Layers Which are the Most Suitable Applications. Tom Bezigian PLC Technologies Film, Sheet & Extrusion Consulting

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7-9-11 Layers Which are the Most Suitable Applications Tom Bezigian PLC Technologies Film, Sheet & Extrusion Consulting

Agenda Introduction Background/technology revisited Benefits of coextrusion Advantages of multilayer lines with example structures The next generation Alternative technologies

Introduction (Equipment) Mono-layer blown film extrusion is very well established Film manufacturing evolved from monolayer to coextrusion for many reasons Equipment developments Resin developments Process development Education Market needs Economic forces Coextrusion development began about 60 years ago UMASS-Lowell Plastics Engineering Department Mono-Layer Blown Film Lab Photo by Tom Bezigian

Alpine 5-Layer Plate Die (Adapted from the UMASS-Lowell Plastics Engineering Department Process Engineering curriculum UML) 7

Stacked Conical Mandrel Coextrusion Blown Film Die 7-Layer Taper Pack Macro Engineering Coextrusion Die for Heat Shrinkable Biax Film, Courtesy Macro Engineering 20-Oct-17 Barrier Films - Comparing Extrusion Technologies

9-Layer Concentric (Nested) Spiral Die (UML) Courtesy Battenfeld Gloucester

Blown Film Die Variation Courtesy Brampton Engineering Courtesy Battenfeld Gloucester Courtesy W+H Plate, or Pancake Die Concentric Spiral Mandrel Stacked Conical Spiral Mandrel All images courtesy Gloucester Engineering

Benefits of Coextrusion So, how did we go from one to three and five layer films to 7, 9, and 11-layer films? What is driving the market to films with more and more layers? It seems all the major manufacturers are offering 7, 9, and 11 layers machines. The big question is why? Is there a real benefit to be gained from the additional capital expenditure, or is it marketing hype?

Benefits of Packaging & Coextrusion Packaging Product protection Puncture and abuse resistance Vapor barrier Moisture barrier Grease barrier Chemical barrier Light barrier Printability Heat seal strength Heat seal initiation temperature Hot tack Machinability Coextrusion Combining incompatible polymers in one step (lamination not needed) Optimization of film structures for specific applications Improved barrier properties Reduced layer thickness of expensive resins Controlled respiration (O 2 & CO 2 transmission) Improved physical properties Improved Gelbo flex resistance (reduced flexural failures) Thinner, stronger films Improved gloss Additional attributes, such as anti-fog, anti-block, COF, two-sided color Expanded markets, i.e., competes with rigid packaging Reduced cost Use of new polymers

Benefits of Coextrusion Barrier Properties POLYMER OTR @ 20 C, 65%RH (cm 3 20μ / m 2 day atm) GAS BARRIER 27 Mol% Ethylene EVOH 0.2 44 Mol% Ethylene EVOH 1.5 PVDC 2.6 Excellent (High) PA 38 Fair PET 54 (Medium) HDPE 2300 PP 3000 PC 5000 PS 8000 LDPE 10000 EVA 18000 50,000 x Poor (Low)

Benefits of Coextrusion Toughness Using LDPE instead of EVOH as an example would require a 1 meter thick (50000 x 20µ) of LDPE to achieve the same O 2 barrier as EVOH Thinner layers are obviously less stiff than thicker layers, so improved Gelbo flex resistance is anticipated with thinner layers of stiff materials For example, polyamides can be substituted for polyester in a coex structure, allowing for a strong, tough structure with good permeability properties in a one-step blown film process For example, frozen food packaging

Benefits of Coextrusion Heat Seal Heat seal strength, heat seal initiation temperatures, and hot tack strength can be adjusted based on the performance required in the end product From: Kramer, Van den Bossche, New Solutions in Flexible Packaging, TAPPI PLACE, May 2014

1-, and 3-Layer Films These are the backbone of the blown film industry, and certainly will not disappear any time soon Monolayer lines are perfectly suited for commodity, non-barrier films Existing lines require no capital outlay 1- and 3-layer films feed into the adhesive laminating market The limitations of 1- and 3-layer films are barrier, stiffness and heat seal properties

5-Layer Films Offer more options and flexibility than 3-layer films Most typically as a barrier film with an EVOH core layer or a PA/EHOH/PA outer skin LLDPE Tie Layer EVOH Tie Layer LLDPE Cereal liner, lidding & tube stock, meat packaging, medical devices (fin or lap seal) Nylon EVOH Nylon Tie Layer Sealant Frozen food packaging (fin seal)

5-Layer Film Line 5-layer films eliminate the need for the secondary step of adhesive lamination (of simple structures) The modulii of laminated oriented PA, PP or PET films are similar ro unoriented polyamide coex blown films [6] 5 extruders in (more or less) a semicircle Big improvement over 3-layer films, but limited in performance compared to 7, 9, 11-layers Photo courtesy Hosakawa Alpine

7-Layer Films Cost reduction 7-layer structures can utilize a lower-cost LLDPE in the second layer and an expensive, high-performance metallocene LLDPE as the skin layer, which has superior hot tack and heat seal properties. [mll / LL / Tie / EVOH / Tie / LL / mll] optimizes performance and cost, and is used for milk packaging [4] Basically a cost reduction analog to the 5- layer structure previously shown. mlldpe LLDPE Tie Layer EVOH Tie Layer LLDPE mlldpe

7-Layer Films Improved Barrier/Strength Properties If improved barrier properties and toughness are required in the finished product, the following structure is applicable and can be made with a 7-layer die [LL / Tie / Nylon / EVOH / Nylon / Tie / mll] This structure is used as a lidding film with excellent barrier properties and gloss. Flexibility is controlled with thickness The metallocene PE layer can be any mpe, such as POP, etc. LLDPE Tie Layer Nylon EVOH Nylon Tie Layer mlldpe

7-Layer Films Thermoform Fill Seal Trays Substituting the mlldpe with EVA is used in a thermoformable cheese tray The point made here is that more layers offers the package designer more options Thought to be about 100 7-layer lines in use today mlldpe or POP Tie Layer Nylon EVOH Nylon Tie Layer EVA

9-Layer Films Semi-Rigid Barrier Structure 9-layer rigid, high barrier structure using cost/ performance optimized PE resins The thickness of the nylon layers control modulus Similar to the 7-layer structure except that the skin layers can be split into two to optimize cost and performance for a particular application Frozen foods, stand-up pouches, thermoform-fill-seal Approximately 50 9-layer lines are reported to be in use today mlldpe or POP LDPE/LLDPE Tie Layer Nylon EVOH Nylon Tie Layer LDPE/LLDPE mlldpe or POP

11-Layer Films 11-layer retortable, high-barrier structure using cost/performance optimized PP and copolymer PP resins Sous-vide cooking is all the rage today Sous-vide is slow cooking (up to 96 hours) at low temperatures (55-60 C) in a hermetically sealed bag 11-layers appears to give the converter & R&D specialist broad flexibility to optimize barrier, rigidity, heat seal properties, thermoformability, and cost. CoPP PP PP Tie Layer Nylon EVOH Nylon Tie Layer PP PP CoPP

11-Layer Hosakawa Alpine Coex Line (UML) 30

11-layer vs 5 layer vs monolayer Repairs become more challenging than on 11-layer lines vs 1/3/5-layer lines At some point there will be diminishing returns at which the cost, complexity, and maintenance of more extruders limits further development

The Next Generation While it is not possible to predict the future, at some point simply adding more extruders into bigger and bigger dies becomes unfeasible. Layer splitting technology is common now in flat film dies BBS Technologies has developed a nanolayer blown film die (US Patent # 8870561) True nanolayers in a 77-layer structure Photo by Tom Bezigian

Photomicrographs of nanoclay-filled mpe at 1µ, 500 nm, and 200 nm These are photos of a 77-layer polyolefin/polyamide coextrusion The benefits of this die are: Greater strength and modulus due to increased BUR capability (5:1) Improved barrier properties, which effectively halves the amount of polyamide required while retaining stiffness Photomicrographs courtesy of Alpha Marathon Extrusion, Toronto

Thank you for your attention Disclaimer: The author has no business affiliation and has received no compensation from any company or product shown in this presentation. Presented by: Thomas Bezigian, Principal Consultant PLC Technologies +1 315 382 3241 tom.bezigian@gmail.com or Thomas_Bezigian@uml.edu

Bibliography 1. US Patent 2820249, Apparatus for coating articles with multi-layer linings, Colombo Roberto, 21 JAN 1958 2. US Patent 3308508, Die, Walter Schrenk, 14 MAR 1967 3. Blown Film Training", The Dow Chemical Company 4. Rethinking Technology Innovations for High Barrier Applications", Kurt Freye, Reifenhäuser Kiefel Extrusion 5. Properties, Processing and Handling of EVAL TM EVOH Resins, Gene Medlock, AIMCAL, Oct 2014 6. "The Influence of Sealant Modulus on the Bending Stiffness of Multilayer Films", Morris & VanSant, DuPont Packaging White Paper, 2009 7. Coextrusion - The Pros and Cons of More Layers", Bill Hellmuth, Gloucester Engineering 8. Nano-layer - Micro-layer Structural Advances in Shrink Films, Schirmer et al, 2013 SPE International Polyolefins Conference, Houston, Texas, USA 9. http://plasticsengineeringblog.com/2013/01/04/new-technologies-in-stretching-and-touching/ 10. US Patent number 8870561, Layer sequence repeater module for a modular disk co-extrusion die and products thereof, Henry Schirmer, 28 OCT 2014