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Improved performance with PA6 in multilayer
barrier films
PA6 with modified rheology



Ted Brink
Application Development Extrusion



DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Overview                                          2



•   Introduction
•   Why PA6 in food packaging
•   Trends in barrier films
•   Akulon XP – high productivity PA6
•   Conclusion




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
DSM: over a century of successful
                                                                                             3
transformations

Evolution                                                  Bioterials / Biologics

                                                  Life Science Products

                                      Performance Materials

                           Petrochemicals

               Fertilizers

    Coal

                                                                 Technological competences
1902       1930       1950       1970        1990      2000
                                                                  Mechanical engineering
                                                                  Chemical engineering
                                                                  Polymer technology
                                                                  Material science
                                                                  Fine chemicals
                                                                  Biotechnology


DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
DSM today                                                                                 4



• Globally active “multi-specialty” chemical company
      • active on 5 continents, more than 200 locations
      • approximately ~ 21.000 employees
• Leadership positions in ~75 % of the portfolio
• R&D spending ~ 5 % of sales
                                           Life
• Solid balance sheet                      Science
      • € 8 billion sales in 2005                                 Products
                                                  Performance
                                                     Materials
                                                                        DSM Nutritional
                 DEP                               Other                  Products
                                                           Industrial
   DSM Engineering Plastics
                                                           Chemicals
   €705 million sales in 2005
       1300 employees

DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
DEP: partner for innovative film concepts                     5



•   Today one of the leading PA6 film resin suppliers    H    O
                                                          N
•   New plant started with 18.000 t/y capacity in 2001
•   Additional capacity of 35.000 t/y in 2005
•   Introduction of Akulon XP
•   Portfolio of resins for the film industry




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
DSM product portfolio for film applications                                    6



•   Akulon PA6                         portfolio of standard grades
•   Akulon PA66                        for cast and blown film
•   Akulon XP                        high productivity PA6
•   Yparex                           PE-g-MAH tie resin
•   Stanyl PA46                      high heat resistant for specialty films
•   Arnitel COPE                     breathable film




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
PA6 in barrier film                               7



• food packaging (> 80 %)
      •   meat
      •   cheese
      •   fish
      •   sausage casings
• non-food applications
      •   release films for SMC
      •   medical film
      •   protective bubble film
      •   agricultural film




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Food packaging                                    8




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Why PA6 for film in food packaging?               9



•   Oxygen barrier
•   Aroma and flavour barrier
•   Mechanical protection
•   Puncture resistance
• Printability
• Transparency
• Heat resistance




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Oxygen versus water permeation                                                                                10


                                                                                      film thickness 100μm
                                          10000
  oxygen permeability




                                                                   LDPE     EVA
                                                        HDPE                        PS
                        [ml/m2*day*bar]




                                          1000
                                                               PP     PVC-P           PC
                                                   BOPP
                                           100

                                            10                        PET
                                                                                       PA6

                                             1
                                                        PVDC
                                                                   EVOH 44 %                     cellophane
                                            0.1
                                                  0.1          1               10          100          1000
                                                    water permeation at 23 °C, 85 % RH [g/m2*day]



DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Trends in PA barrier film                                       11



• Use of BOPA
• Improvement of barrier properties
      • nanocomposites
      • oxygen scavengers
      • blends
•   Active & intelligent packaging
•   More complex film structures                  (Akulon XP)
•   Down gauging – improved productivity          (Akulon XP)
•   Shift from PA6.66 to PA6



DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Examples of coextruded multilayer structures                  12




   cheese/meat
                                                    PA
                                                  tie layer
                                                    PE

    fresh meat
                                                     PP
                                                  tie layer
                                                     PA
                                                    EVOH
                                                     PA
                                                  tie layer
                                                     PE
DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Multilayer film with viscosity match                                  13




                                                  desired situation




However, in practice ideal situations are rare




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Multilayer film with viscosity mismatch                                    14




                                                  Viscosity mismatch:
                                                  • limits flexibility
                                                     • more grades
                                                       required
                                                     • different film
         polymer with higher viscosity                 structures on one
                                                       machine not
                                                       always feasible
                                                  • quality risk
                                                  • more material use



DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Viscosity curves of LDPE and PA6                                                15




                    10000
 viscosity [Pa.s]




                    1000
                                                                       LDPE
                                                                       Akulon F132
                     100



                      10
                        0.01   0.1         1      10      100   1000
                                       shear rate [1/s]


DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Polymer flow in a coat hanger die                 16




Coat hanger die:
• different flow rates in the die
• multilayer structures require viscosity match
  to prevent interface disturbances

DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Standard materials result in interfacial
                                                                                                      17
                   instability
                              Rheology mismatch PA6 and LDPE
                                                          processing window
                   10000
viscosity [Pa.s]




                   1000
                                                                        PA6
                                                                        LDPE
                    100


                     10
                       0.01      0.1    1          10      100   1000
                                       shear rate [1/s]                        leads easily to problems


                      poor elasticity and viscosity
                      match creates wave effect

                      one component
                      missing at edges


                   DSM Engineering Plastics
                   PAGEV Turkish Plastics Industry Congress - 2006
Viscosity curves of unmodified materials                                          18




                    10000
 viscosity [Pa.s]




                                                                       LDPE
                    1000
                                                                       Akulon   F126
                                                                       Akulon   F130
                                                                       Akulon   F132
                     100
                                                                       Akulon   F136


                      10
                        0.01   0.1         1      10      100   1000
                                       shear rate [1/s]


DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
What determines interfacial stability?            19



Rheology of different components:
• shear viscosity
• normal stress
• elongational viscosity




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
The Akulon XP solution                                                                20



                   Minimizes the difference in melt viscosity and melt elasticity
                   of coextruded materials.
                   Result: widening of processing window

                   10000                                                Akulon XP
                                                                                     Akulon XP exhibits:
                                                                                     enhanced
viscosity [Pa.s]




                    1000
                                                                                       shear-thinning
                                                                                       behaviour:
                     100        LDPE                                                 • less motor power at
                                MFI 1.9                                                high rpm
                      10
                                                                                     • higher zero shear
                         0.01         0.1           1           10    100    1000      viscosity
                                                   shear rate [1/s]

                                                                                wide processing window

                   DSM Engineering Plastics
                   PAGEV Turkish Plastics Industry Congress - 2006
The “trick”: branching of the PA6 chain                   21



Random long chain branching of PA6
• increase of zero-viscosity
• flow behaviour becomes more shear thinning
• enhanced melt strength in elongational flow

Furthermore:
• branching allows very high molecular weights, not possible
  with linear PA6




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Effects of branched polymers                                                       22



Linear polymers show Newtonian flow behaviour




Short chain branching:                             Long chain branching:
• reduction of density                             • strong influence on rheology
• minor influence on rheology                      • enhanced shear thinning
                                                   • strain hardening
 DSM Engineering Plastics
 PAGEV Turkish Plastics Industry Congress - 2006
Effects of branching                                           23



Control of viscosity
• melt stability (uncontrolled polymerization)
• gels !!

Controlled branching is realized by:
• branching agent: addition of a trifunctional compound
• to prevent formation of gels: addition of a monofunctional
  compound




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Neck-in on cast film and extrusion coating                       24




                                   maximum die width


                      standard PA6                   Akulon XP
                                       extruded film width
 chill
 roll



DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Web stability in cast film and extrusion
                                                                    25
coating


                                                  die


                      standard PA6                      Akulon XP

 chill
 roll



                                           web instability
DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Improved layer thickness distribution                                   26




                                                            classical PA6


                    thin sections are quality risk
edge trim                  and determine             edge trim
                 barrier and mechanical properties




                                                             Akulon XP


 DSM Engineering Plastics
  PAGEV Turkish Plastics Industry Congress - 2006
The thermoforming process                                          27




                                                       IR heater


                                                       film
                                                       mould


                                              vacuum



DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
The thermoforming process                                          28




                                                       IR heater


                                                       film
                                                       mould


                                              vacuum



DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Thermoforming issues                                                   29




                                                  thin corners



                                                       Issues:
                                                       • thin corners
                                                       • limited elongation




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Thermoforming behaviour                           30



• drawing is influenced by:
      •   temperature
      •   stretch ratio
      •   drawing rate
      •   polymer viscosity
      •   molecular structure
      •   crystallization rate




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Thermoforming of COPA and PA6                           31



• advantage COPA is lower crystallization rate
• drawing of PA6 can be improved by:
      • keep the sheet as amorphous as possible
      • addition of amorphous polyamide
      • addition of COPA



• improved thermoformability of Akulon XP compared to
  regular PA6
      • more even thickness in the corners
      • higher elongation possible



DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Effects of Akulon XP in multilayer cast film                               32



• less neck-in                                    waste reduction (side trims)
                                                  improved machine efficiency
• better web stability                            higher production speed
• improved layer thickness                        less material use
  distribution                                    better quality
• wider processing window                         less down-time
                                                  higher output
• shear thinning                                  less motor power at high rpm
                                                  higher output possible


DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Akulon XP properties                                  33



• improved processing efficiency
      •   cast film
      •   blown film
      •   extrusion coating
      •   thermoforming
      •   stretching
• barrier properties same as classical PA6
• mechanical properties comparable to classical PA6
• crystallization behaviour unchanged




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Advantages of Akulon XP in non-film applications                               34



• extrusion blow moulding
      • improved melt strength
• monofilaments
      • improved roundness at large diameters
• stock shapes
      • improved symmetry in tubes with large diameters due to high melt stabilty
• convoluted tubes
      • improved dimensional stability at low diameters tube




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
Conclusion                                        35



Akulon XP is a new polyamide 6
with improved processing
behaviour, which can lead to lower
conversion costs and improved
film properties




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
More information                                  36




       Contacts and more information:

       www.dsmep.com
       www.akulon.com




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006
37




  İLGİNİZ İÇİN TEŞEKKÜR EDERİM




DSM Engineering Plastics
PAGEV Turkish Plastics Industry Congress - 2006

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Pagev dsm presentation pa6 in film

  • 1. 1 Improved performance with PA6 in multilayer barrier films PA6 with modified rheology Ted Brink Application Development Extrusion DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 2. Overview 2 • Introduction • Why PA6 in food packaging • Trends in barrier films • Akulon XP – high productivity PA6 • Conclusion DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 3. DSM: over a century of successful 3 transformations Evolution Bioterials / Biologics Life Science Products Performance Materials Petrochemicals Fertilizers Coal Technological competences 1902 1930 1950 1970 1990 2000 Mechanical engineering Chemical engineering Polymer technology Material science Fine chemicals Biotechnology DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 4. DSM today 4 • Globally active “multi-specialty” chemical company • active on 5 continents, more than 200 locations • approximately ~ 21.000 employees • Leadership positions in ~75 % of the portfolio • R&D spending ~ 5 % of sales Life • Solid balance sheet Science • € 8 billion sales in 2005 Products Performance Materials DSM Nutritional DEP Other Products Industrial DSM Engineering Plastics Chemicals €705 million sales in 2005 1300 employees DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 5. DEP: partner for innovative film concepts 5 • Today one of the leading PA6 film resin suppliers H O N • New plant started with 18.000 t/y capacity in 2001 • Additional capacity of 35.000 t/y in 2005 • Introduction of Akulon XP • Portfolio of resins for the film industry DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 6. DSM product portfolio for film applications 6 • Akulon PA6 portfolio of standard grades • Akulon PA66 for cast and blown film • Akulon XP high productivity PA6 • Yparex PE-g-MAH tie resin • Stanyl PA46 high heat resistant for specialty films • Arnitel COPE breathable film DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 7. PA6 in barrier film 7 • food packaging (> 80 %) • meat • cheese • fish • sausage casings • non-food applications • release films for SMC • medical film • protective bubble film • agricultural film DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 8. Food packaging 8 DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 9. Why PA6 for film in food packaging? 9 • Oxygen barrier • Aroma and flavour barrier • Mechanical protection • Puncture resistance • Printability • Transparency • Heat resistance DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 10. Oxygen versus water permeation 10 film thickness 100μm 10000 oxygen permeability LDPE EVA HDPE PS [ml/m2*day*bar] 1000 PP PVC-P PC BOPP 100 10 PET PA6 1 PVDC EVOH 44 % cellophane 0.1 0.1 1 10 100 1000 water permeation at 23 °C, 85 % RH [g/m2*day] DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 11. Trends in PA barrier film 11 • Use of BOPA • Improvement of barrier properties • nanocomposites • oxygen scavengers • blends • Active & intelligent packaging • More complex film structures (Akulon XP) • Down gauging – improved productivity (Akulon XP) • Shift from PA6.66 to PA6 DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 12. Examples of coextruded multilayer structures 12 cheese/meat PA tie layer PE fresh meat PP tie layer PA EVOH PA tie layer PE DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 13. Multilayer film with viscosity match 13 desired situation However, in practice ideal situations are rare DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 14. Multilayer film with viscosity mismatch 14 Viscosity mismatch: • limits flexibility • more grades required • different film polymer with higher viscosity structures on one machine not always feasible • quality risk • more material use DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 15. Viscosity curves of LDPE and PA6 15 10000 viscosity [Pa.s] 1000 LDPE Akulon F132 100 10 0.01 0.1 1 10 100 1000 shear rate [1/s] DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 16. Polymer flow in a coat hanger die 16 Coat hanger die: • different flow rates in the die • multilayer structures require viscosity match to prevent interface disturbances DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 17. Standard materials result in interfacial 17 instability Rheology mismatch PA6 and LDPE processing window 10000 viscosity [Pa.s] 1000 PA6 LDPE 100 10 0.01 0.1 1 10 100 1000 shear rate [1/s] leads easily to problems poor elasticity and viscosity match creates wave effect one component missing at edges DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 18. Viscosity curves of unmodified materials 18 10000 viscosity [Pa.s] LDPE 1000 Akulon F126 Akulon F130 Akulon F132 100 Akulon F136 10 0.01 0.1 1 10 100 1000 shear rate [1/s] DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 19. What determines interfacial stability? 19 Rheology of different components: • shear viscosity • normal stress • elongational viscosity DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 20. The Akulon XP solution 20 Minimizes the difference in melt viscosity and melt elasticity of coextruded materials. Result: widening of processing window 10000 Akulon XP Akulon XP exhibits: enhanced viscosity [Pa.s] 1000 shear-thinning behaviour: 100 LDPE • less motor power at MFI 1.9 high rpm 10 • higher zero shear 0.01 0.1 1 10 100 1000 viscosity shear rate [1/s] wide processing window DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 21. The “trick”: branching of the PA6 chain 21 Random long chain branching of PA6 • increase of zero-viscosity • flow behaviour becomes more shear thinning • enhanced melt strength in elongational flow Furthermore: • branching allows very high molecular weights, not possible with linear PA6 DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 22. Effects of branched polymers 22 Linear polymers show Newtonian flow behaviour Short chain branching: Long chain branching: • reduction of density • strong influence on rheology • minor influence on rheology • enhanced shear thinning • strain hardening DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 23. Effects of branching 23 Control of viscosity • melt stability (uncontrolled polymerization) • gels !! Controlled branching is realized by: • branching agent: addition of a trifunctional compound • to prevent formation of gels: addition of a monofunctional compound DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 24. Neck-in on cast film and extrusion coating 24 maximum die width standard PA6 Akulon XP extruded film width chill roll DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 25. Web stability in cast film and extrusion 25 coating die standard PA6 Akulon XP chill roll web instability DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 26. Improved layer thickness distribution 26 classical PA6 thin sections are quality risk edge trim and determine edge trim barrier and mechanical properties Akulon XP DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 27. The thermoforming process 27 IR heater film mould vacuum DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 28. The thermoforming process 28 IR heater film mould vacuum DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 29. Thermoforming issues 29 thin corners Issues: • thin corners • limited elongation DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 30. Thermoforming behaviour 30 • drawing is influenced by: • temperature • stretch ratio • drawing rate • polymer viscosity • molecular structure • crystallization rate DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 31. Thermoforming of COPA and PA6 31 • advantage COPA is lower crystallization rate • drawing of PA6 can be improved by: • keep the sheet as amorphous as possible • addition of amorphous polyamide • addition of COPA • improved thermoformability of Akulon XP compared to regular PA6 • more even thickness in the corners • higher elongation possible DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 32. Effects of Akulon XP in multilayer cast film 32 • less neck-in waste reduction (side trims) improved machine efficiency • better web stability higher production speed • improved layer thickness less material use distribution better quality • wider processing window less down-time higher output • shear thinning less motor power at high rpm higher output possible DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 33. Akulon XP properties 33 • improved processing efficiency • cast film • blown film • extrusion coating • thermoforming • stretching • barrier properties same as classical PA6 • mechanical properties comparable to classical PA6 • crystallization behaviour unchanged DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 34. Advantages of Akulon XP in non-film applications 34 • extrusion blow moulding • improved melt strength • monofilaments • improved roundness at large diameters • stock shapes • improved symmetry in tubes with large diameters due to high melt stabilty • convoluted tubes • improved dimensional stability at low diameters tube DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 35. Conclusion 35 Akulon XP is a new polyamide 6 with improved processing behaviour, which can lead to lower conversion costs and improved film properties DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 36. More information 36 Contacts and more information: www.dsmep.com www.akulon.com DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006
  • 37. 37 İLGİNİZ İÇİN TEŞEKKÜR EDERİM DSM Engineering Plastics PAGEV Turkish Plastics Industry Congress - 2006

Editor's Notes

  1. Life Science Products includes: Fine Chemicals, Pharmaceuticals, Anti-infectives, Food Specialties and Bakery Ingredients. DSM Nutritional Products includes: vitamins, biochemicals and fine chemicals for human and animal nutrition. Industrial Chemicals includes: Fibre Intermediates including caprolactam (2004),
  2. Film thickness 100 micron, measuring temperature 23 °C Source: Kompendium zum Thema Barrierefolien und Barriereeigenschaften, by Andreas Neumann, Nordenia, January 2001
  3. Measured at 260 °C
  4. Measured at 260 °C
  5. LDPE = Stamylan LD2102T