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Packaging Innovation

through Nanotechnology

Professor Barry Park

GBP Consulting Ltd

Food Matters Live - 20th November 2014

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Focus of the talk is to:-

provide an overview of at least some of the

applications of nanotechnology in packaging

and

stimulate thinking about how and where

nanotechnology could be further used in

packaging


Nanotechnology is the technology of the

very small

1 nanometre = 1 billionth of a metre

ie 10-9

m

To put this size into context: - the diameter of a red blood cell is c.7000nm - a sheet of paper is about 100,000nm thick - the average thickness of a human hair is of the order of 80,000 to 100,000nm - human nails grow at a rate of 1 to 10nm per second

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On 18th October 2011, the EC adopted the following

recommendation on the definition of a nanomaterial

According to the Recommendation, a nanomaterial means:-

A natural, incidental or manufactured material containing particles, in an

unbound state or as an aggregate or as an agglomerate and where, for 50

% or more of the particles in the number size distribution, one or more

external dimensions is in the size range 1nm - 100nm.

In specific cases and where warranted by concerns for the environment,

health, safety or competitiveness the number size distribution threshold of

50 % may be replaced by a threshold between 1 and 50 %.

By derogation from the above, fullerenes, graphene flakes and single wall

carbon nanotubes with one or more external dimensions below 1nm

should be considered as nanomaterials

This definition will be re-evaluated by December 2014

EC Recommendation on the

definition of a nanomaterial GBP Consulting Ltd


So…… Nanomaterials are (generally) those materials

that have at least one dimension of size in the

range 1nm to 100nm and they can be considered

under the following three headings:

Natural

Anthropogenic

Engineered

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Natural nanomaterials are created

independently of man, and include a wide

range of materials such as sea salt resulting

from the evaporation of water from sea

spray, soil dust and volcanic dust

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Anthropogenic nanomaterials are

created as a result of action by man with the

main example of this type of nanomaterial

being soot produced from the combustion of

fossil fuels. Other anthropogenic

nanomaterials include welding fume

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Normal room

15,000 per cm3

Forest

50,000 per cm3

Urban street

100,000 per cm3

LIVING WITH NANOPARTICLES

Background GBP Consulting Ltd


Engineered nanomaterials have been

designed and manufactured specifically by

man

These have been synthesised for a specific

purpose and can be found in several

different shapes including platelet-like, wire-

like and spheroidal-like, ie they are of one,

two or three dimensions respectively

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It is these Engineered Nanomaterials

that are of particular commercial interest…..

Engineered Nanoparticles can be

produced via a ‘top down’ or a

‘bottom up’ approach

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Top down • Larger particles are broken down into nano-sized

material

• Processes include milling and homogenisation

Bottom up • Manufacturing processes include self assembly,

crystallisation, layer-by-layer deposition, solvent

extraction/evaporation

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Why nanoparticles?

• Nanoparticles may exhibit completely different

optical, electronic and chemical behaviour

compared to bulk materials

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Why nanoparticles?




• Nanoparticles may have unique properties

because of their very large surface area per unit

weight

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Why nanoparticles?






weight

• They can be coated with various substances

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Why nanoparticles?






weight


• They can be incorporated into many different

carriers, both liquid and solid

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Why nanoparticles?

• Nanoparticles may exhibit completely different optical,

electronic and chemical behaviour compared to bulk materials

• Nanoparticles may have unique properties because of their

very large surface area per unit weight


• They can be incorporated into many different carriers, both

liquid and solid

Products containing nanoparticles have been

developed for use in many different applications in

many different market sectors

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Nanoparticles

Energy Electronics Coatings

Sport

Cosmetics

Transport

Packaging

Medical Food

Engineering

Clothing

ICT

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Transport - carbon black in tyres

- reinforcement

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- reinforcement

Sport - nanoclays in tennis balls

- barrier properties

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- reinforcement



Medical - silver in wound dressings

- antimicrobial properties

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- reinforcement





Cosmetics - titanium dioxide and zinc oxide in sunscreens

- UV protection

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- reinforcement






- UV protection

Electronics - copper inks

- printed electronics

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- reinforcement






- UV protection

Electronics - copper inks

- printed electronics

Can properties that have been used

successfully in these and other

applications be used in packaging?

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Nanoparticles

Energy Electronics Coatings

Sport

Cosmetics

Transport

Packaging

Medical Food

Engineering

Clothing

ICT

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Leading the use of nanomaterials in

packaging are food and pharma packaging

Why is this?


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In the food arena, there is a need for

longer shelf life and monitoring of food

safety and quality to minimise waste


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In the food arena, there is a need for

longer shelf life and monitoring of food

safety and quality to minimise waste

In the pharma arena, there is a growing

demand for improved packaging

materials that provide protection from

the environment as new medicines

become more complex and less stable


So, nanotechnology is already a major

and growing component in food and

beverage and in pharma packaging

Where food and pharma are

going, others will follow

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Report from iRAP in 2009 entitled “Nano-

enabled Packaging for the Food and Beverage

Industry – a Global Technology, Industry and

Market Analysis”

Highlights

• Total nano-enabled food and beverage packaging

market in 2008 was estimated as $4.13B

• This was expected to grow in 2009 to $4.21B and

to $7.4B by 2014

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Report from iRAP in 2009 entitled “Nano-

Enabled Packaging for the Pharmaceutical

Industry – A Global Technology, Industry and

Market Analysis”

Highlights

• The total market for nano-enabled packaging for

pharma was estimated as $3.8B in 2009

• This was expected to grow to $8.1B by 2014

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GLOBAL NANO PACKAGING MARKET 2013-2023 - Opportunities for Nanotechnology

• The availability of nano packaging can provide some

differentiation as it constitutes a unique, new form of

packaging

• Visiongain expected the global nano packaging

market to attain $20B in 2013

“The report provides an analytical overview with detailed sales projections and analysis of the market, the

competitors, and the commercial drivers and restraints”


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Nanocomposites

Active Materials

Intelligent or Smart Packaging


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Nanocomposites


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Nanocomposites incorporating metal or metal

oxide nanoparticles have been developed for:

• Barrier properties

• Mechanical strength

• Temperature and moisture stability

• Durability


Nanocomposites

Nanoclays based on Montmorillonite account

for the largest use of nanomaterials in

packaging

• Nanoclays are in the form of platelets, c.1nm thick with a

surface area of c.1000nm by c.1000nm

• The structure containing nanoclay platelets leads to gases

following a tortuous path slowing their transmission and

significantly extending the shelf life of stored food and

beverages

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1nm

1μm

e.g. oxygen clay platelets


Nanoclays based on Montmorillonite account

for the largest use of nanomaterials in

packaging

• Thus, for a carbonated beverage such as beer, a barrier to

ingress of oxygen and loss of carbon dioxide is achieved

• Mechanical properties are also enhanced even at lower

weight

• Nanoclays are used at levels of 2-5% in PE, PP, PA, PS,

PU, PET plus natural polymers such as PLA

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Nanomer® Nanoclays

Supplied as microfine powders ready for use directly into the

resin system

They are available for an expanding number of resin matrices

including but not limited to:-

Polyamides

Epoxies

Polyurethanes

EPDM

Engineering Resins


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Durethan® KU2-2601 • KU2-2601 is a nylon 6 nanocomposite containing

clay for films and paper coating

• It is designed for medium barrier applications

requiring excellent clarity


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Carbonated Soft Drink and Carbonated Water

Packaging

Aegis® CSDE barrier nylon resin … is a passive (non-scavenging) nylon formulated for the

high carbon dioxide retention demands of carbonated soft

drink and carbonated water applications

… provides an excellent barrier to carbon dioxide while

delivering glass-like clarity and recyclability

… is well suited to the co-injection process, because the

recommended processing temperature of Aegis® CSDE

barrier nylon resin is similar to that of PET


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Beverage packaging - Project funded by

SABMiller at CRANN in Ireland starting in 2012

• Scientists at CRANN, the nanoscience institute based at

Trinity College Dublin, have partnered with world-leading

brewing company SABMiller on a project starting in 2012 to

increase the shelf life of bottled beer in plastic bottles

• The approach is exfoliation of nano-sheets of boron nitride,

mixing them with plastic, resulting in a material that is extremely impervious to gas molecules


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While beverage cans are by far the largest

aluminium packaging application by weight,

accounting for nearly 90% of all aluminium

use in packaging, laminates comprising

aluminium as one of the layers are used

extensively, but with minimal amount of

aluminium per package


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Laminates

A 40-50nm layer of aluminium nanoparticles

applied directly to plastic film can replace the

need for thicker aluminium foil laminates

The nanoparticles are commonly applied by vapour deposition

They provide a barrier, especially to oxygen and

carbon dioxide and permit the downgrading of the

film thickness, limit disposal impact and save cost


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The InnoPET Plasmax 12D barrier coating system

provides the optimum barrier characteristics of a glass

bottle with the weight advantages of a PET bottle

In this process, the inside of a PET bottle is coated

with an ultra-thin protective layer of silica


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As well as high-quality fruit juice, Plasmax-coated

PET bottles are also used for wine, beer, soft drinks,

ketchup, sauces and other liquid foodstuffs

The coating created by Plasmax+ is more flexible and

more resistant with all applications and is generally

used for products with a pH of more than 4.5


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Appearance

• Colour changes are another feature

of nanotechnology

• The colour in butterfly wings is not due to

pigments, but results from the light bouncing

off nano-layers causing us to see bright colours

• Mother of pearl shells exploit similar structures

Such effects have been copied on packaging

including perfume bottles that have a mother

of pearl effect created by putting two nano-

scale layers on the inside of the glass bottle


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Active Packaging


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Active Packaging is sensing followed

by manipulation of the environment in

the package to better retain food or

other content microbiological or

biochemical quality


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Antimicrobials

UV absorbers

Oxygen scavenging materials


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Silver is one of the oldest known

antimicrobials and has been used in storage

vessels and in the treatment of wounds for

centuries

Nanoparticulate silver has gained wide

acceptance as an antimicrobial agent and has

been incorporated in food packaging for some

time and also immobilised onto the surface of

packaging



Based on the antimicrobial action of

nanoparticulate silver, food contact materials

have been developed that are claimed to

preserve the food longer by inhibiting the

growth of microorganisms

Product examples containing nanoparticulate

silver include food packaging and food storage

containers



However….

• The antimicrobial properties of nano zinc

oxide and magnesium oxide have also been

exploited

• Compared to nanosilver, the nanoparticles of

zinc oxide and magnesium oxide are

expected to provide more affordable and

safe food packaging solutions in the future


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• Nanoparticulate titanium dioxide and zinc

oxide deliver superior UV protection and

significantly improved transparency

compared to traditional larger particle metal

oxide powders

• These nanoparticulate UV absorbers protect

both the packaging and the contents from

the harmful effects of UV light, giving

consumer products greater shelf appeal and

longer shelf life

UV Protection


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Control

After

24hrs in

UV

cabinet

Protected

with

Solasorb

In shrink

sleeve

UV colour fade protection of commercial sports drink

Solasorb 100F and 200F

from Croda based on

titanium dioxide and zinc

oxide respectively have

food contact approval


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• SCHOTT has brought coated products to market

for packaging solutions that are needed for drugs

that contain potent bio molecules like proteins

• Plasma Impulse Chemical Vapour Deposition

(PICVD) technology uses a pulsed plasma in

combination with oxygen and a volatile precursor

gas to apply an oxide coating inside the container

Pharma Packaging


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• Plasma Impulse Chemical Vapour Deposition

(PICVD) technology offers advantages for the

deposition of sub-micron functional layers on 3-

dimensional substrates, especially the interior

deposition of hollow bodies

• The PICVD coating technology makes it possible to

improve the properties of plastic materials as well as

glass with different container types cartridges,

syringes and vials able to be coated

Pharma Packaging


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• The removal of oxygen from packaging retains the

natural colour and preserves nutritive value of food

• The two most common substances used as oxygen

scavenging materials within packaging are iron

powder and ascorbic acid delivered in sachets

• Spain-based NanoBioMatters have introduced O2

Block® – a new family of oxygen scavengers it

claims simplifies and reduces the cost of

scavenging technology for applications in food and

pharmaceutical packaging


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O2Block® by NanoBioMatters is an oxygen

scavenging additive for polymer-based materials

• The O2Block® technology is based on surface-

modified phyllosilicate clay that is functionalized

with active iron to create a naturally sourced and

highly efficient oxygen scavenging product for

maximum shelf life in barrier packaging

• O2 Block® is suitable for use with packaging

materials based on PE, PP and PET, as well as

PLA, at loading levels of 1-10%


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Juice, Tea, and Condiment Packaging with Aegis®

HFX Barrier Nylon Resin

• Aegis® HFX is an oxygen scavenging polyamide composition

formulated specifically containing montmorillonite nanoclay plus

proprietary oxygen scavenger for use in high performance

packaging applications where high gas barrier is required

• Aegis® HFX offers high oxygen barrier, even at high humidity,

outstanding delamination resistance and whitening resistance,

clarity and easy processing (particularly in the PET co-injection

stretch blow moulding process)


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Beer & FAB Packaging with Aegis® OXCE Barrier

Nylon Resin

• Aegis® OXCE barrier nylon resin is an oxygen-scavenging nylon

formulated containing montmorillonite nanoclay plus proprietary

oxygen scavenger for the high-oxygen barrier demands of plastic

beer and flavoured alcoholic beverage (FAB) bottles

• Multilayer polyethylene terephthalate (PET) bottles made with

Aegis® OXCE barrier nylon resin demonstrate near zero oxygen

transmission rates for extended periods of time, depending on

barrier loading.


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• Ethylene accelerates the respiration rate and

subsequent senescence of fruit, vegetables and

flowers

• There are a number of ethylene removal technologies

- catalysts eg platinum, titanium dioxide, potassium

permanganate

- sorbents eg activated carbon, clays, zeolites

• Studies are ongoing on all of these materials in nano

form with delivery of the material key to its action

Ethylene Scavengers


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• Intelligent packaging can be used to address issues

with counterfeit food and pharma packaging

• Intelligent Packaging may incorporate nanosensors

to monitor the condition of the food or other contents

• Key factor to general use of Intelligent packaging

is reducing the cost of sensors.

• Price can be very low if the sensor is printed

directly onto the inside of the package using the

same inkjet technology that is used to print the

label on the outside of the package



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• Intelligent packaging is growing at a faster rate than

active packaging

• Customers prefer traceable packaging, since it offers

information such as expiry date and best use period

and potentially also the present state of the contents

• Intelligent packaging is mostly used for fruits and

vegetables, meat products, and beverages



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• Time Temperature Indicators have been proposed

incorporating gold or silver nanorods with a simple

colour indicating freshness

• Barcodes and RFID tags based on nanotechnology

are used in pharma and food and beverage

packaging



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Radio Frequency IDentification

• RFID tags consist of a silicon microchip providing

memory for data and a coupling element which acts

as an antenna to access this information

• Nanotechnology can bring additional functionality to

the antenna

• Key to their future success will be reducing the unit

cost to compete with barcodes


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• Ink jet printing of antenna can provide a low cost process to

deliver conductive inks

• These conductive inks can be based on silver, but

copper is lower cost and Intrinsiq Materials have

developed a nanocopper based ink, Intrinsiq CI,

that can be applied in RFID antennas

• Vorbeck Materials are offering the first graphene-

based conductive inks, Vor-ink™, to be used for

imprinting RFID antennas on substrates such that

each tag can be printed for a fraction of a cent

RFID

Radio Frequency IDentification


So, lots of current and future applications

of nanotechnology in packaging, but what

about safety of this technology?

Safety is an issue that is supported by

existing regulation and has to be

addressed irrespective of any new or

proposed regulation

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The safety of nanomaterials is of interest

and concern to many different groups

including the following:-

Researchers

Nanomaterial producers

Nanomaterial converters

Product users

Regulators/legislators

Insurers

Waste managers

Consumers

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All of these groups share the

common goal that engineered

nanomaterials or nanomaterial based

products should be ‘safe to

manufacture, safe to use and safe

to dispose of’

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Potential Safety Issues for nano based

packaging

• Possible migration into food and drinks or pharma

products

• Exposure to the environment after disposal of the

packaging

• Fate during recovery and recycling to make new packaging materials


So, could nanoparticles

transfer from packaging

into the contents or into

the environment?

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Studies conducted at Food and Environment

Research Agency (FERA) in UK found:-

- No detectable migration of nanoclay from PET - No detectable silver migration from PP - Lack of migration of TiN from PET also noted

On basis of modelling, it could be predicted that any detectable

migration of nanoparticles from packaging into food might take

place only in the case of very small nanoparticles – of the order

of 1nm – that are not bound in the polymer matrices

Otherwise, appreciable migration would be unlikely

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Fraunhofer Institute study showed no

evidence that nanoparticles of silver and

titanium nitride with spheric shape

incorporated at various levels into LDPE

migrated into food simulants even under

extreme test conditions

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Migration of nanoparticles to food and

beverages from nanocomposite based

packaging may therefore not be significant

However, further migration studies are

needed for different (bio)polymer

nanocomposite matrices as new product

combinations are developed

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While Regulatory Authorities debate

how to define nanoparticles and

potentially how they should be tested

and regulated, companies continue to

focus on how to take advantage of

properties of nanoparticles for

packaging applications

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But, sustainability is likely to overtake cost

as the number one purchasing decision for

packaging

Efficient solutions that consume fewer

resources, use fewer materials throughout the

supply chain and are quantified by lifecycle

analysis will become the norm


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So…

Can nanotechnology help to support the

focus on sustainability?

and

What further can be learned from the use

of nanotechnology in other applications?

These are the challenges for the future


And, finally……

Is this the earliest use of nanotechnology in drinks

packaging?

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© Trustees of the British Museum

This extraordinary cup is the only complete example of a very special

type of glass, known as dichroic, which changes colour when held up to

the light

The opaque green cup turns to a glowing translucent red when light is

shone through it. The glass contains tiny amounts of colloidal/nano

gold and silver, which give it these unusual optical properties

The Lycurgus Cup - from 4th Century AD


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Thank you!


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