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Pigment Wetting

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Agenda
 Principles of pigment wetting

 Methods of analysis

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 Experimental work and results discussion

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 Pigments Dispersion Principles
 Lipsticks consist of a mixture of oils and waxes with
pigments dispersed throughout

 Dispersion of pigments in a liquid medium is

typically accomplished in 2 steps:

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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)

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

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 It can be influenced by:
 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.
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Importance of Effective
Pigment Wetting
 Effective wetting facilitates particles separation, so
agglomerates are easily milled and offer consistent
colour dispersion throughout
Intrinsic colour strength

Effective wetting

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Poor wetting

Mill time

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Importance of Effective
Pigment Wetting
 Poor wetting leads to higher viscosity of the
dispersion hence lower pigment load and higher
processing time and costs

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Viscosity

Poor wetting

Effective
wetting

Pigment
concentration

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

 At very low shear, internal

First Newtonian plateau
friction of the particles is at

Log viscosity
maximum and viscosity is Shear thinning region

apparently independent of shear rate

(first Newtonian plateau) Second Newtonian plateau

 As shear increases, the system will 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

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 Pigment Wetting – Methods
of Measurement
 The pigment wetting ability of oils can be quantified by
relative viscosity measurements and analysing rheology of
pigment dispersions

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

dispersing medium)

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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

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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)

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CS Rheometer - Test Types

 Rotational tests  Oscillation tests

 Upper plate rotates  Upper plate oscillates

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Steady State Flow Experiment
 Provides information on wetting ability of dispersing
medium and dispersion stability

 Successive shear values applied

 Data sampled under defined equilibrium conditions

 Elimination of start effects or time-dependent
transition effects

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Torque / Shear Stress

Denotes
measurement

Time
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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

 The steeper viscosity curve between the first and the

second Newtonian plateau the narrower molecular weight
distribution – better dispersion quality

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Zero / low shear
Log viscosity

viscosity

Log shear stress

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

 Application of increasing oscillation shear stress,

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

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 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)

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

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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

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 Can also be used to make assumptions about
the stability of a colloidal system

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

 Fixed stress amplitude applied at increasing

frequency

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Stress

Time

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

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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 A – suggests that less agglomerated particles present in
the sample B hence better pigment wetting

Sample A
Sample B

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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

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 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, Recovery

7.00E-4

6.00E-4

5.00E-4

4.00E-4
d isp lacem e n t (ra d)

3.00E-4

2.00E-4

1.00E-4

-1.00E-4
0 50.000 100.000 150.000 200.000 250.000 300.000
time global (s)

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Creep – Recovery Experiment

Product Crodamol OP Supermol L

Poor Wetter Good Wetter

Raw material zero 0.01372 Pa.s 1.926 Pa.s

shear viscosity

45% TiO2 dispersion 715900000 Pa.s 5020 Pa.s

viscosity - Good Stability

Relative zero shear 52179300292 Pa.s 2610 Pa.s

viscosity - Improved wetting

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Other Tests

 Wetting ability of oils and dispersion stability can be

investigated further by performing other rheometric
tests e.g.:

 Oscillation Time Sweep

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 Oscillation Temperature Sweep

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Pigment Wetting – Experimental
Work
 Dispersions of three pigments in a number of
different Croda raw materials and compared to
Castor Oil

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 Assessments were made at different % pigment
(35%; 45% and 55% for inorganic pigments and
25%; 30% and 35% for organic pigment)

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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)

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 Additional data has since been obtained on
rheometer for some of the best performing oils

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Viscosity of Neat Oils

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Titanium Dioxide Dispersions –
Viscosity Measurements

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Titanium Dioxide Dispersions –
Relative Viscosity

 Higher relative viscosity of the grind indicates

poorer wetting

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 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

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35% Untreated
45% Untreated
1.00E+03
55% Untreated

1.00E+02

1.00E+01

1.00E+00
Supermol L
Castor Oil
Procas H3

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Iron Oxide Dispersions –
Relative Viscosity

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D&C Red No7 CA Dispersions –
Relative Viscosity

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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 ■

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Crodamol PTIS ■ ■ ■

Crodamol TTIS ■

Crodasperse™ ■

Cromollient™ DP3-A ■ ■

Monasil™ PCA ■ ■ ■

Novol™ ■

Pripure™ 3759 ■

Procas H3 ■ ■ ■

Procetyl™ AWS ■ ■ ■

Span™ 80 ■ ■ ■

Super Sterol Liquid ■

Supermol™ L ■ ■ ■

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Additional Data
Oscillation Frequency Sweep

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 Additional Data
0.6
Creep Recovery

0.5

0.4

Procas H3 35% Untreated Creep

0.3 Procas H3 35% Untreated Recovery

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Procas H3 55% Untreated Creep
Procas H3 55% Untreated Recovery

0.2

0.1

0
450 500 550 600 650 700 750

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 Additional Data
Creep Recovery
0.7

0.6

0.5
Procas H3 35% Untreated Creep

Procas H3 35% Untreated Recovery

0.4
Castor Oil 35% Untreated Creep

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Castor Oil 35% untreated Recovery
0.3
35% Supermol L 35% Untreated
Creep
Supermol L 35% Untreated Recovery
0.2

0.1

0
450 500 550 600 650 700 750

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Additional Data
LVER Measurement

30

25

20

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35% Untreated
15 45% Untreated
55% Untreated
10

Supermol L
Castor Oil
Procas H3

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Experimental Work -
Conclusion
 6 oils stood out from the
crowd

 3 oils proved to be very

good wetting agents
 Procas H3
 Supermol L

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 Crodamol PTIS

 3 oils proved to increase

the pigment load of the
disperions
 Crestalan
 Cithrol PG3PR
 Procetyl AWS

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Thank You
Any Questions??

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