Nanocomposites for NanoPackaging

Nanomaterials for Nanocomposites / NanoPackaging Industries E. Gaffet Director, Institut Jean Lamour UMR 7198 CNRS / Université de Lorraine Elu à l’Académie Européenne des Sciences (2003 - ….) Président du Comité Scientifique « NanoSciences & Nanotechnologies » / ANR (France) Président et membre Groupe d’Experts ANSES (France) (2005 – 2012 et pérenne 2012 – 2015) Membre du Haut Conseil de Santé Publique (France) Membre SCENIHR (Europe) – Nanodéfinitions , NanoMédecine Président - OCDE / WPMN - Physico – Chemical NanoCharacterisation Community of Practice

Concilier Recherche, Innovation & Sécurité Sanitaire

[email protected] Trans Nano Forum – 10 September 2014, Nancy (France)

Outline

i)

Définitions, Markets, Properties, Applications Définitions, Prospectives, Propriétés, Applications ii) Real Risks, Perceptual Risks, Regulations Risques réels, perçus, réglementation iii) NP Hazard (Eco/Toxicity) Nano(Eco)-toxicité iv) Benefits / Risks analyses

E. Gaffet Trans - Trans NanoNano Forum Forum – 10 September – 10 September 2014,2014, Nancy Nancy (rance) (France)

E. Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

Cheveu : 80.000 nm

http://ccgconsultinginc.com/Documents/Track1%20Alcides%20Lopes%20Leao.pdf E. Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

► i) Définitions, Markets, Properties, Applications Définitions, Prospectives, Propriétés, Applications ii) Real Risks, Perceptual Risks, Regulations Risques réels, perçus, réglementation iii) NP Hazard (Eco/Toxicity) Nanotoxicité

iv) Benefits / Risks analyses

E. Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

NanoMaterials Nanomaterials of  Dimensions : 0 -D : Ultrafine powders, 1 – D : thin multilayers, 2 – D : surface coatings, 3 - D : bulk nanomaterials.

▼ NanoPowders

Massive NanoMaterials ▲ & Nanostructured Powders

H. Gleiter E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France) Acta Mater. 48 (2000) 1 - 29

Particle Number = Fonction of the dimension

1gramme d’oxyde de Titane Bulk Scale Dimension millimétrique Ø = 1mm 54 particules

1 gramme de nanoparticules d’oxyde de Titane – 100 m2

Micrometer Scale Dimension micronique Ø = 1 micromètre 10.000.000.000 particules (10 milliards) Nanometer Scale Dimension nanométrique Ø = 10 nanomètre 1016 particules (10 Quadrillions ou 10 Millions de Milliards) If only 2 grams of 100 nm diameter NPs were to be evenly distributed there would be enough to provide every human worldwide with 300,000 particles each (Hardman 2006). Source : K. Ausman Center for Biological and Environmental Nanotechnology

Surface (ϕ nm) = 10.000.000 x Surface (ϕ cm)

Illustration of the Small Mass: Large Surface Area Paradigm The Relevance for Food Safety of Applications of Nanotechnology in the Food and Feed Industries - Irlande - Septembre 2008

E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

http://dspace.unimap.edu.my/dspace/bitstream/12345678 9/7952/1/An%20Introduction%20And%20Overview.pdf

► i) Définitions, Markets, Properties, Applications Définitions, Prospectives, Propriétés, Applications ii) Real Risks, Perceptual Risks, Regulations Risques réels, perçus, réglementation iii) NP Hazard (Eco/Toxicity) Nanotoxicité iv) Benefits / Risks analyses



TiO2

nClay

ZnO TiO2

nClay

Ag nTC

nClay

nClay nClay

TiO2

TiO2

nTC

Ag


nTC

From R.W. Siegel ( ISEA November 2008) E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

From R.W. Siegel ( ISEA November 2008)



NYLON-MXD6 BARRIER RESIN The critical component of barrier bottles is the barrier resin itself. Barrier resin is typically incorporated at the preform stage as an inner layer with PET on both sides, making PET the beverage contact layer as well as the layer gripped by the consumer. N-MXD6 resin is a product of Mitsubishi Gas Chemical Company, Inc. It is produced by polymerization of MXDA and adipic acid. The resulting resin contains meta-xylylene groups of the following formula:



NanoPackaging (1)

Nanotechnology in Agriculture and Food – NanoForum – May 2006

Optimising product shelf-life. Such packaging systems would be able to repair small holes/tears, respond to environmental conditions (e.g. temperature & moisture changes), & alert the customer if contamination : Modifying the permeation behaviour of foils, increasing barrier properties (mechanical, thermal, chemical, & microbial), improving mechanical & heat-resistance properties, developing active antimicrobic & antifungal surfaces, & sensing as well as signaling microbiological & biochemical changes.

Voridan &Nanocor (for Miller Brewing Co.) Imperm : nanocomposite containing clay nanoparticles. Both lighter and stronger than glass and is less likely to shatter. The nanocomposite structure minimises loss of carbon dioxide from the beer and the ingress of oxygen to the bottle, keeping the beer fresher and giving it up to a six-month shelf life.

Honeywell Specialty Polymers The “Aegis” nylon 6 is the barrier layer in this 3-layered construction and has been used since late 2003 in the 1.6-litre Hite Pitcher beer bottle from Hite Brewery Co. in South Korea has also successfully engineered plastic beer bottles textended shelf life, up to 26 weeks)In a different strategy,

Bayer

Durethan KU2-2601 packaging film, lighter, stronger and more heat resistant than those currently on the market. (prevent contents from drying out and to protect them from moisture and oxygen) a “hybrid system” enriched with an enormous number of silicate nanoparticles. These massively reduce the entrance of oxygen and other gases, and the exit of moisture, preventing food from spoiling.

Kodak Antimicrobial films : ability to absorb oxygen - impeding food deterioration. E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

NanoPackaging (2) Kraft Foods “Electronic tongue” for inclusion in packaging. This consists of an array of nanosensors which are extremely sensitive to gases released by food as it spoils, causing the sensor strip to change colour as a result, giving a clear visible signal of whether the food is fresh or not.

AgroMicron (BioMark) Detection of contamination of food. NanoBioluminescence Detection Spray which contains a luminescent protein that has been engineered to bind to the surface of microbes such as Salmonella and E. coli. When bound, it emits a visible glow, thus allowing easy detection of contaminated food or beverages. The more intense the glow is, the higher the bacterial contamination Applicatiion in ocean freight containerized shipping as well as to fight bioterrorism. Nanotechnology in Agriculture and Food – NanoForum – May 2006


2006 worldwide NanoMarket and 2012 perspectives (in US$) Sector \ Year

2006

2012

2015

Source

Food

410 Millions

5,8 Milliards

--

Cientifica - 2007

Chemical

44 Milliards

90 Milliards

--

Cientifica - 2007

Drug Delivery

3,39 Milliards

26 Milliards

220 Milliards

Cientifica - 2007

Global

83 Milliards

263 Milliards

1.500 Milliards

Cientifica - 2007

135 Milliards

693 Milliards

2.950 Milliards

Cientifica - 2007

(excl. Semis)

Global (incl. Semis)

Nanofood market : 2.6 bn. US$ in 2003, 5.3 bn. US$ in 2005, 20.4 bn. US$ in 2010 En 2015, 40% des aliments industriels Nano – featured Food & beverage packaging : 150 million US$ in 2002, 860 million US$ in 2004, 1.1 bn. US$ in 2005, 3.7 bn US$ in 2010 More than 400 Companies around the world are today active in research and development and production. USA is the leader followed by Japan and China. By 2010 Asia, with more than 50 percent of the world population, will become the biggest market for the Nanofood, with China in the leading position Source : http://www.hkc22.com/Nanofoodconference.html (Helmut Kaiser Consulting) GMR making possible high density hard disk drives (HDD), 450 million HDDs in 2006 - $25 billions Nanoelectronics : 50% electronics components industry by 2010. $120 billions in 2007, $130 billions in 2010 (Cientifica – Nov. 2007) E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

Strong increase in nanofood and molecular food markets in 2005 worldwide 400 Companies worldwide in Research and Development and Production using nanotechnologies and molecular science in food, foodprocessing and packaging. The most up-to-date market development, research and strategies for the application of nanotechnology in food and food packaging industries worldwide Designing and producing food by shaping molecules and atoms is the future of the foodindustry worldwide. On the one side, further breakthroughs in crop DNA decoding and analysing enable the industries to predict, control and improve the agricultural production. On the other side, with technology of manipulating the molecules and the atoms of food, the future food industry has a powerful method to design food with much more capability and precision, lower costs and sustainability. Meanwhile, the combination of DNA and nanotechnology research generates the new nutrition delivery system, which brings the active agents more precisely and efficiently to the wanted parts of the human bodies and cells. Functional food will benefit firstly from the new technologies, followed by standard food, nutraceuticals and others. During last three years, food industries have witnessed that the nanotechnoloy has been really integrated in a number of food and food packaging products. There are now over 300 nanofood products available on the market worldwide. These exciting achievements have encouraged a large increase of R&D investments in nanofood. Today, the nanotechnology is no longer an empty buzzword, but an indispensable reality in the food industry. Any food company who wants keep its leadership in food industries must begin to work with nanotechnology right now. The impact of nanotechnology is huge, ranging from basic food to food processing, from nutrition delivery to intelligent packaging. It is estimated that the nanotechnology and nano-bio-info convergence will influence over 40% of the food industries up to 2015. The risk for the food companies lies in NOT entering the nanotechnology, but entering too late. The nanofood market has been soaring from 2.6 bn. US dollars 2003 to 5.3 bn. US dollars in 2005 and is expected to reach 20.4 bn. US dollars in 2010. Nano-featured food packaging market will grow from US$ 1.1 bn. 2005 to US$ 3.7 bn up to 2010. More than 400 Companies around the world are today active in research and development and production.. USA is the leader followed by Japan and China. By 2010 Asia, with more than 50 percent of the world population, will become the biggest market for the Nanofood, with China in the leading position. Source : http://www.hkc22.com/Nanofoodconference.html E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

Future nanopackaging market worth billions 2004 : less than 40 nanopackaging products – 2007 : over 400 available at present extend shelf life, antibacterial functions, interactive packaging NanoPackaging : 2002 : $150m (€111m), 2004 : $860 (€635m), 2006 : $980m (€724m) 2006 worldwide sales of nanotechnology-related products : $1bn (€739m), Food packaging industry : $30bn (€22bn) Consultants, Helmut Kaiser estimate that nanotechnology will change 25 per cent of the food packaging market, currently worth $100bn (€74bn), in the decade to follow. "Simple traditional "packing" is to be replaced with multi-functional intelligent methods to improve the food quality,“ Krafts, Budweiser and Pepsi have research and development projects in operation. China and Taiwan have already taken a firm foothold in this market and are poised to be challenging competitors in this market.

Nanotechnology—actually nanotechnologies— for packaging will grow from

a $ 66-million business in 2003 to $360 million by 2008, an astonishing 40% annual increase Graham Moore et al. the Packaging Industries Research Association (PIRA, www.piranet.com)

Nanocomposites are a $75 million market globally and are expected to soar to $250 million in 2010, predicts Principia Partners in the company’s recently published study, Nanocomposites 2005. 15/5/2007 http://www.packwire.com/news-by-product/news.asp?id=76538&idCat=&k=Helmut-Kaiser--nanotechnology-shelf-life E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

Nano - Composites Liste de quelques fournisseurs de nanocomposites

From Etats – Unis Sciences Physiques – May 2004



Nano - Composites 2003 : 11.123 Tons – 90.8 Millions $ (BCC) 2008 : 36.000 Tons – 211 Millions $ + 18,4% / an

Packaging Market 2.200 Tons – 2007 45.000 Tons – 2011 (BRG Townsend – 2002)

35957 27739 211.1

178.9 11123 8217 5675

5448

90.8

70.7 Thermoplastiques

Thermodurcis

Total

20.1

32.2

Worldwide Production of polymer nanocomposite (Tons). Worldwide Production of polymer nanocomposite (Millions of dollars)

From Etats – Unis Sciences Physiques – May 2004 E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)


Nanocomposite sales volumes by packaging application (in tonnes),

2003-08 Main applications

2003

Potential nanotechnology applications in packaging (million €), 2003-08

2008

2003

2008

CAGR / year 2003-08

Barrier packaging (nanocomposites)

48.0

112.0

18.4%

Nanocoatings of decorative applications

0.0

1.4

N.A.

2.0

5.7

23.2%

Applications

Food Packaging Carbonated soft drinks

136

3810

Beer

862

1542

Meats

181

726

Package foods & condiments

45

726

Cheese

91

227

Juices

45

91

Functional applications (transparency, antifrog…) Protective applications (antimicrobial, UV filter…)

3.0

10.7

29.4%

Thin film electronics for sensory packaging

0.0

35.7

N.A.

Nanobarcodes for track and trace

0.0

120.0

N.A.

Total

53.0

285.5

40.1%

Others Pet Food

45

91

Electronics

45

91

Pharmaceuticals

45

23

Household appl. & automotive

45

23

Total

1540

7350

SFN Technology Meeting - Bern University of Applied Sciences – Swiss College of Agriculture Tuesday 12th December 2006 - Didier Louvier


► i) Définitions, Markets, Properties, Applications Définitions, Prospectives, Propriétés, Applications ii) Real Risks, Perceptual Risks, Regulations Risques réels, perçus, réglementation iii) NP Hazard (Eco/Toxicity) Nanotoxicité iv) Benefits / Risks analyses


Desirability of Physical Properties in 8 Packaging Applications (Food, Drug, etc) Current packaging for the MRE entree consists of a retortable four-layer pouch using aluminium foil as the barrier along with polyethylene, nylon and polyester. Other food items, such as crackers, are packaged in three-layer foil pouches. This system can only be landfilled because of the aluminium foil. The goal of the research is to remove this aluminium foil barrier and replace the pouch with nanocomposite films. Overall, the amount of trash generated from MREs will be reduced because the packaging will be thinner and lighter as well as being recyclable, biodegradable or both. The MRE's shelf life is three years at 80¼F and six months at 100¼F. With such stringent shelf life requirements, an exceptional barrier material is necessary. The packaging also needs to be robust enough to withstand airdrop and rough handling associated with the military logistics system. Carried within the meal, ready-to-eat (MRE) packaging is the food that fuels the nation's military when hot, cooked meals are unavailable. After MREs are consumed, however, the empty flexible packages, which make up one-third of the weight of the MRE, contribute to significant waste problems for the Army. More than 14,000 tonnes of solid packaging waste are generated annually from the nearly 47 million operational rations consumed by America's military, according to a report from the Department of Defense Combat Feeding Directorate at the US Army Soldier Systems Center in Natick, Massachusetts. E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

Top 10 Uses of NanoTechnology in Food Packaging 1. CONTAMINATION SENSOR: Flash a light to reveal the presence of E. coli bacteria. 2. ANTIMICROBIAL PACKAGING: Edible food films made with cinnamon or oregano oil, or nano particles of zinc, calcium other materials that kill bacteria. 3. IMPROVED FOOD STORAGE: Nano-enhanced barrier keeps oxygen-sensitive foods fresher. 4. ENHANCED NUTRIENT DELIVERY : Nano-encapsulating improves solubility of vitamins, antioxidants, healthy omega oils and other ‘nutraceuticals’. 5. GREEN PACKAGING: Nano-fibers made from lobster shells or organic corn are both antimicrobial and biodegradable. 6. PESTICIDE REDUCTION: A cloth saturated with nano fibers slowly releases pesticides, eliminating need for additional spraying and reducing chemical leakage into the water supply . 7. TRACKING, TRACING; BRAND PROTECTION: Nanobarcodes can be created to tag individual products and trace outbreaks.

8. TEXTURE: Food spreadability and stability improve with nano-sized crystals and lipids for better lowfat foods. 9. FLAVOR: Trick the tongue with bitter blockers or sweet and salty enhancers. 10. BACTERIA IDENTIFICATION AND ELIMINATION: Nano carbohydrate particles bind with bacteria so they can be detected and eliminated. http://www.environmentalleader.com/2009/02/24/top-10-uses-of-nanotechnology-in-food/ E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

I. Nanostructuration



Nano - Additives Currently, natural clays cost about $3–15/lb, synthetic clays about $10–20/lb, and nanostructured silicons up to $200/lb. Thus, the present cost structure for nanocomposites as barrier materials is not necessarily meeting the commercial hopes, an obstacle that faces many new package materials.


Nano-additives (yet used since 1970 !!!) While nanoclays and carbon nanotubes are used to make nanocomposites, other nano-sized materials are being used as plastics additives such as flame retardant synergists and nucleators. "Nano-sized additives have been used long before 'nano' became popular, but there is new interest all around the world in what nanomaterials can do. People are looking at all types of materials to see what properties they have at the nano scale,“ comments Carl Lance, director of marketing at Nyacol® Nano Technologies, Inc. Nyacol's antimony

pentoxides, with particle sizes in the 30-35 nanometer (nm) range, and silica materials in the 20-120 nm range have been used commercially since the early 1970s, beginning in textile coatings and expanding into polymer coatings and plastics. With the use of surface treatments, dispersion is not a problem, says Mr. Lance. Antimony pentoxides (APO) replace antimony oxides (ATO) as a synergist in halogenated flame retardant systems. Compared to ATO, APO offers improvements in physical properties and a refractive index closer to that of the resin, which allows production of translucent or transparent materials, or the use of less pigment in coloured parts, says Mr. Lance. Nyacol's recently commercialized Nucleator Grade Silica (NGS) for polypropylene has a cost advantage over currently available nucleators and clarifying agents, notes Mr. Lance. Nyacol is also developing a colloidal, nano-sized zinc oxide for use as a UV absorber in PET.

Nanocomposites are polymers reinforced with nanomaterials that enable dramatic property improvements at relatively low loading levels.

Automotive and packaging market segments are expected to account for nearly 80% of nanocomposite consumption, notes Jim Morton, senior partner at Principia Partners. Nanoclays are the most dominant commercial nanomaterial, accounting for nearly 70% of the volume used, he adds. Carbon nanotubes, carbon nanofibres, and POSS® Chemicals are also being used commercially in nanocomposites. Plastics Additives & Compounding November/December 2005 E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

Nanotechnology use in food applications: a scientific and regulatory challenge The growing use of nanotechnology in food applications poses new challenges for both science and regulation in Europe’s food and nutrition market, an industry expert has said. EAS-Italy nutritional product regulatory affairs manager Stefanie Geiser said that as the nanotechnology market continues to grow regulators and scientists are actively working to find regulatory and risk assessment models to embrace its research and safety aspects.

The first nano-food contact material (a silicon dioxide coating) has already been approved by the European Food Safety Authority (EFSA) this year (2007), and a second, titanium nitride, is under review. However, EFSA has said that it will not be able to meet the European Commission’s mandate for a complete generic risk assessment of nanotechnology by 31 March 2008, because of the vast range of existing nanomaterials with completely divergent physical/chemical properties and safety profiles. Instead EFSA has proposed to issue only an initial scientific opinion by summer 2008, and now plans to set up a working group of 10 to 15 Member State scientific experts to analyse and build on already generated opinions by EU scientific advisory bodies and third countries. A first discussion on this working strategy for Nanotechnology will be held by the EFSA Scientific Committee on 19/20 November. Discussions will further be followed up at the Brussels EFSA Scientific Forum event on 20-21 November and the next "EFSA Steering Group on Cooperation" meeting on 26 November in Berlin. "It will prove difficult to find a common risk assessment umbrella that can embrace the diversity of all current and future nanomaterial food applications,” Ms Geiser said in a podcast interview. “The Commission is therefore actively involved in finding ways of integrating nanotechnology as far as possible into already existing EU regulatory frameworks. Nanotechnology aspects have recently been included in the Commission's proposals for a revision of the EU Novel foods Regulation and also the revision of the Food Additives and Enzymes Regulations." Nanotechnology refers to invisible particles measuring around one billionth of a meter which, in the food sector, are used in food packaging and direct application in food supplements and functional food ingredients. Its techniques and products include 'micro-encapsulation' of antioxidants/minerals/fatty acids to increase body absorption of specific nutrients, and the incorporation of ingredients into food matrixes that would otherwise not be possible, such as the 'nano-drops liquid carriers' in Canola oil which allow for the absorption of vitamins, minerals and phytochemicals otherwise insoluble in water or fats. http://icon.rice.edu/details.cfm?NID=673 E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

European Food Safety Authority approves TiN nanoparticles safe for use in PET bottles On the 27th November 2008, the European Food Safety Authority (EFSA) adopted the Scientific Opinion of the EFSA Panel on food contact materials, enzymes, flavourings and processing aids (CEF) on 21st list of substances for food contact materials (the EFSA Journal (2008) 888-890, 1-14). (16th December 2008) http://www.nanotechia.org/news/global/european-parliament-to-vote-on-definition-and-labe


On the 27th November (2008) , the European Food Safety Authority (EFSA) adopted the Scientific Opinion of the EFSA Panel on food contact materials, enzymes, flavourings and processing aids (CEF) on 21st list of substances for food contact materials (the EFSA Journal (2008) 888-890, 1-14). The list includes nanoparticles of titanium nitride as a ‘new substance’ (i.e. not previously evaluated by SCF or CEF) for the following use: ‘According to the petitioner, titanium nitride (TiN), nanoparticles, is intended to be used as an additive in polyethylene terephthalate (PET) bottles up to 20 mg/kg . The final product is intended to come into contact with all types of liquid foodstuffs for typical hotfill/pasteurization and/or long time storage at room temperature.’ ‘Titanium nitride as such is chemically inert and completely insoluble in all food simulants tested,’ the Panel found. It is pointed out that ‘in addition, the Panel investigated the potential migration of TiN nanoparticles using theoretical considerations based on diffusion models which are known to overestimate migration. These models estimate that no migration occurs. Based on the above data the Panel considers that the intended use of this nanoparticulate substance does not give rise to exposure via food and therefore to toxicological concern. Consequently toxicological data for this application are not required. In an interview with Foodproductiondaily.com, EFSA stressed that the evaluation of TiN nanoparticles was conducted as per the case-by-case approach recommended in the agency’s Draft Opinion on Risks arising from Nanoscience and Nanotechnologies on Food and Feed Safety. http://www.nanotechia.org/news/global/ european-food-safety-authority-approves-tin-nanopa E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)







Dispersion Techniques Ultrasonication: shock waves promotes the ‘‘peeling off” of individual nanoparticles located at the outer part of the nanoparticle bundles, or agglomerates, and thus results in the separation of individualized nanoparticles from the bundles

Calendering process: the gap width between the rollers can be mechanically adjusted, thus it is easy to get a controllable and narrow size distribution of particles in viscous materials to achieve the desired level of particle dispersion

P.-C. Ma et al. / Composites: Part A 41 (2010) 1345–1367 E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

Dispersion Techniques Ball milling: grinding method used to grind materials into extremely fine powder for use in paints Stir and extrusion: MWCNTs can be dispersed more easily than SWCNTs by employing stir. Extrusion is particularly useful to produce CNT/polymer nanocomposites with a high filler content

P.-C. Ma et al. / Composites: Part A 41 (2010) 1345–1367



II. Mechanical Properties


Mechanical Strength Tensile strength, tensile modulus and heat distortion temperature (HDT) characteristics are improved with the use of nanotechnology. Cloisite®, a nylon nanocomposite produced by Southern Clay Products with a clay loading of 5%, exemplifies these increased mechanical properties. The amount of change in mechanical properties is directly related to the quantity of nanofiller used in the particular nanocomposite. For example,

by adding 2% nanoclay to a nylon 6 nanocomposite increases tensile strength by 49%. However, adding 6% nanoclay dramatically increases the tensile strength by 98% (Ling, et. all, 2004). This pattern also applies to the HDT and flexural modulus characteristics. Other nylon nanocomposite polymers have increased mechanical properties similar to Cloisite®.

+ 23% + 69% + 56% + 68%


Nylon 6 Nanocomposites Nylon 6 nanocomposites containing 2 wt% Nanomer are currently available from two commercial sources, Honeywell Engineered Polymers & Solutions and Bayer AG. Four percent loaded products are under development. Currently available products feature dryas-molded (DAM) strength improvements of 30% and heat distortion increases double those of neat nylon. As loading increases, so too do strengths and HDT’s.


III. Barrier Properties






Barrier PET Beer Bottle Is a Big Hit in Korea—July 2004 ------------------------------------------------------------------------The most impressive success so far in barrier PET beer bottles is a 1.6-liter bottle launched just six months ago that already accounts for 15% of beer consumed in South Korea. The Hite Pitcher brand comes from Hite Brewery Co., Korea’s leading brewer. The bottle, which is said to provide 26-week shelf life, is blow molded by Hyosong Corp. of South Korea. It is blown from three-layer preforms made on a coinjection system from Kortec Inc., Beverly, Mass.

The barrier layer is the Aegis nylon 6/nanoclay compound from Honeywell Specialty Polymers, Morristown, N.J. Honeywell Specialty Polymers 101 Columbia Rd. Morristown, NJ 07962 - Phone (800) 446-3022 Fax (973) 455-6154 http://www.ptonline.com/articles/kuw/12437.html Three hundred billion beer bottles a year worldwide is a mighty tempting target for the plastics industry. http://www.ptonline.com/articles/200001cu2.html E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)


Nano Packaging : « Dual Technologies » (Natick US Lab.)) Current packaging for the MRE (Meat Ready to Eat) entree consists of a retortable fourlayer pouch using aluminium foil as the barrier along with polyethylene, nylon and polyester. Other food items, such as crackers, are packaged in three-layer foil pouches. This system can only be landfilled because of the aluminium foil. The goal of the research is to remove this aluminium foil barrier and replace the pouch with nanocomposite films. Overall, the amount of trash generated from MREs will be reduced because the packaging will be thinner and lighter as well as being recyclable, biodegradable or both. The MRE's shelf life is three years at 80¼F and six months at 100¼F. With such stringent shelf life requirements, an exceptional barrier material is necessary. The packaging also needs to be robust enough to withstand airdrop and rough handling associated with the military logistics system. Carried within the meal, ready-to-eat (MRE) packaging is the food that fuels the nation's military when hot, cooked meals are unavailable. After MREs are consumed, however, the empty flexible packages, which make up one-third of the weight of the MRE, contribute to significant waste problems for the Army. More than 14,000 tonnes of solid packaging waste are generated annually from the nearly 47 million operational rations consumed by America's military, according to a report from the Department of Defense Combat Feeding Directorate at the US Army Soldier Systems Center in Natick, Massachusetts. E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

IV. Enhanced Flame Retardancy of Nanocomposites



Flame Retardant Plastics A rapidly expanding area is fire retardant polyolefin nanocomposites. These materials readily form tough char layers. Char formation impedes the movement of volatilized polymer from the interior of a plastic matrix, denying fuel at the air/surface interface. For 5% loaded products peak heat release rates (HRR) are reduced by

70%. Employed in conjunction with traditional flame retardants, nanocomposites can achieve equivalent fire ratings using significantly reduced FR additive packages. With less FR additive dilution and greater reinforcement via nanocompositing itself, mechanicals are largely restored to levels seen in neat resin and at lower cost. This combination of benefits will likely make fire retardancy the largest use area longterm. Nanocomposites for FR uses are available from Gitto/Global Corporation, Lunenburg, MA. HRR for Polypropylene Nanocomposites


V. UV Protection


New nano product protects plastic from sunlight 22/6/2007 DuPont is about to release a product made using nanotechnology that will protect plastics from sunlight.

DuPont Light Stabilizer 210, a new titanium dioxide-based material. Overlong exposure to sunlight can break down components in plastic packaging, causing a change in colour.

DuPont developed the framework with Environmental Defense, a US non-profit organisation. The two developed the Nano Risk Framework for use around the world by small and large companies, regulatory agencies, universities, and others with an interest in commercialising nanoscale materials. http://www.packwire.com/news-by-product/news.asp?id=77603&idCat=&k=DuPont--nanotechnology-packaging


VI. Rheology Control





VII. Conductivity


Plastics Additives & Compounding November/December 2005


VIII. Active Packaging


NanoSilva Integrated Antimicrobial Solutions Engineered For Polymer Applications

FOOD AND BEVERAGE: • PACKAGING • PROCESS EQUIPMENT • BULK STORAGE CONTAINERS • PROTECTIVE CLOTHING • REFRIGERATION EQUIPMENT

HEALTH CARE: • SURGICAL INSTRUMENTS • SURGICAL EQUIPMENT • MEDICAL IMPLANTS • PACKAGING • SURGICAL APPAREL/GLOVES • MEDICAL DEVICES • WOUND CARE

HOUSE WARES: • FOOD STORAGE CONTAINERS • BATHROOM ACCESSORIES • REFUGE CONTAINERS • KITCHEN ACCESSORIES • COOKWARE • FURNITURE • KITCHEN APPLIANCES



NanoxClean : Emballages Alimentaires à base de Nano Argent Une technologie brésilienne permet de tripler la durée de validité des aliments L’entreprise Nanox, dont le siège est situé à São Paulo, fabrique des particules antimicrobiennes nanostructurées à base de molécules d’argent qui, appliquées aux emballages alimentaires, permettent de multiplier par trois la durée de validité des aliments qu’ils contiennent. Le « NanoxClean » a été créé en 2005 par trois chercheurs de l’Institut de Chimie de l’Université Fédérale de São Carlos (UFSCar), avec un financement de plusieurs institutions publiques d’appui à la recherche et à l’innovation. Ce matériel, qui se présente sous la forme d’une poudre, a d’abord été appliqué sur la superficie de métaux (instruments médicaux et dentaires, sèche-cheveux, purificateur d’eau, résines...) pour ensuite être développé à partir de 2007 sur les emballages alimentaires. Cela inclue autant les films plastiques souples, que les polymères durs utilisés par exemple pour les pots de yaourts. Les nanoparticules d’argent ont un effet sur les fonctions vitales des bactéries, et empêchent ces dernières de proliférer. Selon Luiz Gustavo Pagotto Simões, le directeur de l’entreprise Nanox, « un produit qui durait 6 mois, par exemple, durera de huit mois à un an en étant contenu dans un emballage qui utilise le matériel bactéricide ». Déjà commercialisé au Brésil et au Mexique, la technologie « NanoxClean » a obtenu l’enregistrement de la Food and Drug Administration (FDA), agence régulatrice des aliments aux Etats-Unis, pour la diffusion de ce produit dans le pays. Les principaux concurrents du NanoxClean sont des entreprises japonaises et allemandes. Néanmoins, la technologie brésilienne a l’avantage d’être moins coûteuse, puisque l’argent contenu dans le produit se présente en concentrations moins élevées, pour un résultat plus efficace. Sources Site de l’entreprise Nanox http://agencia.fapesp.br/17050 http://redirectix.bulletins-electro... http://www.nanox.com.br/site/?p=182... http://redirectix.bulletins-electro... ADIT, BE Brésil (n°145, le 29 mai 2013)



http://www.bluemoongoods.com/images/food_container.jpg


Foods can easily last 2, 3, even 4 times longer in the Fresh Box silver nano food storage containers compared to other high quality food storage containers like Tupperware ™ and Rubbermaid ™. Fresher food is more nutritious, better tasting and safer. Check out the photos below. The tomatoes on the left have been stored in a Fresh Box container for 15 days. The tomatoes on the right were stored during the same period in a standard food container without silver nano particles. Which do you want in your salad? The silver nanoparticles in Fresh Box containers naturally kill bacteria and limit mold growth without toxins. http://www.bluemoongoods.com/silver_nanoparticle_food_containers.htm

The Fresh Box Nano-Silver Food Containers can extend food life up to 15 days beyond standard Tupperware ™ and Rubbermaid ™ type food containers. E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

Toxic Nanoparticles Might Be Entering Human Food Supply Aug. 22, 2013 — Over the last few years, the use of nanomaterials for water treatment, food packaging, pesticides, cosmetics and other industries has increased. For example, farmers have used silver nanoparticles as a pesticide because of their capability to suppress the growth of harmful organisms. However, a growing concern is that these particles could pose a potential health risk to humans and the environment. In a new study, researchers at the University of Missouri have developed a reliable method for detecting silver nanoparticles in fresh produce and other food products.

Lin and his colleagues, including MU scientists Azlin Mustapha and Bongkosh Vardhanabhuti, studied the residue and penetration of silver nanoparticles on pear skin.

First, the scientists immersed the pears in a silver nanoparticle solution similar to pesticide application. The pears were then washed and rinsed repeatedly (Journal of Agricultural and Food Chemistry)

Results showed that four days after the treatment and rinsing, silver nanoparticles were still attached to the skin, and the smaller particles were able to penetrate the skin and reach the pear pulp http://www.sciencedaily.com/releases/2013/08/130822194530.htm?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3 A+sciencedaily%2Ftop_news%2Ftop_science+%28ScienceDaily%3A+Top+News+--+Top+Science%29


Email incisives de rat

Nano - Bio / Mimetism Gerris remigis

Lotus – Effect

Figure 10. Email des incisives de rat. La disposition des microstructures rend l'émail particulièrement résistant. (Jodaikin et al., Journal of Ultrastructure Research, 89, 324, 1984).

Aile de Papillon

Gecko Abalone

1m2 / 1 Car

100 g cmNancy height E.Gaffet - Trans Nano Forum – 10 September 15 2014, (France)

Nano - Bio - Mimetism Lotus – Effect Revêtement Anti-Buée

Self Cleaning Window (St Gobain)


Singapore Consortium Learns from Nature to Produce New Chemical-free, Antibacteria Plastic 'Skins' Source:Nanowerk Author:n/a Researchers from Singapore's Agency for Science, Technology and Research (A*STAR) are using nanotechnology to create synthetic, chemical-free, anti-bacterial surfaces. The technique uses nanoimprint technology, which has been developed by A*STAR's Institute of Materials Research and Engineering (IMRE), to make complex nanometer-sized patterns on surfaces to mimic the texture of natural surfaces. The surfaces can reduce infections and can be used on common plastics, medical devices, lenses and ship hulls. The A*STAR technology does not use potentially harmful metal ions, nanoparticles, chemicals or UV-radiation, like most conventional methods. Dr. Low Hong Yee, IMRE's Director for Research and Innovation, says "[W]ith millions of years of experience behind her, nature has produced some of the most rugged, adaptable life forms. Who better to learn engineering from than Mother Nature?" The textured surface gives the engineered material such "natural" properties as luminescence, adhesiveness, water-proofing and anti-reflectivity. The article can be viewed online at the link below. http://www.nanowerk.com/news/newsid=19556.php Dec. 2010 E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

IX. Improving Packaging’s Security features



RFID / Hitachi Ses mensurations (0,05 x 0,05 mm2) lui ont valu le nom de « poudre »

2006 Hitachi vient de présenter la plus petite puce RFID jamais réalisée. Ses mensurations (0,05 x 0,05 mm2) lui ont valu le nom de « poudre ».

150 micromètres x 150 micromètres x 7.5 micromètres !! Cette puce est tout de même 64 fois plus petite que la plus petite puce avant elle et 9 fois plus petite que le prototype présenté par Hitachi l’année dernière. Elle contient une ROM de 128 bits permettant de stocker un numéro d’identité de 38 chiffres et peut être facilement intégrée dans une feuille de papier. Pour rappel, une puce RFID (Radio Frequency Identification) permet une identification automatique du contenu qu’elle transporte. Les puces RFID peuvent contenir toute sorte d’information et se trouvent sur de moult supports comme sur un passeport aux étiquettes de produits vendus en supermarché en passant par des billets de concert. L’apparition de « poudre » de RFID permet de faciliter leur intégration sur de plus en plus de support.

http://www.presence-pc.com/actualite/RFID-poudre-Hitachi-21816/ E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)





X. Developing Intelligent Packaging




Film that changes color with oxidation of food inside package Based on nanocrystallinesemiconductor technology Printable on paper, plastic, or metal Easily handled Color, sensitivity can be changed E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

Recovering audio from videos Researchers at MIT, Microsoft, and Adobe have developed an algorithm that can reconstruct an audio signal by analyzing minute vibrations of objects depicted in video. In one set of experiments, they were able to recover intelligible speech from the vibrations of a potato-chip bag photographed from 15 feet away through soundproof glass. In other experiments, they extracted useful audio signals from videos of aluminum foil, the surface of a glass of water, and even the leaves of a potted plant.

high-speed camera that captured 2,000 to 6,000 frames per second

http://www.kurzweilai.net/recovering-audio-fromvideos?utm_source=KurzweilAI+Daily+Newsletter&utm_campaign=34ad08a82d-UA946742-1&utm_medium=email&utm_term=0_6de721fb33-34ad08a82d-281950285 E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

XI. Edible NanoPackaging


Nano (?) Particle Film Technology

Edible Packaging

Peaches, plums, apples, cherries, apricots, pears and nectarines usually need at least two sprays of Surround after the flower petals fall off the tree and two weeks later. These timely sprays will keep worms and/or larvae such as plum curculio, oriental fruit moths, and codling moths from your fruit. Surround protects with a cover of clay that prevents insects from laying eggs on your fruit. This spray is a major celebration for gardeners who wish to grow organically delicious, tree ripened fruit in the Roseacious family. It works on Japanese Beetles, too. Talk about a safe spray!

It's actually edible!

OMRI listed crop protectant. (The Organic Materials Review Institute (OMRI) is a national nonprofit organization that determines which input products are allowed for use in organic production and processing. OMRI Listed or Approved products may be used on operations that are certified organic under the USDA National Organic Program. ) The Pest Management Regulatory Agency (PMRA) recently announced the approval of a minor use label expansion for Surround WP Crop Protectant (kaolin) for reduction in damage from leafhoppers on dry beans, potatoes, carrots, strawberries, raspberries and leafy vegetables (crop group 4, including celery, lettuce, parsley and spinach)

http://www.eatit.com/plants.php?func=view&id=261

in Canada.

http://attra.ncat.org/attra-pub/PDF/kaolin-clay-grapes.pdf

http://www.orfeteknik.com.tr/MyNewDir2/pdf/US.grape.brochure.pdf


Nanomaterials for Nanocomposites / NanoPackaging Industries Summary : Nanocomposites for NanoPackaging : Yet on the Market !! Effects of NanoFillers in Polymer NanoComposites Mechanical Properties Thermal Properties Flame Resistancre Permeability to gasses Dimensional Stability Electrical Properties Optical Properties Environmental Resistance (Dependance on the effective dispersion on the interaction with the matrix) E.Gaffet - Trans Nano Forum – 10 September 2014, Nancy (France)

Nanomaterials for Nanocomposites / NanoPackaging Industries

Questions Discussion

Thank you very much for your attention [email protected]

Tin Whisker (Peter Bush, SUNY at Buffalo)
