciprocating<br />
Screw<br />
38 bioplastics MAGAZINE [03/14] Vol. 9
From Science & Research<br />
(c) hydrostatic pressure applied to the<br />
polymer; (d) temperature of the system;<br />
and (e) viscoelastic properties of the<br />
single-phase polymer–gas solution.<br />
Other than processing parameters,<br />
materials formulations such as fillers<br />
and polymer blends also have strong<br />
influence on cell nucleation and<br />
growth. Especially, addition of fillers,<br />
which act as nucleating agents, leads<br />
to heterogeneous cell nucleation. They<br />
provide a large number of nucleation<br />
sites leading to higher cell densities<br />
and smaller cell sizes. Thus, increased<br />
adoption of bioplastics, specifically with<br />
new formulation designs comprising<br />
biobased blends and green composites,<br />
will benefit significantly from the SCF IM<br />
process.<br />
Polylactic Acid-Hyperbranched<br />
Polyester-Nanoclay<br />
Bionanocomposite Foams<br />
This study conducted by the authors<br />
exemplifies structure, morphology and<br />
properties of polylactic acid (PLA)-<br />
hyperbranched polyester (HBP)-<br />
nanoclay composite foams processed<br />
via SCF IM technology [7]. Poly (maleic<br />
anhydride-alt-1-octadecene) (PA) was<br />
used as a cross-linking agent for the<br />
HBP. As shown in Table-1, PLA was<br />
combined with PA, HBP, and nanoclay<br />
into a variety of formulations using a<br />
twin-screw extruder. Table-2 presents<br />
the processing conditions for the SCF<br />
IM process. For comparison, samples<br />
were also fabricated without SCF. Non-<br />
SCF samples are herein after termed<br />
as ‘solid’ and SCF samples are termed<br />
as ‘microcellular’. As can be observed,<br />
using SCF process, a 5ºC reduction in<br />
processing temperature was achieved<br />
which is due to the plasticizing effect<br />
of the SCF. This testifies the enhanced<br />
processability of SCF assisted<br />
technology.<br />
A<br />
C<br />
E<br />
B<br />
D<br />
F<br />
Fig. 3:<br />
Representative SEM images of the fracture<br />
surfaces of solid and microcellular PLA and<br />
PLA-HBP blends:<br />
(a) Pure PLA (Solid),<br />
(b) Pure PLA (Microcellular),<br />
(c) PLA-6%(H2004+PA) (Solid),<br />
(d) PLA-6%(H2004+PA) (Microcellular),<br />
(e) PLA-12%(H2004+PA) (Solid),<br />
(f) PLA-12%(H2004+PA) (Microcellular),<br />
(g) PLA-12%(H2004+PA)-2%Nanoclay (Solid),<br />
(h) PLA-12%(H2004+PA)-2%Nanoclay<br />
(Microcellular),<br />
(i) PLA-12%(H20+PA) (Solid),<br />
(j) PLA-12%(H20+PA) (Microcellular)<br />
G<br />
I<br />
H<br />
J<br />
bioplastics MAGAZINE [03/14] Vol. 9 39
From Science & Research<br />
Fig. 4:<br />
Tensile properties of solid and microcellular PLA and PLA-HBP blends: (a) Specific<br />
toughness, (b) Strain–at–break, (c) Specific modulus, (d) Specific tensile strength.<br />
Solid<br />
Microcellular<br />
Specific Toughness<br />
[MPa/(Kg/m 3 )]<br />
Strain-at-break<br />
[%]<br />
Specific Modulus<br />
[MPa/(Kg/m 3 )]<br />
Specific Tensiles Strenght<br />
[MPa/(Kg/m 3 )]<br />
PLA<br />
PLA - 6% (H2004 + PA)<br />
PLA - 12% (H2004 + PA)<br />
PLA - 12% (H2004 + PA) -2% NC<br />
PLA - 12% (H20 + PA)<br />
PLA - 12% (H2004 + PA)<br />
0 0.005 0.01 0.015 0.02<br />
0 15 30 40 60<br />
0 0.4 0.8 1.2 1.6<br />
0 0.02 0.04 0.06<br />
Fig. 3 shows the morphology of the<br />
solid and microcellular samples. The<br />
cell morphology of the microcellular<br />
foams showed that the addition of HBPs<br />
and nanoclay decreased the average<br />
cell size while increasing the cell<br />
density. Moreover, among all the solid<br />
and microcellular PLA–HBP blends,<br />
PLA–12%(H2004+PA)–2%nanoclay<br />
composites exhibited the highest<br />
specific toughness and strain-at-break<br />
followed by PLA–12%(H2004+PA) and<br />
PLA–6%(H2004+PA) (Fig. 4). On the<br />
other hand, PLA–12%(H20+PA) had a<br />
similar specific toughness and strainat-break<br />
values as the pure PLA for<br />
both solid and microcellular samples.<br />
Furthermore, the addition of HBPs+PA<br />
and HBP–nanoclay caused a slight<br />
reduction in specific modulus and<br />
a considerable reduction in specific<br />
strength compared with pure PLA in<br />
all solid and microcellular PLA–HBP<br />
blends. Overall, using SCF process,<br />
a weight reduction of 10–16% was<br />
achieved which testifies reduced<br />
materials consumption.<br />
Conclusions<br />
The advocacy of certain bioplastics<br />
specifically in areas currently dominated<br />
by conventional plastics will be realized<br />
only after sustained alleviation in the<br />
process and materials properties<br />
limitations of such bioplastics. In<br />
this regard, SCF assisted injection<br />
moulding technology plays a vital role<br />
specifically in lowering the viscosity of<br />
these bioplastics thereby lessening its<br />
processing temperature or widening<br />
the processing window, reducing the<br />
materials consumption through the<br />
development of low density foams without<br />
compromising on the specific materials<br />
properties, promoting the impact<br />
resistance of the materials, inducing<br />
stress-free and thus reduced warped<br />
parts, high throughout production, etc.<br />
Despite these extraordinary benefits,<br />
the science of SCF aided bioplastics<br />
is at a nascent state. Thus, significant<br />
innovations need to be created to pioneer<br />
and establish this technology within the<br />
commercial space. <br />
By:<br />
Srikanth Pilla*<br />
Clemson University, South Carolina, USA<br />
Shaoqin Gong<br />
University of Wisconsin-Madison, USA<br />
*: Corresponding author: spilla@clemson.edu<br />
References<br />
1. J. Xu, Microcellular Injection Moulding,<br />
Chapter 1, p. 15, 2010.<br />
2. N. P. Suh, Innovation in Polymer Processing,<br />
Ed. J. F. Stevenson, Chapter 3, p. 93, 1996.<br />
3. J. Xu, and D. Pierick, J. Injection Moulding<br />
Technol., Vol. 5, p. 152, 2001.<br />
4. D.F. Baldwin, N.P. Suh, SPE ANTEC Tech.<br />
Papers, Vol. p. 1503, 1992.<br />
5. J.E. Martini, F.A. Waldman, N.P. Suh, SPE<br />
ANTEC Tech. Papers, Vol. 40, p. 674, 1982.<br />
6. K.A. Seeler, V. Kumar, Cell. Polym., Vol. 38, p.<br />
93, 1992.<br />
7. S. Pilla, A. Kramschuster, J. Lee, S. Gong<br />
and L-S. Turng, J. Materials Sci., Vol. 45, p.<br />
2732, 2010.<br />
Table-2:<br />
Injection-moulding conditions used<br />
to mould the tensile bars<br />
(S-Solid; M-Microcellular)<br />
Table-1:<br />
Percent composition of the materials compounded<br />
Experiment Sample PLA PA HBP Naugard-10<br />
(0.2wt% total<br />
formulation)<br />
Naugard-524<br />
(0.2wt% total<br />
formulation)<br />
Cloisite ®<br />
30B<br />
1 PLA 99.6 0.0 0 0.2 0.2 0<br />
2 PLA-6%(H2004+PA) 93.6 1.5 4.5 0.2 0.2 0<br />
3 PLA-12%(H2004+PA) 87.6 3.0 9.0 0.2 0.2 0<br />
4 PLA-12%(H2004+PA)-2%NC 85.6 3.0 9.0 0.2 0.2 2<br />
5 PLA-12%(H20+PA) 87.6 7.4 4.6 0.2 0.2 0<br />
S M<br />
Mould Temp (ºC) 20 20<br />
Nozzle Temp (ºC) 175 170<br />
Injection Speed (cm 3 /sec) 20 20<br />
Wt% SCF Content n/a 0.56<br />
Pack Pressure (bar) 795 -<br />
Pack Time (sec) 7.5 -<br />
Screw Recovery Speed (RPM) 280 280<br />
Cooling Time (sec) 35 35<br />
Microcellular Process Pressure (bar) n/a 190<br />
40 bioplastics MAGAZINE [03/14] Vol. 9
Materials<br />
he stars of today’s bioplastics industry are polymers<br />
like PLA or PBS. However, in a growth<br />
market like bioplastics, other substances are<br />
coming to market all the time. One such compound<br />
is 5-hydroxymethylfurfural (5-HMF), named by the US<br />
Department of Energy as one of the most versatile<br />
and promising renewable platform chemicals.<br />
Since February 2014, 5-HMF has been produced<br />
commercially by AVA Biochem, a Swiss-based<br />
company who recently developed a technological<br />
breakthrough in the continuous, automated and<br />
highly-scalable production of 5-HMF by means of<br />
modified hydrothermal carbonisation (HTC). Located<br />
in Switzerland, AVA Biochem’s plant produces 20<br />
tonnes of 5-HMF per year, at purities of up to 99.9%.<br />
Currently, 5-HMF is being produced using fructose<br />
sourced in Europe. The modified HTC technology<br />
however, will allow for the use of several different<br />
biomass streams in the future, including waste<br />
biomass.<br />
The scale-up potential of the AVA Biochem process<br />
means bulk 5-HMF prices should be possible in the<br />
near future. If co-located with an efficient feedstock<br />
supply and at a suitable scale, 5-HMF could achieve<br />
cost parity with petro-based chemicals soon and<br />
therefore become cheaper to use in bioplastics<br />
applications.<br />
Capacity at the plant could be increased to 40<br />
tonnes/year through process improvements and<br />
efficiency gains. Scale-up, together with bulk 5-HMF<br />
prices, will have significant consequences, opening<br />
new opportunities and potentially revolutionising the<br />
bioplastics industry.<br />
Renewable 5-HMF can already replace petrobased<br />
5-HMF as a drop-in in many applications,<br />
such as adhesives used as plasticisers. One of the<br />
most promising routes is 2,5 furandicarboxylic acid<br />
(FDCA), produced as an intermediate when 5-HMF<br />
is oxidised. It can substitute terephthalic acid in<br />
polyester, especially polyethylene terephthalate<br />
(PET). Global PET output in 2009 was 49.2 million<br />
tonnes and PET fibre accounted for about two-thirds.<br />
PET for packaging and films accounted for 34%.<br />
Other increasingly significant markets are biopolyamides<br />
and resins, where 5-HMF derivatives<br />
caprolactam and 2,5-Bishydroxymethylfuran (2,5-<br />
BHF) play an important part.<br />
By conducting technical, lifecycle and market<br />
analyses, clearly defining end-product specifications<br />
and potential applications, the bio-based industries<br />
can help strengthen market pull for bioplastics.<br />
Application development done in conjunction with<br />
partners is also key to bringing more bioplastics<br />
technologies to market.<br />
Discussions between AVA Biochem and potential<br />
industry partners have begun and the company is<br />
optimistic that cooperation will help further develop<br />
the downstream chemistry pathways. The industrialscale<br />
production of 5-HMF has the potential to open<br />
the door to more innovative and highly interesting<br />
applications – in bioplastics and beyond. MT<br />
http://www.ava-biochem.com<br />
O<br />
HO<br />
Renewable<br />
5-HMF<br />
Biobased platform chemical<br />
presents opportunities for<br />
bioplastics sector<br />
Figure 1:<br />
Production route for<br />
bio-based 5-HMF<br />
Figure 2:<br />
Potential applications<br />
for 5-HMF<br />
RO<br />
O<br />
O<br />
H<br />
5-Alkoxymethylfurfural<br />
O<br />
O<br />
OH<br />
2,5-Furandicarboxylic acid<br />
O<br />
HO<br />
O<br />
OH<br />
5-Hydroxymethylfuroic acid<br />
HO<br />
O<br />
OH<br />
5-Hydroxymethylfuroic acid<br />
N O<br />
H<br />
Caprolactam<br />
HO<br />
O<br />
5-HMF<br />
O<br />
O O<br />
Caprolactone<br />
O<br />
H<br />
O<br />
O<br />
HO<br />
1,6-Hexanediol<br />
O<br />
HO<br />
O<br />
O<br />
Bis(5-methylfurfurly)ether<br />
OH<br />
O<br />
Adipic acid<br />
O<br />
Levulinic acid<br />
O<br />
H<br />
O<br />
OH<br />
OH<br />
2,5-Dimethylfuran<br />
bioplastics MAGAZINE [03/14] Vol. 9 41
Market<br />
European and Global Markets<br />
2012 and Future Trends<br />
Wood-Plastic<br />
Composites (WPC)<br />
and Natural Fibre<br />
Composites (NFC)<br />
Table 1: Production of biocomposites<br />
(WPC and NFC) in the European Union<br />
in 2012 (in tonnes) (nova 2014)<br />
In the European Union about 352,000<br />
tonnes of Wood- and Natural Fibre<br />
Composites were produced in 2012.<br />
The most important application sectors<br />
are construction (decking, siding<br />
and fencing) and automotive interior<br />
parts. About 15% of the total European<br />
composite market is covered by Wood-<br />
Plastic Composites (WPC) and Natural<br />
Fibre Composites (NFC). A comprehensive<br />
market study was conducted<br />
by the nova-Institute (Germany) in cooperation<br />
with Asta Eder Composites<br />
Consulting (Austria/ Finland) to give a<br />
detailed picture of the use and amount<br />
such biocomposites in the European<br />
biobased economy. The analysis covers<br />
composites in extrusion, injection and<br />
compression moulding in different sectors<br />
and for different applications.<br />
Total production of<br />
biocomposites<br />
Table 1 summarises the results<br />
of the survey, showing all Wood-<br />
Plastic Composites and Natural<br />
Fibre Composites produced in<br />
the European Union, including all<br />
sectors, applications and processing<br />
technologies.<br />
Decking and automotive are the<br />
most important application sectors for<br />
WPC, followed by siding and fencing.<br />
Only the automotive sector is relevant<br />
for Natural Fibre Composites (NFC)<br />
today. The share of WPC and NFC in<br />
the total composite market – including<br />
glass, carbon, wood and Natural Fibre<br />
Composites – is already an impressive<br />
15%. Even higher shares are to be<br />
expected in the future: NFC are<br />
starting to enter other markets than<br />
just the automotive industry. WPC<br />
granulates for injection moulding are<br />
now produced and offered by global<br />
players and are becoming more<br />
attractive for clients that manufacture<br />
consumer goods, automotive and<br />
technical parts.<br />
With increasing polymer prices and<br />
expected incentives for bio-based<br />
products (the bio-based economy is<br />
one of the lead markets in Europe)<br />
this trend will go from strength to<br />
strength, resulting in two-digit growth<br />
and increasing market shares over the<br />
coming decade.<br />
100% 74% 26%<br />
352,000<br />
Total Volume<br />
Biocomposites<br />
15 % Share<br />
2.4 Million<br />
Composite Production<br />
in European Union<br />
total volume (Glass,<br />
Carbon, WPC and NFC)<br />
(Photo: hammerkauf.de)<br />
260,000<br />
Wood-Plastic<br />
Composites<br />
(Photo: nova)<br />
92,000<br />
Natural Fibre<br />
Composites<br />
90,000 Automotive<br />
2,000 Others<br />
42 bioplastics MAGAZINE [02/14] Vol. 9
Market<br />
t<br />
Global Production of WPC in 2010<br />
and 2012<br />
and Forecast for 2015<br />
2010<br />
2012<br />
900,000<br />
2015<br />
10,000<br />
20,000<br />
220,000<br />
260,000<br />
350,000<br />
10,000<br />
1,100,000<br />
50,000<br />
20,000<br />
40,000<br />
5,000<br />
25,000<br />
70,000<br />
900,000<br />
1,350,000<br />
2010<br />
2012<br />
2015<br />
300,000<br />
2010<br />
2012<br />
1,800,000<br />
2015<br />
30,000<br />
40,000<br />
55,000<br />
40,000<br />
65,000<br />
110,000<br />
Fig 1.<br />
Wood-Plastic Composites –<br />
Decking still dominant, but<br />
technical applications and<br />
consumer goods rising<br />
The typical production process in<br />
Europe is extrusion of a decking profile<br />
based on a PVC or PE matrix followed<br />
by PP. Increasing market penetration<br />
by WPC has meant that WPC volumes<br />
have risen strongly and Europe is now<br />
a mature WPC market.<br />
However, WPC is increasingly used<br />
for applications beyond the traditional<br />
ones like decking or automotive parts.<br />
This includes for example, furniture,<br />
technical parts, consumer goods and<br />
household electronics, using injection<br />
moulding and other non-extrusion<br />
processes. Also, new production<br />
methods are being developed for the<br />
extrusion of broad WPC boards.<br />
In the face of rising plastic prices,<br />
WPC granulates are getting more and<br />
more attractive for injection moulding.<br />
Three big paper companies released<br />
cellulose-based PP granulates for<br />
injection moulding between 2012<br />
and 2013. They use a PP matrix with<br />
cellulose and have fibre contents<br />
between 20 and 50% for new and<br />
interesting applications such as<br />
furniture, consumer goods and<br />
automotive parts.<br />
The report also gives an overview<br />
of the latest market developments in<br />
North-America, Asia and Russia, and<br />
provides an overview of, and a forecast<br />
for, the global WPC market. Worldwide<br />
WPC production will rise from 2.43<br />
million tonnes in 2012 to 3.83 million<br />
tonnes in 2015. Although North America<br />
is still the world’s leading production<br />
region with 1.1 million tonnes, ahead of<br />
China (900,000 t) and Europe (260,000 t),<br />
it is expected that China (with 1.8 million<br />
t by then) will have overtaken North<br />
America (1.4 million t) by 2015. European<br />
production will grow by around 10% per<br />
year and reach 350,000 tonnes in 2015.<br />
WPC and NFC in the<br />
automotive industry<br />
Interior parts for the automotive<br />
industry is by far the most dominant<br />
use of Natural Fibre Composites – other<br />
sectors such as consumer goods are still<br />
at a very early stage. In the automotive<br />
sector, Natural Fibre Composites have<br />
a clear focus on interior trims for highvalue<br />
doors and dashboards. Wood-<br />
Plastic Composites are mainly used for<br />
rear shelves and trims for trunks and<br />
spare wheels, as well as in interior trims<br />
for doors.<br />
Figure 2 shows the total volume of<br />
80,000 tonnes of different wood and<br />
Fig. 2:<br />
Use of wood and natural fibres<br />
for composites in the European<br />
automotive industry in 2012,<br />
including cotton and wood.<br />
Others are mainly jute, coir, sisal and<br />
abaca (nova 2014)<br />
kenaf<br />
hemp<br />
8%<br />
19%<br />
flax<br />
others<br />
5%<br />
7%<br />
cotton<br />
25%<br />
80,000<br />
t<br />
38%<br />
wood<br />
TOTAL<br />
VOLUME<br />
bioplastics MAGAZINE [04/14] Vol. 9 43
Market<br />
Production in 2012<br />
Biocomposites<br />
Forecast production in 2020<br />
without ...<br />
with strong ...<br />
... incentives for<br />
bio-based products<br />
190,000 t<br />
Construction, extrusion<br />
400,000 t<br />
450,000 t<br />
WPC<br />
60,000 t<br />
Automotive, press moulding<br />
& extrusion/thermoforming<br />
80,000 t<br />
300,000 t<br />
15,000 t<br />
Granulates,<br />
injection moulding<br />
100,000 t<br />
> 200,000 t<br />
NFC<br />
90,000 t<br />
2,000 t<br />
Automotive, press moulding<br />
Granulates,<br />
injection moulding<br />
10,000 t ><br />
20,000 t<br />
120,000 t<br />
350,000 t<br />
Table 2: Production of biocomposites (WPC and NFC) in the European<br />
Union in 2012 and forecast 2020 (in tonnes) (nova 2014)<br />
natural fibres used in the 150,000<br />
tonnes of composites for passenger<br />
cars and lorries that were produced<br />
in Europe in 2012 (90,000 tonnes of<br />
Natural Fibre Composites and 60,000<br />
tonnes of WPC). Recycled cotton fibre<br />
composites are mainly used for the<br />
driver cabins of lorries.<br />
Process-wise, compression<br />
moulding of wood and Natural Fibre<br />
Composites are an established and<br />
proven technique for the production of<br />
extensive, lightweight and high-class<br />
interior parts for mid-range and luxury<br />
cars. The advantages (lightweight<br />
construction, crash behaviour,<br />
deformation resistance, lamination<br />
ability and, depending on the overall<br />
concept, price) and disadvantages<br />
(limited shape and design forming,<br />
scraps, cost disadvantages in case of<br />
high part integration in construction<br />
parts) are well known. Process<br />
optimisations are in progress in order<br />
to reduce certain problems such as<br />
scraps and to recycle wastage.<br />
Since 2009, new improved<br />
compression- moulded parts have<br />
shown impressive weight- reduction<br />
characteristics. This goes some way<br />
to explaining the growing interest in<br />
new car models. Using the newest<br />
technology, it is now possible to<br />
get area weight down to 1,500 g/<br />
m2 (with thermoplastics) or even<br />
1,000 g/m2 (with thermosets), which<br />
are outstanding properties when<br />
compared to pure plastics or glass<br />
fibre composites.<br />
Still small in volume but also strong<br />
in innovation: PP and cellulose-based<br />
granulates for injected- moulded<br />
parts were recently introduced onto<br />
the automotive market by big paper<br />
companies in Europe and the USA.<br />
Outlook for WPC and NFC<br />
production in the EU until 2020<br />
The production and use of 150,000<br />
tonnes biocomposites (using 80,000<br />
tonnes of wood and natural fibres) in<br />
the automotive sector in 2012 could<br />
expand to over 600,000 tonnes of<br />
biocomposites in 2020, using 150,000<br />
tonnes of wood and natural fibres<br />
each along with some recycled cotton.<br />
Yet this fast development will not take<br />
place if there are no major political<br />
incentives to increase the bio-based<br />
share of the materials used in cars.<br />
Without incentives the authors forecast<br />
that production will only increase to<br />
200,000 tonnes.<br />
With improved technical properties,<br />
lower prices and bigger suppliers,<br />
huge percentage increases can also be<br />
expected for WPC and NFC granulates<br />
used in injection moulding for all kind<br />
of technical and consumer goods.<br />
Extruded WPC is now well<br />
established as a material for decking,<br />
fencing and facade elements. Its<br />
market share is still growing and<br />
should reach and surpass the level of<br />
tropical wood in most of the European<br />
countries by 2020.<br />
By:<br />
Michael Carus, Lara Dammer<br />
Lena Scholz, Roland Essel, Elke Breitmayer<br />
nova-Institute,Hürth, Germany<br />
Asta Eder<br />
Asta Eder Composites Consulting,<br />
Austria / Finland<br />
Hans Korte<br />
PHK Polymertechnik GmbH, Wismar, Germany<br />
A more comprehensive summary is available for<br />
free at www.bio-based.eu/markets<br />
The full report can be ordered for 1,000 €<br />
plus VAT at www.bio-based.eu/markets<br />
44 bioplastics MAGAZINE [02/14] Vol. 9
Microplastic<br />
Microplastics in the Environment<br />
Sources, Consequences, Solutions<br />
total mass in million tonnes<br />
350<br />
300<br />
250<br />
200<br />
150<br />
100<br />
1950 1970 1990 2010<br />
Global plastic production<br />
Ingress of plastic waste into<br />
the oceans estimations by:<br />
UNEP 2006<br />
Wright et al. 2013<br />
Plastic waste in<br />
the oceans<br />
Diameter<br />
Typical dimensions<br />
of aquatic creatures<br />
Macroplastic > 25 mm Fish, shellfish,<br />
mussels, etc.<br />
Typical dimensions<br />
of industrial plastics<br />
Mesoplastic 5 – 25 mm production of plastic<br />
granules /pellets<br />
Large microplastic<br />
particle<br />
Small microplastic<br />
particle<br />
1 – 5 mm<br />
< 1mm Plankton Application of microplastic<br />
in cosmetics<br />
Tabelle 1<br />
50<br />
0<br />
Table 1: Classification of marine plastic debris on the basis of size<br />
(Source: own representation based on JRC 2013, STAP 2011)<br />
Figure 1: Global plastics production in the period from 1950 to 2012 und estimated<br />
volume of discharge of plastics into the oceans (Source: own representation based<br />
on PlasticsEurope 2013, UNEP 2006, Wright et al. 2013)<br />
Scientific studies have shown that plastics make a huge<br />
contribution to the littering of the seas. In marine pro-<br />
tection, plastic particles with a diameter of less than<br />
5 mm are referred to as microplastics. These can be fragments<br />
created by the breaking up of larger pieces of plastic<br />
such as packaging, or as fibres are washed out of textiles.<br />
They can also be primary plastic particles, produced in microscopic<br />
sizes. These include granulates used in cosmetics,<br />
washing powders, cleaning agents and in other applications.<br />
The following article describes the source of microplastics,<br />
the effects they have on the ecosystem and on people, and<br />
discusses potential solutions. For the first time, on July 1st<br />
2014, a conference will be dedicated to this topic in Germany.<br />
Waste in the oceans and inland waters is dominated by<br />
plastics (Barnes et al. 2009). The United Nations Environment<br />
Programme (UNEP) assumes coverage of up to 18,000 pieces<br />
of plastic for every square kilometre of ocean (UNEP 2006). It<br />
can take centuries for plastic to be broken down in the oceans<br />
by physical, chemical, and biological decomposition processes<br />
(UBA 2010). Along with larger waste items such as<br />
plastic bottles or bags, steadily increasing amounts of<br />
plastic microparticles – commonly known as microplastics s –<br />
are being observed in ocean gyres, sediments, and on beaches,<br />
as well as being found in marine organisms.<br />
The term microplastics, however, is not used consistently.<br />
In the cosmetics industry, it is used to describe plastic<br />
granulates that in many cases are much smaller than 1<br />
mm in diameter. In marine protection, in contrast, plastic<br />
particles with a diameter of less than 5 mm are considered<br />
microplastics (Arthur et al. 2009). On the other hand, Browne<br />
et al. (2011) use the term for plastic particles with a diameter<br />
of less than 1mm. Neither source gives a lower value for the<br />
diameter of particles, meaning that the term microplastics<br />
also includes significantly smaller particles (Leslie et al.<br />
2011). Microplasticss<br />
can therefore be considered an umbrella<br />
term for various plastic particles determined solely on the<br />
basis of size (cf. Table 1).<br />
In accordance with this definition, in the text that follows,<br />
all plastic particles with a diameter smaller than 5mm are<br />
termed microplastics.<br />
46 bioplastics MAGAZINE [02/14] Vol. 9
Microplastic<br />
Sources of microplastics<br />
The most commonly used polymers in cosmetics are<br />
polyethylene (PE), polypropylene (PP) and polyamide (PA). A<br />
whole series of other polymers are also in use (Leslie et al.<br />
2012).<br />
Manufacturers add synthetic polymers to cosmetics for a<br />
number of reasons: some possess film-forming and viscosityregulating<br />
properties, others act as abrasives. They are<br />
designed to remove impurities from the skin or to clean teeth.<br />
Along with their use in the cosmetics industry, there are<br />
other applications for plastic microparticles. They are used<br />
as abrasive beads in detergents and cleaning fluids, and as<br />
a blasting abrasive in, for example, the surface cleaning of<br />
stainless steel. They are use as lubricants, separating agents,<br />
or as carriers for pigments, or to adjust the viscosity of hot<br />
melt adhesives. Water softeners can also contain plastic<br />
microparticles.<br />
As well as microplastics produced directly in microscopic<br />
sizes to be used in cosmetics and other products, microparticles<br />
in many cases are secondary fragments produced by the<br />
breakdown of larger pieces of plastic. Plastic microparticles<br />
can originate, for example, from plastic packaging dumped<br />
in the environment, such as bags or boxes, or from plastic<br />
fibres from textiles, or particles released by tyre wear. The<br />
production and recycling of plastics also generates particles.<br />
Ryan et al. (2010) also record direct macroplastic pollution<br />
from ship waste.<br />
Although the sources of microplastics are largely<br />
documented, until now no reliable data has been produced<br />
on the amounts of microplastics from cosmetics and other<br />
implementations, and other sources, actually enter the<br />
environment.<br />
The United Nations Environment Programme refers to the<br />
estimate made in 1997 that in the 1990s, around 6.4 million<br />
tonnes of plastic debris entered the oceans annually, of which<br />
just short of 5.6 million tonnes came from shipping (UNEP<br />
2006). Wright et al. 2013 estimate that, in total, around ten<br />
per cent of global plastics production will find its way into<br />
the ocean at some point. It follows that of the 288 million<br />
tonnes of plastic produced worldwide in 2012 (according to<br />
PlasticsEurope estimates), just short of 30 million tonnes will<br />
sooner or later enter the marine environment and serve as a<br />
potential source of microplastics (cf. Figure 1).<br />
Consequences of microplastics<br />
The presence of microplastics in the environment has a<br />
number of negative consequences for humans and the natural<br />
environment. If animals ingest pieces of plastic, large or<br />
small, mistaking them for food, a permanent feeling of satiety<br />
can result – and they starve to death. In experiments feeding<br />
mussels with microplastics, researchers demonstrated that<br />
plastic particles could penetrate the stomach lining and enter<br />
the bloodstream. Many plastic parts contain chemicals like<br />
softeners or flame retardants. Some of these additives are<br />
harmful to fertility or imitate natural hormones. They are only<br />
weakly bound into the plastic matrix, and can easily leach out<br />
and impact plant and animal life. Long-lasting hydrophobic<br />
pollutants can attach to and accumulate on plastic<br />
microparticles. If marine organisms consume these particles,<br />
these contaminants can enter the food chain (Teuten et al.<br />
2007) and ultimately cause harm to humans.<br />
Can bioplastics be a solution?<br />
Primary microparticles from cosmetics make up only a<br />
small part of the plastics in the oceans in absolute terms.<br />
Strategies designed to reduce the ever-increasing littering of<br />
the world’s seas should therefore not focus solely on the use<br />
of these microparticles, but should apply to all kinds of plastic<br />
waste.<br />
Cosmetics manufacturers can, however, eliminate longlasting<br />
plastic microparticles from their products, or replace<br />
them with microparticles produced from other materials.<br />
Many of these companies are currently on the lookout for<br />
alternatives. Chemicals producers and traders already offer a<br />
selection (cellulose, wood chip, minerals).<br />
Whether or not biodegradable polymers can be an option<br />
is an exciting and important question. Their use would be<br />
of interest above all because the existing production chain<br />
could be kept in use largely unaltered, and the functioning of<br />
the microparticles would also be a very close match for the<br />
plastics previously in use.<br />
Polyhydroxyalkanoates (PHA), and polybutylene succinate<br />
(PBS), are potential candidates, as are polylactic acid (PLA)<br />
produced from maize starch, chitosan from chitin or casein<br />
from animal protein. Current studies suggest that PLA is<br />
probably not the best solution, whereas PHAs have real future<br />
potential (CalRecycle 2012). PHAs are natural thermoplastics,<br />
which degrade quickly in almost any environment (including<br />
in the sea). The greatest challenges lie in ensuring that<br />
breakdown occurs only after the product has been used, and<br />
in developing mass production.<br />
In contrast, so-called oxo-(bio)degradable e plastics are no<br />
solution – in fact, they’re part of the problem. These plastics<br />
aren’t actually biodegradable. They contain predetermined<br />
breaking points that cause the polymers to fragment i.e.<br />
produce microparticles. Up to 80 % of the content (in terms of<br />
the original weight of the product) remains in the environment<br />
and can produce toxic effects (Narayan 2009).<br />
Conclusions<br />
The availability of precise numbers on the amount of plastic<br />
microparticles used in cosmetics and other products is<br />
unsatisfactory. Due to the lack of data, it is difficult to establish<br />
the volumes in which these particles enter the environment,<br />
and what the predominant transport and release mechanisms<br />
are. Their accumulation in the oceans, on the seafloor, on<br />
beaches worldwide, and in numerous organisms (and the<br />
resulting adverse effects for both humans and nature) is<br />
receiving ever more public attention, and demands solutions.<br />
Fragments from plastic debris that has entered the sea are<br />
a far greater source of damage. This means that if we want<br />
to decrease the amount of microplastics in the environment,<br />
and above all in the world’s oceans, it is not enough to focus<br />
on microplastics in cosmetics. Instead, measures need to<br />
bioplastics MAGAZINE [04/14] Vol. 9 47
e taken to drastically reduce the amount of plastic waste<br />
entering the environment in general – not just in Germany<br />
or the EU, but worldwide. The EU is pointing us in the right<br />
direction with its five-step waste hierarchy: reuse – reduce,<br />
recycle, incinerate (waste to energy) – (avoid) landfill.<br />
By:<br />
Roland Essel<br />
Head of Sustainability Department<br />
nova-Institute<br />
Hürth, Germany<br />
The nova-Institute is organising a conference entitled “Microplastics in the<br />
Environment – Sources, Consequences, Solutions” to take place on July 1st<br />
between 9am and 6pm at the Maternushaus conference centre in Cologne,<br />
Germany. Further information about the conference can be found at:<br />
www.bio-based.eu/mikroplastik<br />
References<br />
Arthur, C.; Baker, J. & H. Bamford (2009): Proceedings of the international<br />
Research Workshop on the Occurrence, Effects and Fate of Microplastic<br />
Marine Debris. Sept 9-11, 2008. NOAA Technical Memorandum NOS-<br />
QR&R-30.<br />
Barnes, D.K.A.; Galgani, F.; Thompson, R. C. & M. Barlaz (2009):<br />
Accumulation and fragmentation of plastic debris in global environment. In:<br />
Philosophical Transaction of the Royal Society B (biological sciences) 364:<br />
1985-1998<br />
Browne, M.A.; Crump, P.; Niven, S.J.; Teuten, E.; Tonkin, A.; Galloway, T. & R.<br />
Thompson (2011): Accumulation of Microplastic on Shorelines Worldwide:<br />
Sources and Sinks. In: Environmental Science & Technology 45: 9175-9179<br />
CalRecycle – California Department of Resources Recycling and Recovery<br />
(2012): PLA and PHA Biodegradation in the Marine Environment. State of<br />
California, Department of Resources Recycling and Recovery, Sacramento,<br />
California<br />
Gouin, T.; Roche, N.; Lohmann, R. & G. Hodges (2011): A thermodynamic<br />
approach for assessing the environmental exposure of chemicals absorbed to<br />
microplastic. In: Environmental Science & Technology 45: 1466-1472<br />
JRC – Joint Research Centre (2013): Guidance on Monitoring of Marine<br />
Litter in European Seas – A guidance document within the Common<br />
Implementation Strategy fort he Marine Strategy Framework Directive. MSFD<br />
Technical Subgroup on Marine Litter. European Union, 2013<br />
Leslie, H.; van der Meulen, M. D.; Kleissen, F. M. & A. D. Vethaak (2011):<br />
Microplastic Litter in the Dutch Marine Environment – Providing facts and<br />
analysis for Dutch policymakers concerned with marine microplastic litter.<br />
Deltares, the Netherlands<br />
Narayan, R. (2009): Biodegradability... In: bioplastics MAGAZINE [01/09] Vol.<br />
4: 28-31<br />
PlasticsEurope – Association of Plastics Manufacturers (2013): Plastics – the<br />
Facts 2013. An analysis of European latest plastics production, demand and<br />
waste data. PlasticsEurope, Brussels<br />
Ryan, P.G.; Moore, C.J.; van Franeker, J.A. & C.L. Moloney (2010): Monitoring<br />
the abundance of plastic depbris in the marine environment. In: Philpsophical<br />
Transactions of the Royal Society B 364, pp: 1999 - 2012<br />
STAP – Scientific and Technical Advisory Panel (2011): Marine Debris as a<br />
Global Environmental Problem: Introducing a solutions based framework<br />
focused on plastics. Global Environment Facility, Washington, DC.<br />
Teuten, E.L., Rowland, S.J., Galloway, T.S. & Richard C. Thompson<br />
(2007): Potential for plastics to transport hydrophobic contaminants. In<br />
Environmental Science and Technology 41, 7759-7764<br />
Thompson, Richard C. (2014): The challenge: Plastics in the marine<br />
Environment. Environmental Toxicology and Chemistry 33: 6-8<br />
UBA - Umweltbundesamt (2010): Abfälle im Meer – ein gravierendes<br />
ökologisches, ökonomisches und ästhetisches Problem. Umweltbundesamt,<br />
Dessau-Roßlau<br />
UNEP – United Nations Environment Programme (2006): Ecosystems and<br />
Biodiversity in Deep Waters and High Seas. UNEP Regional Seas Reports and<br />
Studies No. 178. UNEP /IUCN, Switzerland<br />
Wright, S. L.; Thompson, R. & T. S. Galloway (2013): The physical impacts of<br />
microplastics on marine organisms: A review. In: Environmental Pollution<br />
177: 483-492<br />
48 bioplastics MAGAZINE [02/14] Vol. 9
Basics<br />
Injection Moulding<br />
Injection moulding is a plastics processing technique for the<br />
fully automated production of plastic parts with complex<br />
geometries. Almost all sizes and shapes of plastic parts<br />
can be made by injection moulding. About 60% of all plastics<br />
processing machines are injection moulding machines [1].<br />
Injection moulded parts range from a few milligrams (e.g.<br />
cogwheels in Swatch ® whatches) up to many kilograms (e.g.<br />
dashboards or bumpers for automobiles). The possible applications<br />
for injection moulding are almost endless. Some<br />
examples are ball-point pens, rulers and other office accessories,<br />
disposable cutlery, garden furniture, beverage crates,<br />
knobs and handles, small mechanical parts, and lots more.<br />
The process<br />
In the injection moulding process molten plastic material<br />
is injected into a mould. The granular plastic raw material for<br />
the part is fed by gravity from a hopper into a heated barrel.<br />
In this barrel the plastic material is transported forward by a<br />
turning screw.<br />
During this process the plastic is melted, mixed and<br />
homogenized. At the same time the crew slowly moves<br />
backward during the melting process to enable a shot<br />
of melted plastic to build up in front of the screw tip<br />
(Fig. 1).<br />
Once the quantity needed for one shot is reached the screw<br />
moves forward and presses the melt through a pre-heated<br />
nozzle and under pressure through the feed channel to the<br />
cavity of the cold mould, the so-called tool. The plastic now<br />
cools down in the tool and is ejected as a finished moulded<br />
part [1].<br />
Injection moulding of bioplastics [4]<br />
In contrast to blown film production, which uses existing<br />
machinery that has already proved to be effective, some<br />
reservations still exist in terms of the injection moulding of<br />
bioplastics.<br />
Fig 1: The injection moulding process (picture: according to<br />
www.fenster-wiki.de)<br />
cooling<br />
heating screw granules<br />
plasticizing<br />
The most important requirement for successfully<br />
injection moulding bioplastics is the compatibility of existing<br />
production equipment. Frankly, existing machinery and<br />
production tools that are designed for common plastics such<br />
as PP, PS or ABS are perfectly suitable for the processing<br />
bioplastics (such as FKuR’s BIO-FLEX ® or BIOGRADE ® )<br />
However, a small investment may be necessary concerning<br />
the hot runner system and the clearances within existing<br />
tools.<br />
One key to success is to reduce the residence time of the<br />
material. When compared with PS, for example, there are<br />
some bioplastics that can be processed with a reduction of<br />
30% of the whole cycle time while others, such as PLA need<br />
longer cooling times due to the crystallisation process. While<br />
the mass temperature should not fall outside the defined<br />
temperature profile the processor should be informed,<br />
through recommended processing conditions, that the<br />
injection pressure and speed can be modified to fill the<br />
mould properly. The small processing window of bioplastics<br />
in terms of the temperature profile may result in the need<br />
for a new hot runner system. Commonly hot runner systems<br />
do not have a constant temperature along the whole length.<br />
This, along with the tendency of the materials to either freeze<br />
immediately or to burn if the temperature goes outside the<br />
processing window, can cause problems if improper hot<br />
runner systems are used.<br />
After resolving the issues of the hot runner by applying a<br />
suitable system then the only thing that the machine operator<br />
needs is a bioplastic grade designed for injection moulding<br />
(pre-dried if necessary) as well as a little practice with the<br />
new materials. Some examples of successful products made<br />
from FKuR’s bioplastics in both multi and single cavity tools<br />
with hot and cold runners are consumer electronics, office<br />
equipment and catering articles. MT<br />
References:<br />
[1]: Stitz, S.; Keller, W.: Spritzgießtechnik, Carl Hanser Publishers,<br />
2001<br />
[2]: Thielen,M.: Bioplastics - Basics. Applications. Markets,<br />
Polymedia Publisher, 2012<br />
[3]: Wikipedia<br />
[4]: Lohr, C.: Bioplastics Designed for rigid parts,<br />
bioplastics MAGAZINE (Vol. 5) Issue 03/2010<br />
mould<br />
melt<br />
drive<br />
injection, cooling<br />
with after-pressure<br />
demoulding<br />
Injection moulding machine<br />
(picture: Ferromatik Milacron)<br />
bioplastics MAGAZINE [03/14] Vol. 9 49
Events<br />
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Event Calendar<br />
Biochemicals & Bioplastics 2014<br />
10.06.2014 - 11.06.2014 - Duesseldorf, Germany<br />
Renaissance Hotel<br />
http://ci43.actonsoftware.com/acton/ct/<br />
6204/s-005c-<strong>1403</strong>/Bct/l-0051/l-0051:587/ct0_0/1<br />
GreenTech<br />
10.06.2014 - 12.06.2014 - Amsterdam, The Netherlands<br />
Amsterdam RAI Convention Centre<br />
www.greentech.nl/e/Pages/default.aspx<br />
4th Biobased Performance Materials Symposium<br />
12.06.2014 - Wageningen, Netherlands<br />
Hotel De Wageningsche Berg<br />
www.wageningenur.nl<br />
fip solution plastique<br />
17.06.2014 - 18.06.2014 - Lyon, France<br />
Lyon Euroexpo, France<br />
www.f-i-p.com<br />
Biobased Materials<br />
24.06.2014 - 25.06.2014 - Stuttgart, Germany<br />
10th Congress for Biobased Materials, Natural Fibres and WPC<br />
www.biobased-materials.com<br />
ISSN 1862-5258<br />
May/June<br />
03 | 2014<br />
Mikroplastik in der Umwelt –<br />
Quellen, Folgen und Lösungen2nd International<br />
01.07.2014 – Cologne, Germany<br />
Maternushaus<br />
http://bio-based.eu/mikroplastik<br />
Highlights<br />
Injection Moulding | 10<br />
Thermoset | 34<br />
Conference Bio-based Polymers and Composites<br />
24.08.2014 - 28.08.2014 - Visegrád, Hungary<br />
www.bipoco2014.hu<br />
Bio-based Global Summit 2014<br />
09.09.2014 - 10.09.2014 - Brussels, Belgien<br />
Thon EU Hotel Brussels<br />
www.biobased-global-summit.com<br />
bioplastics MAGAZINE Vol. 9<br />
... is read in 91 countries<br />
International Symposium on BioPolymers - ISBP2014<br />
29.09.2014 - 01.10.2014 - Santos, Brazil<br />
www.isbp2014.com<br />
BioEnvironmental Polymer Society<br />
14.10.2014 - 17.10.2014 - Kansas City, USA<br />
Kauffman Foundation Conference Center<br />
www.beps.org<br />
+<br />
Mention the promotion code ‘watch‘ or ‘book‘<br />
and you will get our watch or the book 3)<br />
Bioplastics Basics. Applications. Markets. for free<br />
or<br />
1) Offer valid until 31 July 2014<br />
3) Gratis-Buch in Deutschland nicht möglich, no free book in Germany<br />
Forum Kunststoffgeschichte 2014 „Plastics Heritage“<br />
22.10.2014 - 24.10.2014 - Berlin, Germany<br />
Hochschule für Technik und Wirtschaft HTW in Berlin<br />
www.forum-kunststoffgeschichte.de<br />
Ecochem<br />
The Global Sustainable Chemistry & Engineering Event<br />
11.11.2014 - 13.11.2014 - Switzerland, Germany<br />
Congress Center Basel<br />
http://ecochemex.com<br />
3rd Conference on Carbon Dioxide as Feedstock<br />
for Chemistry and Polymers<br />
02.12.2014 - 03.12.2014 - Essen, Germany<br />
Haus der Technik<br />
www.co2-chemistry.eu/registration<br />
9th European Bioplastics<br />
02.12.2014 - 03.12.2014 - Brussels, Belgien<br />
The Square, Brussels<br />
www.european-bioplastics.org<br />
You can meet us! Please contact us in advance by e-mail.
Suppliers Guide<br />
1. Raw Materials<br />
AGRANA Starch<br />
Thermoplastics<br />
Conrathstrasse 7<br />
A-3950 Gmuend, Austria<br />
Tel: +43 676 8926 19374<br />
lukas.raschbauer@agrana.com<br />
www.agrana.com<br />
Shandong Fuwin New Material Co., Ltd.<br />
Econorm ® Biodegradable &<br />
Compostable Resin<br />
North of Baoshan Road, Zibo City,<br />
Shandong Province P.R. China.<br />
Phone: +86 533 7986016<br />
Fax: +86 533 6201788<br />
Mobile: +86-13953357190<br />
CNMHELEN@GMAIL.COM<br />
www.sdfuwin.com<br />
FKuR Kunststoff GmbH<br />
Siemensring 79<br />
D - 47 877 Willich<br />
Tel. +49 2154 9251-0<br />
Tel.: +49 2154 9251-51<br />
sales@fkur.com<br />
www.fkur.com<br />
39 mm<br />
Simply contact:<br />
Tel.: +49 2161 6884467<br />
suppguide@bioplasticsmagazine.com<br />
Stay permanently listed in the<br />
Suppliers Guide with your company<br />
logo and contact information.<br />
For only 6,– EUR per mm, per issue you<br />
can be present among top suppliers in<br />
the field of bioplastics.<br />
For Example:<br />
Dammer Str. 112<br />
41066 Mönchengladbach<br />
Germany<br />
Tel. +49 2161 664864<br />
Fax +49 2161 631045<br />
info@bioplasticsmagazine.com<br />
www.bioplasticsmagazine.com<br />
Showa Denko Europe GmbH<br />
Konrad-Zuse-Platz 4<br />
81829 Munich, Germany<br />
Tel.: +49 89 93996226<br />
www.showa-denko.com<br />
support@sde.de<br />
DuPont de Nemours International S.A.<br />
2 chemin du Pavillon<br />
1218 - Le Grand Saconnex<br />
Switzerland<br />
Tel.: +41 22 171 51 11<br />
Fax: +41 22 580 22 45<br />
plastics@dupont.com<br />
www.renewable.dupont.com<br />
www.plastics.dupont.com<br />
Tel: +86 351-8689356<br />
Fax: +86 351-8689718<br />
www.ecoworld.jinhuigroup.com<br />
jinhuibio@126.com<br />
Jincheng, Lin‘an, Hangzhou,<br />
Zhejiang 311300, P.R. China<br />
China contact: Grace Jin<br />
mobile: 0086 135 7578 9843<br />
Grace@xinfupharm.com<br />
Europe contact(Belgium): Susan Zhang<br />
mobile: 0032 478 991619<br />
zxh0612@hotmail.com<br />
www.xinfupharm.com<br />
1.1 bio based monomers<br />
Corbion Purac<br />
Arkelsedijk 46, P.O. Box 21<br />
4200 AA Gorinchem -<br />
The Netherlands<br />
Tel.: +31 (0)183 695 695<br />
Fax: +31 (0)183 695 604<br />
www.corbion.com/bioplastics<br />
bioplastics@corbion.com<br />
1.2 compounds<br />
GRAFE-Group<br />
Waldecker Straße 21,<br />
99444 Blankenhain, Germany<br />
Tel. +49 36459 45 0<br />
www.grafe.com<br />
Natur-Tec ® - Northern Technologies<br />
4201 Woodland Road<br />
Circle Pines, MN 55014 USA<br />
Tel. +1 763.225.6600<br />
Fax +1 763.225.6645<br />
info@natur-tec.com<br />
www.natur-tec.com<br />
PolyOne<br />
Avenue Melville Wilson, 2<br />
Zoning de la Fagne<br />
5330 Assesse<br />
Belgium<br />
Tel.: + 32 83 660 211<br />
www.polyone.com<br />
Sample Charge:<br />
39mm x 6,00 €<br />
= 234,00 € per entry/per issue<br />
Sample Charge for one year:<br />
6 issues x 234,00 EUR = 1,404.00 €<br />
The entry in our Suppliers Guide is<br />
bookable for one year (6 issues) and<br />
extends automatically if it’s not canceled<br />
three month before expiry.<br />
Evonik Industries AG<br />
Paul Baumann Straße 1<br />
45772 Marl, Germany<br />
Tel +49 2365 49-4717<br />
evonik-hp@evonik.com<br />
www.vestamid-terra.com<br />
www.evonik.com<br />
API S.p.A.<br />
Via Dante Alighieri, 27<br />
36065 Mussolente (VI), Italy<br />
Telephone +39 0424 579711<br />
www.apiplastic.com<br />
www.apinatbio.com<br />
WinGram Industry CO., LTD<br />
Great River(Qin Xin)<br />
Plastic Manufacturer CO., LTD<br />
Mobile (China): +86-13113833156<br />
Mobile (Hong Kong): +852-63078857<br />
Fax: +852-3184 8934<br />
Email: Benson@wingram.hk<br />
www.facebook.com<br />
www.issuu.com<br />
www.twitter.com<br />
www.youtube.com<br />
Natureplast<br />
11 rue François Arago<br />
14123 Ifs – France<br />
Tel. +33 2 31 83 50 87<br />
www.natureplast.eu<br />
t.lefevre@natureplast.eu<br />
Kingfa Sci. & Tech. Co., Ltd.<br />
No.33 Kefeng Rd, Sc. City, Guangzhou<br />
Hi-Tech Ind. Development Zone,<br />
Guangdong, P.R. China. 510663<br />
Tel: +86 (0)20 6622 1696<br />
info@ecopond.com.cn<br />
www.ecopond.com.cn<br />
FLEX-162 Biodeg. Blown Film Resin!<br />
Bio-873 4-Star Inj. Bio-Based Resin!<br />
1.3 PLA<br />
Shenzhen Esun Ind. Co;Ltd<br />
www.brightcn.net<br />
www.esun.en.alibaba.com<br />
bright@brightcn.net<br />
Tel: +86-755-2603 1978<br />
bioplastics MAGAZINE [03/14] Vol. 9 51
Suppliers Guide<br />
1.4 starch-based bioplastics<br />
6. Equipment<br />
Limagrain Céréales Ingrédients<br />
ZAC „Les Portes de Riom“ - BP 173<br />
63204 Riom Cedex - France<br />
Tel. +33 (0)4 73 67 17 00<br />
Fax +33 (0)4 73 67 17 10<br />
www.biolice.com<br />
Metabolix, Inc.<br />
Bio-based and biodegradable resins<br />
and performance additives<br />
21 Erie Street<br />
Cambridge, MA 02139, USA<br />
US +1-617-583-1700<br />
DE +49 (0) 221 / 88 88 94 00<br />
www.metabolix.com<br />
info@metabolix.com<br />
1.6 masterbatches<br />
www.earthfirstpla.com<br />
www.sidaplax.com<br />
www.plasticsuppliers.com<br />
Sidaplax UK : +44 (1) 604 76 66 99<br />
Sidaplax Belgium: +32 9 210 80 10<br />
Plastic Suppliers: +1 866 378 4178<br />
6.1 Machinery & Molds<br />
Molds, Change Parts and Turnkey<br />
Solutions for the PET/Bioplastic<br />
Container Industry<br />
284 Pinebush Road<br />
Cambridge Ontario<br />
Canada N1T 1Z6<br />
Tel. +1 519 624 9720<br />
Fax +1 519 624 9721<br />
info@hallink.com<br />
www.hallink.com<br />
BIOTEC<br />
Biologische Naturverpackungen<br />
Werner-Heisenberg-Strasse 32<br />
46446 Emmerich/Germany<br />
Tel.: +49 (0) 2822 – 92510<br />
info@biotec.de<br />
www.biotec.de<br />
62 136 LESTREM, FRANCE<br />
00 33 (0) 3 21 63 36 00<br />
www.gaialene.com<br />
www.roquette.com<br />
Grabio Greentech Corporation<br />
Tel: +886-3-598-6496<br />
No. 91, Guangfu N. Rd., Hsinchu<br />
Industrial Park,Hukou Township,<br />
Hsinchu County 30351, Taiwan<br />
sales@grabio.com.tw<br />
www.grabio.com.tw<br />
PSM Bioplastic HK<br />
Room 1901B,19/F, Allied Kajima<br />
Buil- ding 138 Gloucester Road,<br />
Wanchai, Hongkong<br />
Tel: +852-31767566<br />
Fax: +852-31767567<br />
support@psm.com.cn<br />
www.psm.com.cn<br />
1.5 PHA<br />
TianAn Biopolymer<br />
No. 68 Dagang 6th Rd,<br />
Beilun, Ningbo, China, 315800<br />
Tel. +86-57 48 68 62 50 2<br />
Fax +86-57 48 68 77 98 0<br />
enquiry@tianan-enmat.com<br />
www.tianan-enmat.com<br />
GRAFE-Group<br />
Waldecker Straße 21,<br />
99444 Blankenhain, Germany<br />
Tel. +49 36459 45 0<br />
www.grafe.com<br />
PolyOne<br />
Avenue Melville Wilson, 2<br />
Zoning de la Fagne<br />
5330 Assesse<br />
Belgium<br />
Tel.: + 32 83 660 211<br />
www.polyone.com<br />
2. Additives/Secondary raw materials<br />
GRAFE-Group<br />
Waldecker Straße 21,<br />
99444 Blankenhain, Germany<br />
Tel. +49 36459 45 0<br />
www.grafe.com<br />
Rhein Chemie Rheinau GmbH<br />
Duesseldorfer Strasse 23-27<br />
68219 Mannheim, Germany<br />
Phone: +49 (0)621-8907-233<br />
Fax: +49 (0)621-8907-8233<br />
bioadimide.eu@rheinchemie.com<br />
www.bioadimide.com<br />
3. Semi finished products<br />
3.1 films<br />
Huhtamaki Films<br />
Sonja Haug<br />
Zweibrückenstraße 15-25<br />
91301 Forchheim<br />
Tel. +49-9191 81203<br />
Fax +49-9191 811203<br />
www.huhtamaki-films.com<br />
Taghleef Industries SpA, Italy<br />
Via E. Fermi, 46<br />
33058 San Giorgio di Nogaro (UD)<br />
Contact Frank Ernst<br />
Tel. +49 2402 7096989<br />
Mobile +49 160 4756573<br />
frank.ernst@ti-films.com<br />
www.ti-films.com<br />
4. Bioplastics products<br />
Minima Technology Co., Ltd.<br />
Esmy Huang, Marketing Manager<br />
No.33. Yichang E. Rd., Taipin City,<br />
Taichung County<br />
411, Taiwan (R.O.C.)<br />
Tel. +886(4)2277 6888<br />
Fax +883(4)2277 6989<br />
Mobil +886(0)982-829988<br />
esmy@minima-tech.com<br />
Skype esmy325<br />
www.minima-tech.com<br />
NOVAMONT S.p.A.<br />
Via Fauser , 8<br />
28100 Novara - ITALIA<br />
Fax +39.0321.699.601<br />
Tel. +39.0321.699.611<br />
www.novamont.com<br />
President Packaging Ind., Corp.<br />
PLA Paper Hot Cup manufacture<br />
In Taiwan, www.ppi.com.tw<br />
Tel.: +886-6-570-4066 ext.5531<br />
Fax: +886-6-570-4077<br />
sales@ppi.com.tw<br />
ProTec Polymer Processing GmbH<br />
Stubenwald-Allee 9<br />
64625 Bensheim, Deutschland<br />
Tel. +49 6251 77061 0<br />
Fax +49 6251 77061 500<br />
info@sp-protec.com<br />
www.sp-protec.com<br />
6.2 Laboratory Equipment<br />
MODA: Biodegradability Analyzer<br />
SAIDA FDS INC.<br />
143-10 Isshiki, Yaizu,<br />
Shizuoka,Japan<br />
Tel:+81-54-624-6260<br />
Info2@moda.vg<br />
www.saidagroup.jp<br />
7. Plant engineering<br />
EREMA Engineering Recycling<br />
Maschinen und Anlagen GmbH<br />
Unterfeldstrasse 3<br />
4052 Ansfelden, AUSTRIA<br />
Phone: +43 (0) 732 / 3190-0<br />
Fax: +43 (0) 732 / 3190-23<br />
erema@erema.at<br />
www.erema.at<br />
Uhde Inventa-Fischer GmbH<br />
Holzhauser Strasse 157–159<br />
D-13509 Berlin<br />
Tel. +49 30 43 567 5<br />
Fax +49 30 43 567 699<br />
sales.de@uhde-inventa-fischer.com<br />
Uhde Inventa-Fischer AG<br />
Via Innovativa 31<br />
CH-7013 Domat/Ems<br />
Tel. +41 81 632 63 11<br />
Fax +41 81 632 74 03<br />
sales.ch@uhde-inventa-fischer.com<br />
www.uhde-inventa-fischer.com<br />
52 bioplastics MAGAZINE [03/14] Vol. 9
Suppliers Guide<br />
9. Services<br />
10.2 Universities<br />
11 rue François Arago<br />
14123 Ifs – France<br />
Tel. +33 2 31 83 50 87<br />
www. biopolynov.com<br />
t.lefevre@natureplast.eu<br />
Osterfelder Str. 3<br />
46047 Oberhausen<br />
Tel.: +49 (0)208 8598 1227<br />
Fax: +49 (0)208 8598 1424<br />
thomas.wodke@umsicht.fhg.de<br />
www.umsicht.fraunhofer.de<br />
Institut für Kunststofftechnik<br />
Universität Stuttgart<br />
Böblinger Straße 70<br />
70199 Stuttgart<br />
Tel +49 711/685-62814<br />
Linda.Goebel@ikt.uni-stuttgart.de<br />
www.ikt.uni-stuttgart.de<br />
narocon<br />
Dr. Harald Kaeb<br />
Tel.: +49 30-28096930<br />
kaeb@narocon.de<br />
www.narocon.de<br />
nova-Institut GmbH<br />
Chemiepark Knapsack<br />
Industriestrasse 300<br />
50354 Huerth, Germany<br />
Tel.: +49(0)2233-48-14 40<br />
E-Mail: contact@nova-institut.de<br />
www.biobased.eu<br />
Bioplastics Consulting<br />
Tel. +49 2161 664864<br />
info@polymediaconsult.com<br />
UL International TTC GmbH<br />
Rheinuferstrasse 7-9, Geb. R33<br />
47829 Krefeld-Uerdingen, Germany<br />
Tel.: +49 (0) 2151 5370-370<br />
Fax: +49 (0) 2151 5370-371<br />
ttc@ul.com<br />
www.ulttc.com<br />
10. Institutions<br />
10.1 Associations<br />
BPI - The Biodegradable<br />
Products Institute<br />
331 West 57th Street, Suite 415<br />
New York, NY 10019, USA<br />
Tel. +1-888-274-5646<br />
info@bpiworld.org<br />
European Bioplastics e.V.<br />
Marienstr. 19/20<br />
10117 Berlin, Germany<br />
Tel. +49 30 284 82 350<br />
Fax +49 30 284 84 359<br />
info@european-bioplastics.org<br />
www.european-bioplastics.org<br />
IfBB – Institute for Bioplastics<br />
and Biocomposites<br />
University of Applied Sciences<br />
and Arts Hanover<br />
Faculty II – Mechanical and<br />
Bioprocess Engineering<br />
Heisterbergallee 12<br />
30453 Hannover, Germany<br />
Tel.: +49 5 11 / 92 96 - 22 69<br />
Fax: +49 5 11 / 92 96 - 99 - 22 69<br />
lisa.mundzeck@fh-hannover.de<br />
http://www.ifbb-hannover.de/<br />
Michigan State University<br />
Department of Chemical<br />
Engineering & Materials Science<br />
Professor Ramani Narayan<br />
East Lansing MI 48824, USA<br />
Tel. +1 517 719 7163<br />
narayan@msu.edu<br />
‘Basics‘ book on bioplastics<br />
This book, created and published by Polymedia Publisher, maker of bioplastics MAGA-<br />
ZINE is available in English and German language.<br />
The book is intended to offer a rapid and uncomplicated introduction into the subject<br />
of bioplastics, and is aimed at all interested readers, in particular those who have not yet<br />
had the opportunity to dig deeply into the subject, such as students or those just joining<br />
this industry, and lay readers. It gives an introduction to plastics and bioplastics, explains<br />
which renewable resources can be used to produce bioplastics, what types of bioplastic<br />
exist, and which ones are already on the market. Further aspects, such as market development,<br />
the agricultural land required, and waste disposal, are also examined.<br />
An extensive index allows the reader to find specific aspects quickly, and is complemented<br />
by a comprehensive literature list and a guide to sources of additional information<br />
on the Internet.<br />
The author Michael Thielen is editor and publisher bioplastics MAGAZINE. He is a qualified<br />
machinery design engineer with a degree in plastics technology from the RWTH<br />
University in Aachen. He has written several books on the subject of blow-moulding<br />
technology and disseminated his knowledge of plastics in numerous presentations,<br />
seminars, guest lectures and teaching assignments.<br />
110 pages full color, paperback<br />
ISBN 978-3-9814981-1-0: Bioplastics<br />
ISBN 978-3-9814981-0-3: Biokunststoffe<br />
Order now for € 18.65 or US-$ 25.00 (+ VAT where applicable, plus shipping and handling, ask for details)<br />
order at www.bioplasticsmagazine.de/books, by phone +49 2161 6884463 or by e-mail books@bioplasticsmagazine.com<br />
Or subscribe and get it as a free gift (see page 69 for details, outside German y only)<br />
bioplastics MAGAZINE [03/14] Vol. 9 53
Companies in this issue<br />
Company Editorial Advert Company Editorial Advert Company Editorial Advert<br />
Agrana 50<br />
AIMPLAS 18<br />
API 50<br />
Asta Eder Composites Consulting 42<br />
AVA Biochem 41<br />
BASF 6<br />
Biomer 18<br />
Biopolynov 52<br />
Bioserie 22<br />
Biotec 27 52<br />
BPI 52<br />
Braskem 22<br />
Clemson Univ 38<br />
Compac 34<br />
Corbion 18 51<br />
CTAG 18<br />
DSM 17, 34<br />
DTU Wind Energie 35<br />
DuPont 10 50<br />
Erema 51<br />
European Bioplastics 33<br />
Evonik 51, 55<br />
Ferromatik Milacron 49<br />
FiberCore 35<br />
FKuR Kunststoff 19, 23, 49 2, 51<br />
Fraunhofer UMSICHT 19 52<br />
Godfrey Hirst Carpets 11<br />
Grabio Greentzech 51<br />
Grafe 50, 51<br />
Grupo Antolin 18<br />
Hallinnk 51<br />
HBC Bulckaert 11<br />
Huhtamaki 51<br />
Hydal Biotech 17<br />
IMI Fabi 24<br />
Inst. F.Bioplastics & Biocomposites 52<br />
Institut f.Kunststofftechnik 52<br />
Interbros 23<br />
ITKE (Univ. Stuttgart) 28<br />
Jiangsu Clean Environmental 17<br />
Jinhui Zhaolong 50<br />
Kingfa 50<br />
Limagrain Cereales Ingredients 51<br />
Megatech 19<br />
Metabolix 32 52<br />
Michigan State Univ. 52<br />
Minima Technology 51<br />
Mitsubishi Chemical 14<br />
Mohawk 11<br />
Nanobiomatters 19<br />
narocon 52<br />
Natureplast 50<br />
NatureWorks 14, 17, 22, 32<br />
Naturtec 50<br />
NBM 19<br />
Newlight Technologies 7<br />
Nomacorc 22<br />
nova-Institute 42, 46 30, 52<br />
Novamont 50, 51<br />
Pallmann Maschinenfabrik 19<br />
PHK Polymertechnik 42<br />
PIEP 19<br />
plasticker 21<br />
Plastic Suppliers 51<br />
polymediaconsult 52<br />
PolyOne 50, 51<br />
President Packaging 51<br />
ProTec 51<br />
PTT 15<br />
Reverdia 17<br />
RheinChemie 51<br />
RIKEN 20<br />
Roquette 17 52<br />
Sabic 6<br />
Saida 51<br />
Shandong Fuwin 48, 50<br />
Shanghai Disoxidation 17<br />
Shenzhen Esun Industrial 50<br />
Showa Denko 50<br />
Sidaplax 51<br />
Siemens Wind Power 35<br />
Spolvay 37<br />
Sprint 7<br />
Suzhou Cleanet 17<br />
Tahghleef Industries 51<br />
Tianan Biopolymer 51<br />
Toyota 11<br />
UL Thermoplastics 52<br />
Univ. Madison Wisconsin 38<br />
Univ. Minho 19<br />
Universiti Sains Malaysia 20<br />
UPM 5<br />
VTT Tech. Research Ctr. 18<br />
Wacker Chemie 14<br />
WinGram 50<br />
Wuhan Huali 48, 51<br />
Wyss Institute (Harvard) 31<br />
Xinfu Pharm 50<br />
Editorial Planner 2014<br />
Issue Month Publ.-Date<br />
edit/ad/<br />
Deadline<br />
04/2014 Jul/Aug 04.08.14 04.07.14 Bottles /<br />
Blow Moulding<br />
05/2014 Sept/Oct 06.10.14 06.09.14 Fiber / Textile /<br />
Nonwoven<br />
06/2014 Nov/Dec 01.12.14 01.11.14 Films / Flexibles /<br />
Bags<br />
Editorial Focus (1) Editorial Focus (2) Basics Fair Specials<br />
Fibre Reinforced<br />
Composites<br />
Toys<br />
Consumer<br />
Electronics<br />
PET<br />
Building Blocks<br />
Sustainability<br />
Subject to changes<br />
www.bioplasticsmagazine.com Follow us on twitter! Be our friend on Facebook!<br />
54 bioplastics MAGAZINE [03/14] Vol. 9
VESTAMID® Terra<br />
High Performance Naturally<br />
Technical biobased polyamides which achieve<br />
performance by natural means<br />
VESTAMID® Terra DS (= PA1010) 100% renewable<br />
VESTAMID® Terra HS (= PA610) 62% renewable<br />
VESTAMID® Terra DD (= PA1012) 100% renewable<br />
<br />
<br />
<br />
<br />
2<br />
<br />
www.vestamid-terra.com
A real sign<br />
of sustainable<br />
development.<br />
There is such a thing as genuinely sustainable<br />
development.<br />
Since 1989, Novamont researchers have been working<br />
on an ambitious project that combines the chemical<br />
industry, agriculture and the environment: “Living Chemistry<br />
for Quality of Life”. Its objective has been to create products<br />
with a low environmental impact. The result of Novamont’s<br />
innovative research is the new bioplastic Mater-Bi ® .<br />
Mater-Bi ® is a family of materials, completely biodegradable and compostable<br />
which contain renewable raw materials such as starch and vegetable oil<br />
derivates. Mater-Bi ® performs like traditional plastics but it saves energy,<br />
contributes to reducing the greenhouse effect and at the end of its life cycle,<br />
it closes the loop by changing into fertile humus. Everyone’s dream has<br />
become a reality.<br />
Living Chemistry for Quality of Life.<br />
www.novamont.com<br />
Within Mater-Bi ® product