Surface modifications by applying
organic nanoparticles from a water
dispersion


Dr. Dirk Stanssens
Topchim introduction
                                                              2
 - Established in 1996

 - Offices + ...
Market drivers

  • Better performing products at competitive prices

  • Growing awareness for more sustainable solutions...
Topchim’s Nano-particles

  • Development of organic nanoparticles
     – Good interaction with other materials
     – Hig...
Technologies to produce organic nano-particles


   1. Straight synthesis by chemical transformation of
      SMA polymers...
Technology 1: Nanoparticle Synthesis
                                                                              6




 ...
Technology 2: Hybrid systems: precipitation of
the nano-particles on inorganic carriers                          7


Carri...
Technology 3: Nano-encapsulation



                                 +oils or
                                 waxes
SMA: ...
-Technical solution: tunability by SMA type
               -Paper (Ra = 60 nm)
                               174.78 nm
  ...
SMI coating: Chemical interactions
                                                                              10

     ...
Mechanical Stability

Upon drying, the nano dispersed particles coagulate to clusters.
Cohesion between the particles and ...
Hydrophobicity                                                  4,5
                                                      ...
Hydrophobicity


Static contact angle measurements at different temperatures

                                            ...
SMI-coatings: Hydrophobicity
                                                                                             ...
Obtained results for paper coating applications
                                                       15



   • Good pri...
Environmental solution
•   Water based dispersion of 50-65% solids
    – Without use of external surfactants
    – High bi...
Summary
                                 PE foils   Wax/paraffin TopScreen   TopScreen
                                   ...
Applications
  • Corrugated board and boxes for fruit and vegetables

  • Frozen food packaging

  • Beverage cups and foo...
-PE-free beverage paper cups
Market cups

 • 220 billion paper cups/year worldwide

 • 58% North America

 • Growing consumption in emerging markets
TopChim’s technology
 • Coated cup stock

 • No thermoplastic film (like PE or PLA)

 • Standard sealing process

 • Coati...
Performances

 • No leaking, even after 24 hours

 • Tunable for cost efficiency
    – Layer thickness can be chosen

 • C...
Performances




               Verso coating 1-layer 8 gr/m²
Performances




               Recto coating 1-layer 4 gr/m²
Process cup stock production

 • Surface treatment immediately at cup stock production

 • No off-line extrusion treatment...
Process cup production

 • Standard cup production machines

 • Standard sealing processes

 • Waste is repulpable

 • Pri...
Ecological advantages

 • Reduced manufacturing process
    – Less energy and waste
    – Less transport

 • Higher degree...
Potential non-paper applications

 • Use of nano-pigments and nano-dispersions for a.o.:
    – Cosmetics
    – Fibers
    ...
Textile industry: semi-permeable coatings

   • Fully water-borne coatings
   • Good adhesion to several textile substrate...
Ink applications

   •   Water borne formulations, no external surfactants
   •   Encapsulated dyes behave as nano-pigment...
Conclusions
                                                                31
 The imidisation of poly(styrene-maleic anh...
Conclusions
                                                                 32

 The SMI nano-particles can be produced i...
Address



           info@topchim.com

               TOPCHIM NV
           Nijverheidsstraat 98
           2160 Wommelge...
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11.20 dhr stanssens

  1. 1. Surface modifications by applying organic nanoparticles from a water dispersion Dr. Dirk Stanssens
  2. 2. Topchim introduction 2 - Established in 1996 - Offices + laboratories in Belgium and Brazil - R&D mainly focused on paper and card board coatings - 3 actual core-domains: - Rheology and water retention - Barrier coatings (ecological alternatives) - Organic nano-pigments - New development group started for non-paper applications
  3. 3. Market drivers • Better performing products at competitive prices • Growing awareness for more sustainable solutions • Use of renewable materials • Recycling of used materials • Reduction of VOC • Water as an environmentally friendly and save solvent • Cradle to cradle solutions
  4. 4. Topchim’s Nano-particles • Development of organic nanoparticles – Good interaction with other materials – High surface area – Tunable properties – Water borne – High solid content – Without use of external surfactants – High bio-renewability content • Applicable on most substrates • Approved for food contact
  5. 5. Technologies to produce organic nano-particles 1. Straight synthesis by chemical transformation of SMA polymers 2. Precipitation on inorganic carriers 3. Core-shell nanoparticles; encapsulation of active ingredients
  6. 6. Technology 1: Nanoparticle Synthesis 6 SMA: Poly(styrene maleic anhydride) SMI: Poly(styrene maleimide) Nanoparticle formation: •d = 100 to 150 nm (not filled with oil) = 30 to 50 nm (when filled with oil) •Tg > 1900C •Possibility to make the particles non-thermoplastic
  7. 7. Technology 2: Hybrid systems: precipitation of the nano-particles on inorganic carriers 7 Carriers: e.g. glass, kaolinite, CaCO3, delaminated talc, TiO2:
  8. 8. Technology 3: Nano-encapsulation +oils or waxes SMA: Poly(styrene maleic anhydride) SMI: Poly(styrene maleimide) • Imidization in presence of oils or waxes leads to nano- particles that include the oils or waxes • Resulting particles have a core shell structure • Particles can contain up to 70% of oil • The oil can contain active ingredients such as dyes, UV- absorbers, optical brighteners, perfumes, biocides.
  9. 9. -Technical solution: tunability by SMA type -Paper (Ra = 60 nm) 174.78 nm -SMI 1 (Ra = 15 nm) -SMI 2 (Ra = 11 nm) 122.74 nm 55.73 nm -2 µm x 2 µm 0.00 nm 0.00 nm 0.00 nm -Clustering of particles -Homogeneous distribution -(higher imidide content) -Lotus leaf surface
  10. 10. SMI coating: Chemical interactions 10 Chemical interaction of SMI-nanoparticles with paper surface Interaction of nanoparticles with cellulose fibers occurs through hydrogen-bonds and provides good adhesion without need of further binder components SMI-1 SMI-2 Paper Raman shift (cm-1) Region 1000-1100 cm-1: C-O stretching of C-OH groups Cellulose structure
  11. 11. Mechanical Stability Upon drying, the nano dispersed particles coagulate to clusters. Cohesion between the particles and adhesion to the substrate are quite strong. No nano-particles are released upon friction. SMI before friction SMI after friction (Ra = 15.3, Rt = 92 nm) 56.08 nm (Ra = 11.2, Rt = 86 nm) 80.10 nm height height 400nm 400nm 0.00 nm 0.00 nm
  12. 12. Hydrophobicity 4,5 4 y = 0,1438x + 1 Roughness Component R² = 0,9938 3,5 3 Dynamic contact angle measurements: r-parameter 2,5 Nano-scale effects 2 1,5 1 Nano-structured SMI coatings allow for 0,5 “tuning” the contact angle value, 0 0 5 10 15 20 25 according to cos θ* = r cos θ Surface Roughness Ra (nm) 160 θ 160 * Chemical Component 140 140 120 120 100 Contact angle (°) Contact angle(°) 100 80 80 60 120 Calibration curve on 60 y‘flat’ surface = 1.8826x + 52.113 40 100 R² = 0.9993 40 Contact angle (°) 80 20 20 60 0 0 0 0 10 10 40 20 20 % imide 30 30 40 40 % imide 20 0 0 5 10 15 20 25 30 35
  13. 13. Hydrophobicity Static contact angle measurements at different temperatures uncoated paper SMA-coated paper Contact angle (°) SMI-coated paper SMI-coated paper 250°C Time (s)
  14. 14. SMI-coatings: Hydrophobicity 14 Dynamic contact angle measurements: effect of thermal conditioning SMI - 1 SMI – 2 Ra (nm) % imide qa qr Ra (nm) % imide qa qr Non-cured 10.3 25 120 22 7.44 29 138 31 125°C 11.2 27 122 38 6.64 32 141 44 135°C 10.8 29 133 43 6.58 36 145 52 150°C 10.2 27 130 39 6.29 30 138 48 180°C 10.5 24 117 30 5.71 27 134 42 200°C* 1.96 23 98 20 0.65 26 108 32 250°C** 0.89 20 92 42 0.57 23 90 38
  15. 15. Obtained results for paper coating applications 15 • Good print quality and paper strength with less coating weight • Replacing environmental unfriendly substances used in paper and card board production: - Fluorine based additives - Wax emulsions - Polyethylene • Improved repulpability
  16. 16. Environmental solution • Water based dispersion of 50-65% solids – Without use of external surfactants – High bio-renewability content (up to 70% vegetable oil) • Recyclable and compostable alternative for wax and PE treated paper and board • Applicable on online coaters (economically attractive compared to cost for off-line wax treatment or PE-extrusion) • 100% repulpability
  17. 17. Summary PE foils Wax/paraffin TopScreen TopScreen DS3V DS13 Hydrophobicity ++ +++ + +++ Vapor transmission barrier +++ --- +++ --- Oleophobicity +++ --- +++ ++ Repulpability --- --- +++ +++ Recyclability - compostability --- --- +++ +++ Water borne solution --- --- +++ +++ Machinability - online --- --- +++ +++ Heat sealability +++ --- +++ +++ Hot melt gluability ++ -- ++ ++ Eco friendliness -- --- +++ +++
  18. 18. Applications • Corrugated board and boxes for fruit and vegetables • Frozen food packaging • Beverage cups and food plates • Precoat for siliconised paper • Liquid packaging • Meat, Poultry and Fish wrap • Compostable waste packaging (home recycling) • Pizza and fast food containers • Sandwich packaging
  19. 19. -PE-free beverage paper cups
  20. 20. Market cups • 220 billion paper cups/year worldwide • 58% North America • Growing consumption in emerging markets
  21. 21. TopChim’s technology • Coated cup stock • No thermoplastic film (like PE or PLA) • Standard sealing process • Coating chemistry based on particles containing vegetable oil • Competitive alternative for PE treatment • Suitable for cold and hot drinks
  22. 22. Performances • No leaking, even after 24 hours • Tunable for cost efficiency – Layer thickness can be chosen • Condensation barrier; 2 gsm of coating layer sufficient • Additional oleophobicity (e.g. pop-corn cups or salad bowls)
  23. 23. Performances Verso coating 1-layer 8 gr/m²
  24. 24. Performances Recto coating 1-layer 4 gr/m²
  25. 25. Process cup stock production • Surface treatment immediately at cup stock production • No off-line extrusion treatment – Less transport – Less energy – Less waste • Treated cup stock is repulpable (broke and waste) • Higher flexibility on barrier layer weight
  26. 26. Process cup production • Standard cup production machines • Standard sealing processes • Waste is repulpable • Printable
  27. 27. Ecological advantages • Reduced manufacturing process – Less energy and waste – Less transport • Higher degree of recyclability and compostability • Highly reduced dependency on mineral oil based materials
  28. 28. Potential non-paper applications • Use of nano-pigments and nano-dispersions for a.o.: – Cosmetics – Fibers – Inks – Paints • Focus on: – Applying coatings that make substrates hydrophobic – Nano-encapsulating of active ingredients (dyes, optical brighteners, perfumes, sun screen,…) • Market approach by co-operation with development partners
  29. 29. Textile industry: semi-permeable coatings • Fully water-borne coatings • Good adhesion to several textile substrates • Transparent coatings with good water repellency • Nano-particles have a high Tg and are not film forming • The coating layer keeps its porosity and its breathability
  30. 30. Ink applications • Water borne formulations, no external surfactants • Encapsulated dyes behave as nano-pigments • Upon drying ink shows water repellency • Very stable dispersion of pigments in water – Carbon black, carbon nanotubes – Can be used for ink-jet ink applications
  31. 31. Conclusions 31 The imidisation of poly(styrene-maleic anhydride) results in SMI nanoparticles: - of 100 to 150 nm diameter - Tg = 190 – 220°C - with good mechanical resistance - high dispersion stability in water - leading to favorable processing characteristics - having high interaction with other materials
  32. 32. Conclusions 32 The SMI nano-particles can be produced in the presence of a carrier material andor in the presence of oils and waxes. Furthermore, these oils or waxes can contain active ingredients. Properties such as e.g. water repellency, color, UV absorption, gloss can be tuned by choosing the appropriate combination of raw materials. Topchim is open for collaborations on specific projects with clear market needs.
  33. 33. Address info@topchim.com TOPCHIM NV Nijverheidsstraat 98 2160 Wommelgem Belgium Tel: +32 3 350.08.40 Fax: +32 3 350.08.49

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