Vacuum deposited transparent barrier –a clear past, but do we need to protect the

future?

AlOx – a Health & Safety warning!

Steve Jackson, Camvac Limited

Vacuum deposited transparent barrier –a clear past, but do we need to protect the

future?

Steve Jackson, Camvac Limited

History of in-chamber transparent barrier coating

Challenges & Developments

History of in-chamber protective/top-coatings

Challenges & Developments

1969: AlOx coatings disclosed by DuPont, but little interest through 70’s and80’s due to:

- cost v PVdC coated films- performance due to fragile oxide coating- thus no incentive for development

1980’s: interest in developing ceramic coatings for flexible packaging foodapplications grew as legislation drove more environmentally friendlypackaging and thus away from PVdC (toxic) and Alu Foil (high energycontent).

1990’s: major drive for AlOx emerged in the Industrial and Electronics marketswith optical light emitting diodes (OLED’s) for PC’s, mobiles etc.

2000’s: growth continues in both Food and Industrial applications.

Materials: Silicon Oxide (SiOx) and Aluminium Oxide (AlOx) have been the main areas of

development.

Processes: Reactive evaporation of Silicon Monoxide with Oxygen: originally a relatively slow

process that gave a “brown tint” to the finished product - largely died out for packagingapplications.

Electron beam evaporation of Silicon Dioxide (quartz): needs expensive anddedicated equipment and is difficult to control - largely died out for packaging applications.

PECVD of organosilanes: developed to an industrial scale and produces a coating withgood resistance to flexing and elongation. However, organosilanes are expensive andtoxic/inflammable - largely died out for packaging applications.

Electron beam evaporation of Aluminium Oxide: low raw material cost but requiresexpensive and dedicated equipment so little used for packaging applications.

Plasma enhanced reactive evaporation of aluminium with oxygen: low raw materialcost, high process speed and relatively low cost non dedicated equipment, thus being thecurrent preferred process for packaging applications.

COATING ROUTE EQUIPMENT COST MATERIAL

COST PROCESS

COST Al2O3 REACTIVE EVAPORATION LOW LOW LOW

Al2O3 ELECTRON BEAM EVAPORATION MODERATE LOW LOW

SiOx PECVD HIGH MODERATE MODERATE

SiOx ELECTRON BEAM EVAPORATION MODERATE LOW LOW

SiOx REACTIVE EVAPORATION LOW HIGH MODERATE

SiOx/Al2O3 ELECTRON BEAM EVAPORATION MODERATE LOW LOW

DLC PECVD HIGH? LOW? MODERATE?

Production Routes for Transparent Barrier Films - Costs

COATING

ROUTE

EQUIPMENT

COST

MATERIAL

COST

PROCESS

COST

Al2O3

REACTIVE EVAPORATION

LOW

LOW

LOW

Al2O3

ELECTRON BEAM EVAPORATION

MODERATE

LOW

LOW

SiOx

PECVD

HIGH

MODERATE

MODERATE

SiOx

ELECTRON BEAM EVAPORATION

MODERATE

LOW

LOW

SiOx

REACTIVE EVAPORATION

LOW

HIGH

MODERATE

SiOx/Al2O3

ELECTRON BEAM EVAPORATION

MODERATE

LOW

LOW

DLC

PECVD

HIGH?

LOW?

MODERATE?

Camvac developed the first European barrier metallised pack in 1975 (Nestle potatoflake). Aluminium is a highly reactive metal which oxidises rapidly if exposed to oxygen orwater vapour, thus it became obvious that the barrier of metallised film was not due to thealuminium layer solely, but to the thin layer of AlOx on the surface.

A number of process routes to develop an AlOx coated film were examined in the earlydays

- electron beam evaporation- hydrolysis of aluminium metallised film using steam- oxidisation of aluminium metallised film using hydrogen peroxide- anodisation of aluminium metallised film- reactive evaporation of aluminium with oxygen

Surprisingly at the time but the last option gave the most encouraging results, althoughinitially barrier was inconsistent – an issue that was latterly improved by using a slightexcess of oxygen.

Further development showed that if stoichiometric quantities of aluminium and oxygenwere used then a product with good oxygen and moisture barrier and good adhesioncould be produced.

Late 80’s:- reaction of aluminium with oxygen generated a plasma, which improved

oxide adhesion and resistance to barrier loss on flexing/elongation.

- further improvements were later achieved by using an additional plasmagenerator – this process was patented.

- further development work showed that if too much oxygen was introducedthen barrier was affected and, if too much aluminium was used, then theproduct had a grey tinge.

- significant work in improving this recipe lead to us using slightly morealuminium (controlled via OD), this lead to a “greyish” tinge ex metalliserbut this faded back into the correct OD spec over a short period – again,this process was patented.

Early 90’s:- the EU recognised that it had to help European producers develop

technologies otherwise the market would depend heavily on Japan fortransparent barrier technology.

- thus Camvac, Hoechst and the University of Durham was awarded a threeyear Brite-Euram grant to help with the development of the technology.

- this lead to full width (2200mm/87”) process development.

- the mechanism for barrier loss was also heavily researched and found thatalthough some of the oxygen barrier was lost upon elongation/flexing, it“recovered” due to the “swelling” of the oxide layer by moisture.

- details of the Camclear® process was disclosed in a paper presented atSVC by Roger Kelly.

AlOx developments:

- Camclear® O – OTR

- Camclear® M - WVTR

- Camclear® XL - extra light (combined with plasma treatment)

- Camclear® - “convertibility”

PLASMA PRE-TREATMENT

O2

FROM UW

WCR

OD METER

OXYGEN FLOW VALVE

OXIDE DEPOSITION

FEEDBACK LOOP

TO RW

WINDING ZONE / METALLISATION ZONE SEPARATION

OTR

& W

VTR

OTR - 23/50 WVTR - 38/90

EU NA

OTR 3.0 0.19

WVTR 2.0 0.13

0.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.0

Camclear®

Chlorine free barrier coating

Excellent clarity and haze values

High oxygen and moisture barrier

Generally lower cost than alternatives

Barrier independent of polyester gauge

Lower gauge than PVdC therefore increasing machine efficiencies and area cost

High surface tension thus printable

Sterilisable (depends on conditions)

Pasteurisable

Microwaveable

Metal detector transparent

Excellent elongation with Camclear® - 4%

Toppan

Dai Nippon

Ultimet

Amcor - Ceramis

Uflex

Camvac

JBF

Machinery suppliers

Vacuum deposited transparent barrier –a clear past, but do we need to protect

the future?

So, after:

- c. 25 years of production- X ‘000 tonnes of external sales- X ‘000 tonnes of internal lamination- numerous external converters experiences- etc. etc.

• There is still undoubtedly a perception and a fear that the AlOx surfacecan be damaged during conversion.

• And maybe also a desire for higher barrier.

1990’s: Initial trials conducted with Catalina Coatings, Sigma Technologies andGalileo (EB curing).

2000’s: Ideas/discussions/thoughts etc.“Look-see” at a machinery manufacturer.

Initial investigations with the late Bernard Henry at Oxford University (EB polymerisation).

Regular trials at Oxford University - main obstacle being adhesion.

Breakthrough on adhesion.

Started work with John Topping of MFN Technologies (plasma polymerisation).Breakthrough with high energy curing.Installed pilot machine at Camvac.

Commissioning of new pilot line.Improving unit design.Breakthrough on distributing the “coating” and on adhesion.

2010’s: Continual design and process improvements and refinements

Scaled up to 2200mm/87”

Achieved very high barriers

Refining wide width process (v original pilot scale)

Pilot machine working on variants

Variants scaled up to wide width

Breakthrough on delivery system

Customer trials

FCA & FDA compliance

In line thickness monitoring

New pumps and injector designs

Coating distribution:resolved with injection designnozzle designinternal design of boiler & slot gap

Thickness measurement:spectral reflectometry – existing system couldn’t measure our coating levels, thus work needed to write specific software and develop an in-line system.

Barrier measurement:initially out sourced testing as our equipment not sensitive enough.new test procedures introduced to record OTR barriers down to 0.005 cm3/m2/day. new test equipment being designed.

During the development stages three key strands were followed:

Planarising Layers:Camplus Extra® : – Al Barrier Camclear Extra® : – AlOx Barrier

Polymer Multi-layers (PML’s):Camquest® – Al Barrier

Protective Top Coats:Camshield® M – Al Barrier Camshield® T – AlOx Barrier

Monomer deposited onto moving substrate (typically a polymer web).

Monomer plasma polymerised and cured.

In line barrier layers added either pre and/or post IVC coating.

IVC Delivery Unit

Plasma Curing

Chamber Wall

Moving Web

Basic Process Organic monomer (typically an acrylate) is fed into delivery unit.

Flash vaporisation of monomer at ~250 OC.

WCR

OD METER

OXYGEN FLOW VALVE

OXIDE DEPOSITION

FEEDBACK LOOP

PLASMA CURING

ALTERNATIVE POSITION FOR OD METER

TO RW

ORGANIC COATING DELIVERY

WINDING ZONE / METALLISATION ZONE SEPARATION

O2

PLASMA PRE-TREATMENT

FROM UW

OTR

& W

VTR

OTR - 23/50 WVTR - 38/90

EU NA

OTR 1.5 0.1

WVTR 1.5 0.1

0.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.0

Camshield® T

DCM / Knowfort

Sigma Technologies

Celplast

UFlex

Camvac

Others.....??

http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=YIcmy58GLbv18M&tbnid=npIbSBYO6px4SM:&ved=0CAgQjRwwAA&url=http://willyfood.com/retort.htm&ei=QUpEUruFLIGO0AXdm4DgCg&psig=AFQjCNG2xjhAHeOF5gRIlo8YV0x5h1G-qQ&ust=1380293569767134http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=YIcmy58GLbv18M&tbnid=npIbSBYO6px4SM:&ved=0CAgQjRwwAA&url=http://willyfood.com/retort.htm&ei=QUpEUruFLIGO0AXdm4DgCg&psig=AFQjCNG2xjhAHeOF5gRIlo8YV0x5h1G-qQ&ust=1380293569767134http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=gH3Pn5Rgnk5EzM&tbnid=Lma4QlhCgM9PqM:&ved=0CAgQjRwwAA&url=http://www.plumdistrict.com/deals/nurturme-27-for-two-18-count-variety-packs-of-organic-baby-toddler-food-plus-one--AnCKnq&ei=qEpEUqPVD8Ow0QWGuIGwCg&psig=AFQjCNHzJUbq5BIlhr3osxV0rarByoeHDA&ust=1380293672309232http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=gH3Pn5Rgnk5EzM&tbnid=Lma4QlhCgM9PqM:&ved=0CAgQjRwwAA&url=http://www.plumdistrict.com/deals/nurturme-27-for-two-18-count-variety-packs-of-organic-baby-toddler-food-plus-one--AnCKnq&ei=qEpEUqPVD8Ow0QWGuIGwCg&psig=AFQjCNHzJUbq5BIlhr3osxV0rarByoeHDA&ust=1380293672309232http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=vNpM3GgFgfYY9M&tbnid=jJBUWtJUpI-vEM:&ved=0CAgQjRwwAA&url=http://www.plasticstoday.com/articles/Is-plastic-packaging-the-silent-hero-to-the-global-food-waste-problem0313201301&ei=1EpEUsCiC4GV0AXC5IH4Cw&psig=AFQjCNEE5E1zGFN_5rqm-lk40eCAlBZyBg&ust=1380293716232835http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=vNpM3GgFgfYY9M&tbnid=jJBUWtJUpI-vEM:&ved=0CAgQjRwwAA&url=http://www.plasticstoday.com/articles/Is-plastic-packaging-the-silent-hero-to-the-global-food-waste-problem0313201301&ei=1EpEUsCiC4GV0AXC5IH4Cw&psig=AFQjCNEE5E1zGFN_5rqm-lk40eCAlBZyBg&ust=1380293716232835

http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=q43JdQ6tIqNP9M&tbnid=xsI-xtnDJq8GaM:&ved=0CAgQjRwwAA&url=http://www.isuppli.com/Photovoltaics/Pages/Products.aspx&ei=NEhEUuXPCMbN0QW2mYD4Cg&psig=AFQjCNF1Fh6eQIpT9Y5F7VvGaEeCYzXEUA&ust=1380293044189206http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=q43JdQ6tIqNP9M&tbnid=xsI-xtnDJq8GaM:&ved=0CAgQjRwwAA&url=http://www.isuppli.com/Photovoltaics/Pages/Products.aspx&ei=NEhEUuXPCMbN0QW2mYD4Cg&psig=AFQjCNF1Fh6eQIpT9Y5F7VvGaEeCYzXEUA&ust=1380293044189206http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=RGmco3v6nFI-YM&tbnid=0UC5tH7q5uzx8M:&ved=0CAgQjRwwAA&url=http://electronics.howstuffworks.com/oled.htm&ei=kkhEUpylM-eb1AXizoCICw&psig=AFQjCNE11LHPT3_xJZlzphgJdDq69G22xQ&ust=1380293138892509http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=RGmco3v6nFI-YM&tbnid=0UC5tH7q5uzx8M:&ved=0CAgQjRwwAA&url=http://electronics.howstuffworks.com/oled.htm&ei=kkhEUpylM-eb1AXizoCICw&psig=AFQjCNE11LHPT3_xJZlzphgJdDq69G22xQ&ust=1380293138892509http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=mqAIK0S0rXl6RM&tbnid=tbtnyH-3upEWVM:&ved=0CAgQjRwwAA&url=http://www.mardenedwards.com/medical-packaging&ei=ukhEUpbJFqmp0QWi8YCoCw&psig=AFQjCNGxFVyDj3gb4GKZk0z-eBxSoT_5yA&ust=1380293178419417http://www.google.co.uk/url?sa=i&source=images&cd=&cad=rja&docid=mqAIK0S0rXl6RM&tbnid=tbtnyH-3upEWVM:&ved=0CAgQjRwwAA&url=http://www.mardenedwards.com/medical-packaging&ei=ukhEUpbJFqmp0QWi8YCoCw&psig=AFQjCNGxFVyDj3gb4GKZk0z-eBxSoT_5yA&ust=1380293178419417

http://www.google.co.uk/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=blK3ivBQJVoN0M&tbnid=glJgbRkejJd2tM:&ved=0CAUQjRw&url=http://www.123rf.com/photo_5770450_sexy-chocolate-woman-wrapped-into-foil-eat-chocolate-isolated-on-white.html&ei=Tj1EUtDsAsmMtAbPr4GICA&bvm=bv.53217764,d.bGE&psig=AFQjCNH8GwgJ4M18g-m1tAu2AEvQXw1dbg&ust=1380290212875494http://www.google.co.uk/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&docid=blK3ivBQJVoN0M&tbnid=glJgbRkejJd2tM:&ved=0CAUQjRw&url=http://www.123rf.com/photo_5770450_sexy-chocolate-woman-wrapped-into-foil-eat-chocolate-isolated-on-white.html&ei=Tj1EUtDsAsmMtAbPr4GICA&bvm=bv.53217764,d.bGE&psig=AFQjCNH8GwgJ4M18g-m1tAu2AEvQXw1dbg&ust=1380290212875494

Oxide coated films have been in production since the early 90’s.

They have demonstrated strong growth - mainly fresh and chilled food applications, buthave also been used for dry food, liquid and some industrial applications.

They have been successfully converted (printing, slitting and lamination) by numerouscompanies over the years, with good OTR and WVTR being maintained, thusdemonstrating the ability to survive flexing/elongation.

However, top/protective coated oxide films are probably an inevitable next stage formany applications.

Off-line top/protective coatings are available but by nature are probably not ideal, norcost competitive.

In-chamber coatings have been/are being developed by a select few companies.

They offer far more versatility than off-line coatings.

They offer protection for the oxide (and metallised) layer.

They provide even higher OTR and WVTR.

Indirect food contact can be/has been achieved.

However, the technology is still new and development is ongoing.

AlOx – a Health & Safety warning!

Steve Jackson, Camvac Limited

The Fire Triangle

Fuel for the fire to burn

Removal of any one of the sides of the Fire Triangle will extinguish the fire.

For a fire to thrive and spread, it requires 3 things:

Air for the fire to breatheHeat for the fire to continue burning

Heat

The Fire Triangle

Shale Chemistry - What is shale?

• Shale is the evaporated aluminium that does notdeposit on the web.

• It is a rich source of aluminium, but the surface quicklyoxidises to prevent reaction of the core of the shale.

• AlOx shale has aluminium and oxygen embeddedwithin the structure of aluminium oxide.

• Trapped aluminium and oxygen want to react with eachother and do so slowly as they are controlled by thebarrier of the oxide.

Al Al

Al AlAl

AlAl Al

Al AlAl

Al

Al Al

AlAl

Al

Al Al

Al

Al

Al

Al Al

AlAl

Al

Al Al

AlAl

Al

Al Al

Al Al

Al

Al Al

Al

Al

Al

Al Al

AlAl Al

Al

Al Al

Al

Al Al

Al

Al

AlAlAl

AlAl

Al

AlAlAl

AlAlAl

AlAl

Al

AlAlAl

AlAl

O OO O

O OO O

O OO O

Al Shale

AlOx Shale

Shale Chemistry - Aluminium oxidationThe Fire TriangleShale can ignite – what is shale?

Shale Chemistry - Why Shale Fires?

• Aluminium reacts with oxygen (AlOx production) exothermically

4 Al 2 Al2O3+ => +

3 O2 HEAT

• Aluminium also reacts with water exothermically

2 Al Al2O3+ => +

3 H2O 3 H2+

HEAT

• If both occur and produce enough heat, the free hydrogen will ignite explosively and if left unchecked, the reaction will self-sustain and cannot be extinguished.

AlAl

Al

Al

O O

Al

Al

Shale Chemistry - What is shale?Shale Chemistry - Aluminium oxidationThe Fire TriangleWhy shale fires?

Shale Chemistry - Shale Fire Hazards

• There are two main hazards with a shale fire:

– Flames indicating that the hydrogen has ignited.

– If in a contained vessel, this can have explosive consequences and hasblown drum lids into our neighbours yard!

– Heat from aluminium fire: the hydrogen ignition can speed up the ignition ofthe aluminium fire itself and this will burn at >1000°C.

Shale Chemistry - Why Shale Fires?Shale Chemistry - What is shale?Shale Chemistry - Aluminium oxidationThe Fire TriangleShale fire hazards

Shale Chemistry - Control Measures

• Shale Alarms

– Having conducted experiments on the speed of ignition of a shale fire, ithas been determined that a difference of only a few degrees fromambient indicates an ignition could be imminent.

– These give operators an early warning to get the bins outside beforethey catch fire.

21

21

Sensor A readout

Sensor B readout

Alarm

Sensor A

To sensor B

Shale Chemistry - Shale Fire HazardsShale Chemistry - Why Shale Fires?Shale Chemistry - What is shale?Shale Chemistry - Aluminium oxidationThe Fire TriangleControl measures

Shale Chemistry - Control Measures

• Bin Lids

– These work on the same principle as cigaretteash trays and circulate the vapours to smotherthemselves.

– The lids suppress the flames given off by thehydrogen burning, but allow any explosivepressure to dissipate safely.

– The lids have been designed to be in place at alltimes other than dispensing into the collectiondrums: shale can be swept up and disposed ofthrough the lid and the gap is large enough toallow the extinguisher wand to penetrate.

Shale Chemistry - Control MeasuresShale Chemistry - Shale Fire HazardsShale Chemistry - Why Shale Fires?Shale Chemistry - What is shale?Shale Chemistry - Aluminium oxidationThe Fire TriangleControl measures

Shale Chemistry - Control Measures

• Fire Extinguishers

– Class D Powder extinguisher with low pressure wand.

– Suppresses the flames, in order to take bin outside.Do not use the extinguisher and leave the fire unattended in the building as it WILL REIGNITE!

• SOP

– Please read and follow the procedure instructionsas they are the safest way to deal with the Shale.

• House Keeping

– Camclear (AlOx) shale is most dangerous when fresh and if swept up in a pile as this allows the heat from the oxidation reaction to be contained and build up

– Although it may sound counter intuitive part of the SOP instructs the operator to leave Camclear (AlOx) shale on the floor for 30mins before sweeping up. This time allows the shale to slowly react with atmospheric oxygen and moisture without heat building up in one place risking a fire.

Shale Chemistry - Control MeasuresShale Chemistry - Control MeasuresShale Chemistry - Shale Fire HazardsShale Chemistry - Why Shale Fires?Shale Chemistry - What is shale?Shale Chemistry - Aluminium oxidationThe Fire TriangleControl measures

Shale Chemistry - Control Measures

• Containment

– As the shale is collected, it is taken outside and stored for a minimum of 2 weeks in a 30ft container.

– The time period should be more than enough to allow the AlOx shale to react and become as safe as standard shale.

– The drum lids are left loose until the end of the time period and holes are drilled in the tops of the drums to allow any hydrogen to escape.

– Should anything explode, the container will protect anyone in the vicinity.

– Note: The container doors are left open to ensure no build up of explosive hydrogen in the container.

Shale Chemistry - Control MeasuresShale Chemistry - Control MeasuresShale Chemistry - Control MeasuresShale Chemistry - Shale Fire HazardsShale Chemistry - Why Shale Fires?Shale Chemistry - What is shale?Shale Chemistry - Aluminium oxidationShale Chemistry - Control MeasuresShale Chemistry - Control MeasuresShale Chemistry - Control MeasuresShale Chemistry - Shale Fire HazardsShale Chemistry - Why Shale Fires?Shale Chemistry - What is shale?Shale Chemistry - Aluminium oxidationThe Fire TriangleControl measures

Vacuum deposited transparent barrier –a clear past, but do we need to protect the

future?

AlOx – a Health & Safety perspective

Steve Jackson, Camvac Limited

Vacuum deposited transparent barrier – �a clear past, but do we need to protect the future?��AlOx – a Health & Safety warning! Vacuum deposited transparent barrier – �a clear past, but do we need to protect the future?��Slide Number 3Slide Number 4Slide Number 5Slide Number 6Slide Number 7Slide Number 8Slide Number 9Slide Number 10Slide Number 11Slide Number 12Slide Number 13Slide Number 14Slide Number 15Vacuum deposited transparent barrier – �a clear past, but do we need to protect the future?Slide Number 17Slide Number 18Slide Number 19Slide Number 20Slide Number 21Slide Number 22Slide Number 23Slide Number 24Slide Number 25Slide Number 26Slide Number 27Slide Number 28Slide Number 29Slide Number 30Slide Number 31Slide Number 32��AlOx – a Health & Safety warning! The Fire TriangleShale Chemistry - What is shale?Shale Chemistry - Why Shale Fires?Shale Chemistry - Shale Fire HazardsShale Chemistry - Control MeasuresShale Chemistry - Control MeasuresShale Chemistry - Control MeasuresShale Chemistry - Control MeasuresSlide Number 42Vacuum deposited transparent barrier – �a clear past, but do we need to protect the future?��AlOx – a Health & Safety perspective