Vous êtes sur la page 1sur 36

Kiss

Technology

Pigment Wetting

Innovation you can build on TM

Kiss Technology Pigment Wetting Innovation you can build on

Kiss Technology

Agenda

  • Principles of pigment wetting

  • Methods of analysis

Kiss Technology Agenda  Principles of pigment wetting  Methods of analysis  Experimental work and
  • Experimental work and results discussion

Innovation you can build on TM

Kiss Technology Agenda  Principles of pigment wetting  Methods of analysis  Experimental work and

Kiss Technology

Pigments Dispersion Principles

  • Lipsticks consist of a mixture of oils and waxes with pigments dispersed throughout

Kiss Technology Pigments Dispersion Principles  Lipsticks consist of a mixture of oils and waxes with
  • Dispersion of pigments in a liquid medium is

typically accomplished in 2 steps:

1. Wetting the surface of the primary particles and agglomerates

2. Milling the dispersion to break apart any agglomerates (by means of mill or high speed mixer)

Innovation you can build on TM

Kiss Technology Pigments Dispersion Principles  Lipsticks consist of a mixture of oils and waxes with

Kiss Technology

Pigment Wetting

  • Pigment wetting is the replacement of absorbed air on the pigment surface with the liquid medium

Kiss Technology Pigment Wetting  Pigment wetting is the replacement of absorbed air on the pigment
  • It can be influenced by:

Kiss Technology Pigment Wetting  Pigment wetting is the replacement of absorbed air on the pigment
  • Particles size, shape and surface characteristics

  • Particle-particle interactions the stronger the poorer the wetting

  • Absorption ability of the oils by the pigments the higher the poorer the wetting

  • Processing e.g. milling time, energy etc.

Innovation you can build on TM

Kiss Technology Pigment Wetting  Pigment wetting is the replacement of absorbed air on the pigment

Kiss Technology

Importance of Effective

Pigment Wetting

  • Effective wetting facilitates particles separation, so agglomerates are easily milled and offer consistent colour dispersion throughout

Effective wetting Poor wetting Intrinsic colour strength
Effective wetting
Poor wetting
Intrinsic colour strength

Mill time

Innovation you can build on TM

Kiss Technology Importance of Effective Pigment Wetting  Effective wetting facilitates particles separation, so agglomerates are
Kiss Technology Importance of Effective Pigment Wetting  Effective wetting facilitates particles separation, so agglomerates are

Kiss Technology

Importance of Effective

Pigment Wetting

  • Poor wetting leads to higher viscosity of the dispersion hence lower pigment load and higher processing time and costs

Poor wetting Effective wetting Viscosity
Poor wetting
Effective
wetting
Viscosity

Pigment

concentration

Innovation you can build on TM

Kiss Technology Importance of Effective Pigment Wetting  Poor wetting leads to higher viscosity of the
Kiss Technology Importance of Effective Pigment Wetting  Poor wetting leads to higher viscosity of the

Viscosity of Pigment Dispersions

  • Particulate dispersions tend to be shear thinning (viscosity reduces with applied shear)

  • At very low shear, internal

friction of the particles is at

maximum and viscosity is

apparently independent of shear rate (first Newtonian plateau)

  • As shear increases, the system will

First Newtonian plateau Shear thinning region Second Newtonian plateau Log viscosity
First Newtonian plateau
Shear thinning region
Second Newtonian plateau
Log viscosity

Log shear stress

yield and the viscosity becomes shear dependent (shear thinning region)

  • At very high shear rates, the viscosity will again become independent of shear where internal friction of the particles is at minimum (second Newtonian plateau)

N.B. Viscosity of dispersing medium influences the viscosity of pigment grind

Innovation you can build on TM

Viscosity of Pigment Dispersions  Particulate dispersions tend to be shear thinning (viscosity reduces with applied

Kiss Technology

Pigment Wetting Methods of Measurement

  • The pigment wetting ability of oils can be quantified by relative viscosity measurements and analysing rheology of pigment dispersions

Kiss Technology Pigment Wetting – Methods of Measurement  The pigment wetting ability of oils can

Relative viscosity = (viscosity of pigment grind) / (viscosity of

dispersing medium)

  • Advantages of rheometric test methods over standard ‘Brookfield tests’

    • Cover much broader shear rate/stress range - possible to measure zero/low shear viscosity or high shear viscosity

    • Provide information on viscoelastic behaviour enable to make assumptions on dispersion quality and stability

    • Possible to make steady state measurements no transient effects during data collection

Innovation you can build on TM

Kiss Technology Pigment Wetting – Methods of Measurement  The pigment wetting ability of oils can

Kiss Technology

Kiss Technology Controlled Stress Rotational Rheometer  Fundamentally a CS rotational rheometer will  Apply torque

Controlled Stress Rotational Rheometer

  • Fundamentally a CS rotational rheometer will

    • Apply torque (force)

    • Measure an angular displacement (how far the sample goes)

    • Calculate a rate of displacement (speed/velocity)

Kiss Technology Controlled Stress Rotational Rheometer  Fundamentally a CS rotational rheometer will  Apply torque

Innovation you can build on TM

Kiss Technology Controlled Stress Rotational Rheometer  Fundamentally a CS rotational rheometer will  Apply torque
Kiss Technology Controlled Stress Rotational Rheometer  Fundamentally a CS rotational rheometer will  Apply torque

CS Rheometer - Test Types

  • Rotational tests

    • Upper plate rotates

    • Oscillation tests

      • Upper plate oscillates

CS Rheometer - Test Types  Rotational tests  Upper plate rotates  Oscillation tests 
Kiss Technology
Kiss Technology

Innovation you can build on TM

CS Rheometer - Test Types  Rotational tests  Upper plate rotates  Oscillation tests 

Kiss Technology

Steady State Flow Experiment

  • Provides information on wetting ability of dispersing medium and dispersion stability

  • Successive shear values applied

Kiss Technology Steady State Flow Experiment  Provides information on wetting ability of dispersing medium and
  • Data sampled under defined equilibrium conditions

    • Elimination of start effects or time-dependent transition effects

Denotes measurement Torque / Shear Stress
Denotes
measurement
Torque / Shear Stress

Time

Innovation you can build on TM

Kiss Technology Steady State Flow Experiment  Provides information on wetting ability of dispersing medium and

Kiss Technology

Steady State Flow Experiment

  • The lower relative zero/low shear viscosity (zero/low shear viscosity of dispersion divided by viscosity of neat oil) the better wetting ability

  • The higher zero/low shear viscosity the better dispersion resistance to sedimentation

Kiss Technology Steady State Flow Experiment  The lower relative zero/low shear viscosity (zero/low shear viscosity
  • The steeper viscosity curve between the first and the second Newtonian plateau the narrower molecular weight distribution better dispersion quality

Zero / low shear viscosity Log viscosity
Zero / low shear
viscosity
Log viscosity

Log shear stress

Innovation you can build on TM

Kiss Technology Steady State Flow Experiment  The lower relative zero/low shear viscosity (zero/low shear viscosity

Kiss Technology

Oscillation Stress Sweep

  • Gives information on pigment wetting ability and dispersion stability

  • Application of increasing oscillation shear stress,

Kiss Technology Oscillation Stress Sweep  Gives information on pigment wetting ability and dispersion stability 

usually in a logarithmic ramp, at a constant frequency and temperature

  • Measuring the induced strain enables calculation of the storage modulus G’ (which describes elastic / solid-like behaviour) and the loss modulus G’’ (which describes viscous / liquid-like behaviour)

  • The main aim of the oscillation stress sweep test is to determine the length of linear viscoelastic region (LVR)

Innovation you can build on TM

Kiss Technology Oscillation Stress Sweep  Gives information on pigment wetting ability and dispersion stability 

Kiss Technology

What is LVR?

  • The moduli initially are independent of stress applied, giving a plateau known as the linear viscoelastic region (LVR)

 
Kiss Technology What is LVR?  The moduli initially are independent of stress applied, giving a
Kiss Technology What is LVR?  The moduli initially are independent of stress applied, giving a
Kiss Technology What is LVR?  The moduli initially are independent of stress applied, giving a
 
Kiss Technology What is LVR?  The moduli initially are independent of stress applied, giving a
Kiss Technology What is LVR?  The moduli initially are independent of stress applied, giving a
Kiss Technology What is LVR?  The moduli initially are independent of stress applied, giving a

Innovation you can build on TM

Kiss Technology What is LVR?  The moduli initially are independent of stress applied, giving a
Kiss Technology What is LVR?  The moduli initially are independent of stress applied, giving a

Kiss Technology

Importance of LVR

  • LVR indicates the range of stresses that are non-destructive to the sample - vital for setting

test conditions to probe sample’s structure e.g.

oscillation frequency sweep

Kiss Technology Importance of LVR  LVR indicates the range of stresses that are non-destructive to
  • Can also be used to make assumptions about the stability of a colloidal system

Innovation you can build on TM

Kiss Technology Importance of LVR  LVR indicates the range of stresses that are non-destructive to

Kiss Technology

Oscillation Frequency Sweep

Experiment

  • Gives information on pigment wetting ability and dispersion stability

  • Fixed stress amplitude applied at increasing

frequency

Time Stress
Time
Stress
Kiss Technology Oscillation Frequency Sweep Experiment  Gives information on pigment wetting ability and dispersion stability

N.B. To ensure validity of the analysis, it is necessary to make all measurements in the linear viscoelastic region (LVER)

  • Measured parameters: G’, G’’, δ

Innovation you can build on TM

Kiss Technology Oscillation Frequency Sweep Experiment  Gives information on pigment wetting ability and dispersion stability

Oscillation Frequency Sweep Experiment

  • Analysis of G’,G’’ and δ can provide information on particles association in pigment dispersion hence effectiveness of pigment wetting

 Sample B starts to behave more liquid like (G’’>G’) at lower frequencies compared to sample
Sample B starts to behave more liquid like (G’’>G’) at lower frequencies
compared to sample A – suggests that less agglomerated particles present in
the sample B hence better pigment wetting
Sample A
Sample B
Innovation you can build on TM

Creep Recovery Experiment

  • Creep Recovery tests are used to obtain the most accurate zero shear (“on the shelf”) viscosity

  • Strength of interactions

  • Speed at which at interactions recover

  • Better wetting = more liquid

    • higher displacement

    • lower relative zero shear viscosity

  • Better stability = higher total zero shear viscosity

  • Innovation you can build on TM

    Creep – Recovery Experiment  Creep – Recovery tests are used to obtain the most accurate

    Creep Recovery Experiment

    Supermol L 50% TiO2 3 pass-0001c

    • Supermol L 50% TiO2 3 pass-0001c, Creep

    • Supermol L 50% TiO2 3 pass-0001c, Recovery

    • Crodamol OP 50% TiO2 3 pass-0001c, Creep

    • Crodamol OP 50% TiO2 3 pass-0001c, Recover

    7.00E-4 6.00E-4 5.00E-4 4.00E-4 3.00E-4 2.00E-4 1.00E-4 0 -1.00E-4 0 50.000 100.000 150.000 200.000 250.000 300.000
    7.00E-4
    6.00E-4
    5.00E-4
    4.00E-4
    3.00E-4
    2.00E-4
    1.00E-4
    0
    -1.00E-4
    0
    50.000
    100.000
    150.000
    200.000
    250.000
    300.000
    displacement (rad)

    Innovation you can build on TM

    time global (s)

    Creep – Recovery Experiment Supermol L 50% TiO2 3 pass-0001c Supermol L 50% TiO2 3 pass-0001c,

    Creep Recovery Experiment

    Product

    Crodamol OP Poor Wetter

    Supermol L Good Wetter

    Raw material zero shear viscosity

    0.01372 Pa.s

    1.926 Pa.s

    45% TiO 2 dispersion

    715900000 Pa.s

    • 5020 Pa.s

    viscosity

    - Good Stability

    Relative zero shear

    52179300292 Pa.s

    • 2610 Pa.s

    viscosity

    - Improved wetting

    Innovation you can build on TM

    Creep – Recovery Experiment Product Crodamol OP Poor Wetter Supermol L Good Wetter Raw material zero

    Kiss Technology

    Other Tests

    • Wetting ability of oils and dispersion stability can be investigated further by performing other rheometric tests e.g.:

      • Oscillation Time Sweep

      • Oscillation Temperature Sweep

    Kiss Technology Other Tests  Wetting ability of oils and dispersion stability can be investigated further

    Innovation you can build on TM

    Kiss Technology Other Tests  Wetting ability of oils and dispersion stability can be investigated further

    Kiss Technology

    Pigment Wetting Experimental Work

    • Dispersions of three pigments in a number of different Croda raw materials and compared to Castor Oil

    Kiss Technology Pigment Wetting – Experimental Work  Dispersions of three pigments in a number of
    Kiss Technology Pigment Wetting – Experimental Work  Dispersions of three pigments in a number of
    • Assessments were made at different % pigment (35%; 45% and 55% for inorganic pigments and 25%; 30% and 35% for organic pigment)

    Innovation you can build on TM

    Kiss Technology Pigment Wetting – Experimental Work  Dispersions of three pigments in a number of

    Kiss Technology

    Pigment Wetting Experimental Work

    • Viscosity measurements were taken for each pigment grind

    Kiss Technology Pigment Wetting – Experimental Work  Viscosity measurements were taken for each pigment grind
    • Due to the lack of rheometer at the time most of the study was performed using viscometer (Brookfield)

    • Additional data has since been obtained on

    rheometer for some of the best performing oils

    Innovation you can build on TM

    Kiss Technology Pigment Wetting – Experimental Work  Viscosity measurements were taken for each pigment grind

    Kiss Technology

    Viscosity of Neat Oils

    Kiss Technology Viscosity of Neat Oils Innovation you can build on
    Kiss Technology Viscosity of Neat Oils Innovation you can build on

    Innovation you can build on TM

    Kiss Technology Viscosity of Neat Oils Innovation you can build on

    Kiss Technology

    Titanium Dioxide Dispersions Viscosity Measurements

    Kiss Technology Titanium Dioxide Dispersions – Viscosity Measurements Innovation you can build on
    Kiss Technology Titanium Dioxide Dispersions – Viscosity Measurements Innovation you can build on

    Innovation you can build on TM

    Kiss Technology Titanium Dioxide Dispersions – Viscosity Measurements Innovation you can build on

    Kiss Technology

    Titanium Dioxide Dispersions Relative Viscosity

    • Higher relative viscosity of the grind indicates poorer wetting

    Kiss Technology Titanium Dioxide Dispersions – Relative Viscosity  Higher relative viscosity of the grind indicates

    Innovation you can build on TM

    Kiss Technology Titanium Dioxide Dispersions – Relative Viscosity  Higher relative viscosity of the grind indicates

    Kiss Technology

    Rheometer vs Brookfield

    • Some of the oils were tested on rheometer

     The same trend has been observed as in Brookfield study 1.00E+06 1.00E+05 1.00E+04 35% Untreated
    The same trend has been observed as in Brookfield study
    1.00E+06
    1.00E+05
    1.00E+04
    35% Untreated
    45% Untreated
    1.00E+03
    55% Untreated
    1.00E+02
    1.00E+01
    1.00E+00
    Supermol L
    Castor Oil
    Procas H3
    Kiss Technology Rheometer vs Brookfield  Some of the oils were tested on rheometer  The

    Innovation you can build on TM

    Kiss Technology Rheometer vs Brookfield  Some of the oils were tested on rheometer  The

    Kiss Technology

    Iron Oxide Dispersions Relative Viscosity

    Kiss Technology Iron Oxide Dispersions – Relative Viscosity Innovation you can build on
    Kiss Technology Iron Oxide Dispersions – Relative Viscosity Innovation you can build on

    Innovation you can build on TM

    Kiss Technology Iron Oxide Dispersions – Relative Viscosity Innovation you can build on

    Kiss Technology

    D&C Red No7 CA Dispersions Relative Viscosity

    Kiss Technology D&C Red No7 CA Dispersions – Relative Viscosity Innovation you can build on

    Innovation you can build on TM

    Kiss Technology D&C Red No7 CA Dispersions – Relative Viscosity Innovation you can build on

    Kiss Technology

    Better or Similar Pigment Wetting Performance Compared to Castor

    Oil

     

    Product Name

    Titanium Dioxide

    Iron Oxide

    D&C Red No7 Ca

    Arlamol™ PC10

       

    Arlamol PS15E

       

    Cithrol™ PG3PR

    Cithrol PG32IS

     

    Cithrol PGMIS

       

    Crestalan

    Crodaderm™ S

       

    Crodamol™ GTIS

       

    Crodamol OC

     

     

    Crodamol PTIS

    Crodamol TTIS

       

    Crodasperse

       

    Cromollient™ DP3-A

     

    Monasil™ PCA

    Novol

       

    Pripure™ 3759

       

    Procas H3

    Procetyl™ AWS

    Span™ 80

    Super Sterol Liquid

       

    Supermol™ L

    Innovation you can build on TM

    Kiss Technology Better or Similar Pigment Wetting Performance Compared to Castor Oil Product Name Titanium Dioxide
    Kiss Technology Better or Similar Pigment Wetting Performance Compared to Castor Oil Product Name Titanium Dioxide

    Kiss Technology

    Additional Data

    Oscillation Frequency Sweep

    Kiss Technology Additional Data Oscillation Frequency Sweep Innovation you can build on
    Kiss Technology Additional Data Oscillation Frequency Sweep Innovation you can build on
    Kiss Technology Additional Data Oscillation Frequency Sweep Innovation you can build on
    Kiss Technology Additional Data Oscillation Frequency Sweep Innovation you can build on
    Kiss Technology Additional Data Oscillation Frequency Sweep Innovation you can build on
    Kiss Technology Additional Data Oscillation Frequency Sweep Innovation you can build on
    Kiss Technology Additional Data Oscillation Frequency Sweep Innovation you can build on
    Kiss Technology Additional Data Oscillation Frequency Sweep Innovation you can build on

    Innovation you can build on TM

    Kiss Technology Additional Data Oscillation Frequency Sweep Innovation you can build on
    Kiss Technology Additional Data Oscillation Frequency Sweep Innovation you can build on
    Kiss Technology Additional Data Oscillation Frequency Sweep Innovation you can build on

    Kiss Technology

    Additional Data

    Creep Recovery

    0.6 0.5 0.4 0.3 0.2 0.1 0 450 500 550 600 650 700 750
    0.6
    0.5
    0.4
    0.3
    0.2
    0.1
    0
    450
    500
    550
    600
    650
    700
    750
    • Procas H3 35% Untreated Creep

    • Procas H3 35% Untreated Recovery

    • Procas H3 55% Untreated Creep

    • Procas H3 55% Untreated Recovery

    Innovation you can build on TM

    Kiss Technology Additional Data Creep Recovery 0.6 0.5 0.4 0.3 0.2 0.1 0 450 500 550
    Kiss Technology Additional Data Creep Recovery 0.6 0.5 0.4 0.3 0.2 0.1 0 450 500 550

    Kiss Technology

    Additional Data Creep Recovery

    0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 450 500 550 600 650 700 750
    0.7
    0.6
    0.5
    0.4
    0.3
    0.2
    0.1
    0
    450
    500
    550
    600
    650
    700
    750

    Innovation you can build on TM

    • Procas H3 35% Untreated Creep

    Kiss Technology Additional Data Creep Recovery 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 450 500
    • Procas H3 35% Untreated Recovery

    • Castor Oil 35% Untreated Creep

    • Castor Oil 35% untreated Recovery

    • 35% Supermol L 35% Untreated Creep

    • Supermol L 35% Untreated Recovery

    Kiss Technology Additional Data Creep Recovery 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 450 500

    Kiss Technology

    Additional Data

    LVER Measurement

    30 25 20 35% Untreated 15 45% Untreated 55% Untreated 10 5 0 Supermol L Castor
    30
    25
    20
    35% Untreated
    15
    45% Untreated
    55% Untreated
    10
    5
    0
    Supermol L
    Castor Oil

    Procas H3

    Innovation you can build on TM

    Kiss Technology Additional Data LVER Measurement 30 25 20 35% Untreated 15 45% Untreated 55% Untreated
    Kiss Technology Additional Data LVER Measurement 30 25 20 35% Untreated 15 45% Untreated 55% Untreated
    Experimental Work - Conclusion  6 oils stood out from the crowd  3 oils proved
    Experimental Work -
    Conclusion
    6 oils stood out from the
    crowd
    3 oils proved to be very
    good wetting agents
    Procas H3
    Supermol L
    Crodamol PTIS
    3 oils proved to increase
    the pigment load of the
    disperions
    Crestalan
    Cithrol PG3PR
    Procetyl AWS
    Innovation you can build on TM
    Kiss Technology

    Kiss

    Technology

    Thank You

    Any Questions??

    Innovation you can build on TM

    Kiss Technology Thank You Any Questions?? Innovation you can build on