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					         Workshop on Colorimetry and Color Imaging
               24th-26th September’08, Almuñércar




      Colorimetric Properties of
       Thermoplastic Polymers
     Coloured with Nanopigments
      and Conventional Pigments

F. Martínez Verdú, A. Marcilla,
   Martínez Verdú,
   M. Beltrán, V. Marchante
      Beltrán,
Nanopigments
Index
 • Definition and Synthesis
 • Application in thermoplastic polymers:
   Colorimetric Characterization
   – Samples
   – Measurements
   – Parameters
 • Recent conclusions
 • Future applications and research lines.
 Nanopigments                         SYNTHESIS
                                   Nanoclay
                                                          H2O deionized
                                   Sieving

                                               Dispersion
                                                   +
                                             Colorant solution


                                              Ionic Exchange


• Planocolors® (TNO, Eindhoven):
                                        Washing and Filtering
  Combination of nanoclay and
  organic dye molecules                          Drying
Nanopigments in polymers:
Colorimetric Characterization

Samples Preparation                    Measurements
• Materials                               • Measures
   – Polymer: LLDPE     Blue Phthalocyanin   – ρ0W, ρ0B
                        Blue Ultramarine
   – Pigment: 0.1 %w    Planocolor® Blue     – ρW, ρ B
• Procedure             Blue Nanopigment     − Δλ = 10 nm
   – Pre-mixing                              – Black and White
   – Kneader:                                  substrate
     180 ºC, 40 rpm, 10 min.              • Equipment
   – Hot Plates Press                        – Spectrophotometer
     180 ºC, 7 min.                            KONICA MINOLTA
                                               CM-2600d
Nanopigments in polymers:
Colorimetric Parameters

  • Spectral Reflectance
  • Absorption and Scattering
  • Colorimetric Performance
    – Hiding Power
    – Transparency
    – Coloring Power
     Nanopigments in polymers:
     Spectral Reflectance
                   Spectral Reflectance
 1,0                 White Substrate

 0,8
                                    LLFTA
                                    LLAU
 0,6
                                    LLNA (TNO)
ρW




 0,4
                                    LLNA (UA)
                                                                                              40
                                    WHITE SUBSTRATE                                     120                60

                                                                                              30
 0,2
                                                                               150                                    30
                                                                                              20

 0,0                                                                                          10
       400   450      500     550         600   650   700




                                                            blue - yellow b*
                               λ (nm)                                                          0
                                                                          -40 -30 -20 -10 0           10   20    30         40
                                                                                        -10

                                                                               210            -20                     330


                                                                                              -30
                                                                                        24                 300
                                                                                              -40
                                                                                     green - red a*
Nanopigments in polymers:
Absorption and Scattering Coefficients
                   Absorption Coefficent (K)

      3,5                                Blue Phthalocyanine
         3                               Blue Ultramarine
                                         Blue Nanopigment (TNO)
      2,5
                                         Blue Nanopigment (UA)
         2
     K




      1,5
         1
      0,5
         0
             400          500              600           700
                                λ (nm)
Nanopigments in polymers:
Absorption and Scattering Coefficients
               Scattering Coefficient (S)
      3,5
                               Blue Phthalocyanine
         3
                               Blue Ultramarine
      2,5
                               Blue Nanopigment (TNO)
         2
     S




      1,5                      Blue Nanopigment (UA)

         1
      0,5
         0
             400         500             600            700
                                λ (nm)
Nanopigments in polymers:
Colorimetric Performance
1,8    1,62
1,6
              Hiding Power                        10
                                                                                    9,76
                                                           Transparency
1,4             D (m2/L)                           9
                                                             T (mL/m2)
                                                   8
1,2                                                                        6,42
                                                   7
1,0                                                6
0,8                                                5             4,43
0,6                                                4
                                                   3    2,49
0,4                   0,23     0,24
              0,16                                 2
0,2                                                1
0,0                                                0
      LLFTA   LLAU    LLNA     LLNA                    LLFTA    LLAU       LLNA   LLNA (UA)
                     (TNO)     (UA)                                       (TNO)

                         1,0
                         0,9           Coloring Power
                         0,8              Φ (m2/L)
                         0,7
                         0,6                            0,51
                         0,5
                                                                0,38
                         0,4    0,30
                         0,3
                                           0,17
                         0,2
                         0,1
                         0,0
                               LLFTA      LLAU         LLNA    LLNA
                                                       (TNO)   (UA)
Conclusions
 • Colorimetric Assessment:
    – Colour Performance similar or better than conventional
      pigments.
    – Intermediate behaviour between organic and inorganic
      pigments.
    – More transparency (T) and more colouring power (Φ) than
      other pigments.
 • They can be an attractive alternative to toxic inorganic
   pigments:
    – They improve mechanical properties while avoiding using
      other additives. Application in other processing methods
      (rotomolding).
    – Better colour performance.
    – Not contaminant: they don’t have heavy metal in their
      composition.
Future perspectives:
Applications and Research Lines
  • Development of new nanopigment: different
    types of organic dyes and nanoclays.
    Nanopigments with special properties.
  • Application in a wide range of fields (printing
    inks, powder coatings, textile fibers, etc.)
  • Development of continuous synthesis
    process at pilot plant scale.