Pele Oy

Rheology in Paper and Paperboard Coating

Pekka Komulainen
Pekka.Komulainen@clarinet.fi
19 April, 2016
Pele Oy
Rheology in Paper and Paperboard Coating

Contents Page

 Coated Paper and Board Grades 3

 Introduction to Rheology 11
 Particles in Coating Color 19
 Properties of Coating Colors 44
 Rheology od Paper Coatings 69
 Thank You for Your Attention 102

2
Pele Oy

Coated Paper and Board Grades

Pele Oy
Chemical and mechanical pulps

 Chemical pulp papers are called woodfree papers and more than 10% mechanical pulp
containing grades are called mechanical grades.

4
Pele Oy
Publishing paper grades in Europe

 Standard newsprint, improved newsprint and SC magazine papers are uncoated grades.

5
Pele Oy
European coated publishing paper grades

 Coated papers for publishing can be single, double or triple coated. They can be
mechanical papers or woodfree grades. They can be made to matt, silk or glossy finish
and can be delivered in rolls or sheets.
 Usual printing methods are heat set web offset, rotogravure or sheet fed offset.

6
Pele Oy
Coating rheology - important for paperboards

Table origin: www.zumbiel.com

7
Pele Oy
Coated grades by finish

 Matt papers are not calendered or only slightly calendered.

 Silk papers are mostly calendered with two soft nips.
 Gloss papers are fully calendered - at least four or more soft nips.

*Hunter gloss
8
 Surface of paper coating
Pele Oy

Fine kaolin clay

Ground Calcium Carbonate

Pictures: SMI
Precipitated Calcium Carbonate

9
Pele Oy
Coating compared to base paper

 The share of coating layer thickness is only half of the share of grammage because
density of coating is about double in calendered paper. Base paper must be smooth
and have good formation to get a good coated paper surface.

4 - 5 µm

38 - 40 µm

Picture: KCL

Coating density 2000 kg/m3 Coating is a thin layer

Base paper density 1000 kg/m3 compared to base paper

10
Pele Oy

Introduction to Rheology

Dilatancy
Pele Oy
Types of deformation

Coating colors are viscoelastic

Picture: Fapet

12
Pele Oy
Viscoelastic terms

Ideal elastic element – Hookean solid

Deforms when stress is applied. Once stress is removed fully
recovers to the original shape. Modeled as spring.

Ideal viscous element – Newtonian fluid

Flows as long as stress is applied and remains in that shape once
stress is removed. Modeled as dashpot.

Picture: Fapet
13
Pele Oy
Viscoelastic behavior

 Coating colors are viscoelastic. Viscoelastic material has the properties both of
elasticity and viscosity. It is simulated by a Maxwell element. Response of Maxwell
element to strain is the following:

Picture: Fapet
14
Pele Oy
Viscosity, shear stress and shear rate

 Viscosity is resistance of a liquid to flow - molecules slide over one another.

 Viscosity can be defined with a moving plate over a fixed plate. Viscosity η is
Shear stress / Shear rate. In papermaking shear rates are high and viscosities then lower
than with conventional low shear rate measurements.

Pictures: www.viscopedia.com
15
 General flow curve for suspensions
Pele Oy

Picture: Fapet
16
Pele Oy
Types of flow behavior

Shear stress
 Good coating colors are
pseudoplastic to get easy
runnability and good quality.
 If volume concentration is too
high, suspension is easily
dilatant.
 Special binders, rheology
modifiers and lubricants can
help to increase volume
concentration without
dilatancy.
 Dilatant coating colors are
difficult to run leading to
scratches, streaking,
bleeding, too high blade load
and web breaks.

Shear rate 1/s

17
Pele Oy
Types of time-dependent flow behavior

 Coating color should be thixotropic – low viscosity after long shear before and under the
leveling element e.g. blade and high viscosity to start immobilization after the metering
when coating has leveled.

Thixotropic loop

Picture: Fapet
18
Pele Oy

Particles in Coating Color

Pele Oy
Conventional coating color compositions

Picture: SCG-DOW
20
Pele Oy
Typical coating color formulations

 Pigment 100 parts, e.g. Clay (Kaolin), GCC - Ground

Calcium Carbonate, PCC - Precipitated Calcium Carbonate,
Talc, Gypsum, plastic pigment, TiO2 etc.
 Dispersant 0.1-0.5 parts, e.g. polyacrylates, polyphosphates,
lignin sulfonates
 NaOH to adjust pH to 8.5-9
 Binder(s) 5-20 parts, e.g. synthetic binder (XSB, SA, PVAc)
and natural binders (starch and starch based particles, CMC,
casein, soybean protein)
 Cobinder / Thickener 0.5-1.5 parts, e.g. natural products
(starch derivatives, CMC, soy protein, casein) and synthetic
products (PVOH, PVP, HEUR, ASE, HASE, ACT)
 Optical brightener and dyes 0.5-0.8 parts
 Lubricants (calcium stearate, wax, PE- or PP-glycols, soy
lecithin/oleic acid blends) 0.2-0.5 parts
 Other additives, e.g. defoamer/degassing agents, biocides
etc.

21
Pele Oy
Effect of volume fraction on viscosity

 For random packing critical volume fraction of spheres is

0.66 i.e. volume solids is 66%. Volume fraction of dense
tetrahedral packing would be about 74%.
 When shear rate is high, lower than cubic packing (52 %) is
needed to get workable coating color viscosity.
 Mass solids of mineral pigments is always higher than
volume solids because main pigments have densities about
2700 kg/m3 - titanium dioxide even much more.

Pictures: www.wernerblank.com
22
Pele Oy
Low shear rate rheology of GCC/Clay slurries

Picture: Omya

23
Pele Oy
Gloss development of clay/GCC mixtures

Picture: Omya

24
Pele Oy
Solids content and volume fraction

 Titanium dioxide has high particle density (rutile 4230 kg/m3) and latex low density
(max. 1050 kg/m3) compared to mineral pigments. This means that volume fraction is
not directly correlated with mass solids content.

Picture: Omya

25
Pele Oy
Plastic pigments and void volume

 The most efficient pigment is hollow sphere plastic pigment where air filled volume is
55% of the sphere. This means that a very small mass addition increases effective
solids of coating pigments. Effective solids is then much more than actual solids.

Pictures: Rohm and Haas

26
Pele Oy
Particle size effects on viscosity

 The picture on the left means that with smaller particles viscosity is higher.
 Wider particle size distribution = lower viscosity. The picture on the right shows
viscosities for mono-modal, bi-modal and tri-modal particle size distributions.
 Practical coating colors can include foreign particles such as air bubbles, fibers and
fillers from base paper. These increase viscosity.

Picture: Horiba
Log viscosity

100 200 300 nm

Volume Fraction

0.1 0.25 0.50 Picture: www.malvern.com

27
Pele Oy
Particle shape effects on viscosity

 More spherical shape = lower viscosity.

 Viscosity is not related to the static packing rods
Picture: Horiba
density, which would be highest with cubes.
 Viscosity is related to the packing volume of plates
rotating particles.

Log viscosity
 Higher aspect ratio gives higher viscosity
unless particle orientation is reached.
cubes

spheres

0.1 0.25 0.50

Volume Fraction

28
Pele Oy
Viscosity and slurry structure

 High aspect ratio clay and talc can have very

high viscosity if the plates are not aligned but
form structures like house-of-cards.
 Both chemical forces (at low shear) and
mechanical shear forces can form these
highly porous structures.

Picture: www.tulene.edu Picture: www.nature.com

29
Pele Oy
Kaolin structure, charge and pH

 Anisotropic particles such as rods or

plates have different charge at edges
depending on slurry pH.
 It is very important to control constant
pH for this kind of slurries.
 Aspect ratio of kaolin can vary from
10:1 (blocky kaolin) to more than 60:1
(hyperplaty kaolin).

Aspect ratio = L / t = Shape factor

30
Pele Oy
Particle shape and slurry solids

 When solids contents are compared in same viscosity, GCC slurry can be made to 77%
solids and several high aspect ratio clays must have <67%.
 Kaolin is used for paper gloss, better coating coverage and water retention. On the other
hand, higher solids as such compensates very much by improving paper quality, coating
coverage, water retention, print gloss as well as reducing binder demand, which again
improves gloss and smoothness.

GCC

Picture: Imerys

31
Pele Oy
Aspect ratio and in-plane coating strength

 It is interesting to know how platy clays can increase in-plane coating strength and thus
also bending resistance. For packaging grades this is important when both barrier
properties and stiffness increase by using platy grade pigments.

Picture: Imerys

32
Pele Oy
Viscosity and particle shape

 With elongated particles the random orientation leads to an increase in low shear
viscosity. However, under shear these elongated particles can orient themselves to be
streamlined with the direction of flow. They are therefore easier to flow, resulting in a
lower high shear viscosity than the spherical same size equivalent.

Picture: www.azom.com

33
Pele Oy
Bi-modal particle blends

 When two particle sizes are blended the viscosity reaches its minimum
closer to the bigger particles.

Picture: www.azom.com

34
Pele Oy
Viscosity and particle volume fraction

 Coating colors should have high

solids to get good quality and low
water evaporation cost.
 Good water retention also
reduces evaporation energy.
Moistened base paper under the
coating is very difficult to dry
again. Water is not free but
connected to fibers with hydrogen
bonds.
 Fast immobilization after coating
is also important for product
quality and evaporation costs.
 This all means that real coating Picture: www.azom.com
colors must be very close to the
shear thickening range (over 50%
of maximum volume fraction).

35
Pele Oy
Particle size and high shear viscosity

 A higher number of smaller particles results in more particle-particle interactions and an

increased resistance to flow.
 Clearly as shear rate increases, this effect becomes less marked, suggesting that any
particle-particle interactions are relatively weak and broken down at ultrahigh shear rates.
 It is very important to always measure viscosity at ultrahigh shear rate.

Smaller particles – higher

viscosity at low shear rate

Picture: www.azom.com

36
Pele Oy
Blocky and platy pigments

 Blocky particles (carbonates and fine glossing clays) dive into the paper pores and
coating coverage is poor.
 Platy clays stay on the paper surface and improve coating coverage. This is important
for first coating but not as much for the second coating where pores are smaller.

37
Pele Oy
Viscosity explanations

 NPSD or Narrow Particle Size Distribution GCC gives more bulky coating and higher
coating color viscosity.
 BPSD or Broad Particle Size Distribution GCC gives denser coating, lower viscosity and
higher solids coating color.

Picture: Omya

38
Pele Oy
General viscosity order of main coating pigments

 Platy coarse clay is suitable for precoating and fine clay for topcoating if needed
at all.

Picture: Omya

39
Pele Oy
Particle charges and viscosity

 The simplest example concerns hard

spherical particles that don't interact, Picture: www.rsc.org
i.e. there are no forces acting
between them.
 Attraction between particles
increases viscosity and can result in
unstable dispersion forming
aggregates.
 Attraction between particles can be
overcome by making the particles
charged, or 'hairy' by adsorbing a
polymer stabilizer on their surface.
 The presence of a stabilizing layer
increases the effective volume of the
particles and tends to give a higher
viscosity than the ideal system.

40
Pele Oy
Clay slurry dispersion optimization

 The picture shows ACAV viscosity of clay slurry with narrow particle size distribution. One
can see that low shear rate viscosity is not telling very much of the real viscosity.

300
Dispersant level
250 0.22
Viscosity (mPas)

0.24
200 0.26 Lowest viscosity
0.28
150

100

50

0
0 1x10
5
2x10
5
3x10
5
4x10
5
5x10
5

Shear rate (1/s)

41
 Ideal pigment properties
Pele Oy

 Chemically stable and low solubility in water

 High light scattering and low absorption at all wavelengths i.e. good brightness and
whiteness
 Free from impurities, no hard and big particles
 Appropriate particle size and particle size distribution
 High refractive index i.e. good combination of brightness and opacity
 Small binder demand
 Good flow properties as an aqueous suspension (low high shear viscosity)
 Mixes easily with water (wettability, dispersability)
 Good glossing properties (eye-pleasing coating gloss and high print gloss)
 Good compatibility with other coating components
 Low density, coating coverage, bulky paper
 Non-abrasive, low dusting, good strength and stiffness properties
 Low water absorption, easy water evaporation
 Cost effective

42
Pele Oy
Conclusion on main viscosity factors

 In practice mass solids content is measured. Volume fraction varies if components have
different densities. Titanium dioxide is high density pigment and volume fraction is not as
high as solids content shows. Solid plastic pigments have about same density as latex.

Picture: www.malvern.com
43
Pele Oy

Properties of Coating Colors

Pele Oy
Main paper coating principles

Picture: Katarina Dimic-Misic

45
Pele Oy
Main coating methods

 There are three different coating

methods: blade, film transfer and curtain
coating.
 It depends on paper grade and speed
which one is most suitable.

Pictures: Valmet

46
Pele Oy
Main blade/rod coating methods

 Blade coating can have three different

color application methods: applicator
roll, jet and short dwell application.
 Most common color leveling methods
are blade or sometimes rod.
 It depends on paper grade and speed
which one is most suitable.

Pictures: Valmet

47
Pele Oy
Blade coating principle

 The most common paper coating method is blade coating. Speed of commercial coaters
is up to 30 m/s (1800 m/min) and in pilot up to 50 m/s (3000 m/min).
 Coating color application can be with a narrow nozzle (picture), with an applicator roll or
so called short dwell time unit close to the leveling blade itself.
 Typical for these methods is that the applied coating color amount must be 10-20 times
the amount left on the paper surface. Application amount and absorption time before
blade varies depending on the application method and speed.

Coated
paper
Incoming web

Backing
roll

Nozzle gap about 1 mm

Blade and blade holder

48
Pele Oy
Calculation example of coating color formulation

Results 2 Results 3

Substance Parts Dry amount Solids Amount

kg % kg
Kaolin, 80% < 2 µm 50 530.5 68 780
GCC, 90% < 2 µm 50 530.5 75 707
SB-latex 11 116.7 50 233
CMC 1 10.6 10 106
Insolubilizer 0.1 1.1 10 11
Lubricant 1 10.6 50 21
Water 141
Total 113.1 1200 60 2000

Inputs 2 Result 1 Input 1 Result 4

49
Pele Oy
Rheology of coating colors

 Coating colors are complex materials:

 Their viscosity is strongly dependent on shear rate
 Viscosity is dependent on shearing time
 They are viscoelastic
 They may have significant extensional viscosity and/or
normal stresses
 Base paper and water retention have effect on coating
color rheology
 Surface chemistry and hydrodynamics determine viscosity.
 Significance of different factors depends on shear rate. It is
not usually possible to draw conclusion about high shear Picture: Voith
rheology by measuring low shear area, or vice versa.
 Coating colors are shear thinning at low shear rate area.
However, there may be dilatant behavior at higher shear
rates.

50
Pele Oy
Types of coating color flow behavior

 Coating color must be shear thinning = pseudoplastic. Shear thickening =

dilatant is not good for blade coating.

51
 Coating color viscosity depends on shear rate
Pele Oy

2000
Chemical Factors
• Van der Waals
1500 • Electrostatic repulsion/attraction
• Steric factors
Viscosity (mPas)

1000
Hydrodynamics
• Particle size and size distribution
• Particle shape
• Viscosity of water phase
500 • Volume fraction (solids)

PCC-slurry
0
0.0 2.0x105 4.0x105 6.0x105 8.0x105
Shear rate (1/s)
www.aca.fi
52
Pele Oy
Dominating factors at different shear rates

SURFACE CHEMISTRY AT LOW SHEAR

 Volume fraction of particles Brookfield,
 Electric attraction/repulsion rotational
 Van der Waals attraction and capillary
 Steric repulsion viscometers
 Viscosity of water phase

HYDRODYNAMICS AT ULTRA HIGH SHEAR

 Volume fraction of particles
 Particle size
 Shape of the particles
 Particle size distribution
 Viscosity of water phase Capillary and
Slit viscometers

53
Pele Oy
Coating color shear rates in real process

Rod
Blade
Screens

Curtain hitting point

Mixing

Pumping Applicator Nip

Coating color circulation loop

Capillary and slit viscometers

0 102 103 104 105 106 107

www.aca.fi
Shear Rate (1/s)

54
Pele Oy
Shear rate ranges of viscometers

 It is easy to note that coating research without using capillary or slit viscometer is not
relevant. There are still whole countries, where all research and development is made
with rotational viscometers.

Practical Shear
Viscometer Comparison to process
rate (1/s)
Real shear rate 200.000 times
Brookfield 10
higher

Rotational 40 000 Real shear rate 50 times higher

Shear rate comparable to

Capillary 2 Million
process
Possibility to simulate also
Slit 10 Million
highest shear rates

55
Pele Oy
Typical ultrahigh shear viscosity curves

 Especially in blade coating it is important to know and control ultrahigh shear viscosity.
Typical measurement curves of good coating colors are in the picture below.

www.aca.fi

56
Pele Oy
Suspension property effects on coating

 In coating colors intermolecular forces and particle charges have effect on viscosity
measured with conventional viscometers.
 However, practical shear rates of coating colors are so high that more important are
hydrodynamic forces arising from particle shape and rotation in the suspension.
 Viscosity should be measured with capillary/slit viscometers to get practical shear rates.

Change in Effect on Effect on water Effects on process and

Variable
variable viscosity retention quality
Intermolecular Increased low
Increase Better There is an optimum
forces shear viscosity
Particle volume Better quality, runnability
Increase Increase Better
concentration limit
Lower quality, lower binder
Particle size Increase Decrease Lower
demand
Particle size Denser coating, lower
Wider Decrease Better
distribution coating coverage
Less Better gloss, runnability limit
Particle shape Increase Better
spherical

57
 Temperature and coating color viscosity
Pele Oy

 Theoretically increase of temperature decreases viscosity. However, higher

increase of coating color temperature destroys the surface active ingredient of the
latex and ultrahigh viscosity increases with temperature.

80
Logical behaviour below 100.000 1/s
70 60ºC
60
Viscosity mPas

50

40 50ºC
30
30ºC
20

10 Coating shear rates

0
0 200000 400000 600000 800000 1000000 1200000

Shear rate 1/s

58
Pele Oy
Low shear viscosity of coating components

Albagloss is PCC

Picture: Michel-Sanchez Enrique

59
Pele Oy
Example of flow patterns in blade coating

Picture: C.K.Aidun

60
Pele Oy
Coating shear rates

 Paper speed can be up to 30 m/s. The average gap between paper

web and blade is about 20 µm. Average shear rate is then 1.5x106 1/s.
 Minimum distances are much less than the average coating thickness
and maximum local shear rate is higher than the calculated average.
 Coating color should tolerate shear rates of some millions in blade
coating.

Backing Roll
 The risk of dilatancy with shear thickening color is always present –
even if the coater speed is much less than 30 m/s.

Contacts
Blade Coating

Base Paper Color

Base Paper

61
Pele Oy
Ultra high shear viscosity curves

Area Rheology Problems

A High viscosity at low shear rates Pumping and startup problems
B High viscosity at high shear rates Problems in screens and applicators
Blade bleeding and streaking
High viscosity at ultrahigh shear
C rates, dilatant
Problems maintaining target coat weight
Web breaks
Low viscosity at ultrahigh shear
D rates
Uneven coat weight

E Low viscosity at all shear rates Water retention problems

Picture: Valmet
Modified from: www.aca.fi

62
Pele Oy
Curtain coating and extensional viscosity

 Instead of old air knife coating curtain coating is used when a contour coating is needed.
 Extensional viscosity is a color’s resistance to accelerating flow. Extensional viscosity is
most important in curtain coating but also in blade coating after blade.
 Coating colors contain polymeric thickeners, which have considerable effect on
extensional viscosity.
 Extensional viscosity can be measured with ultrahigh shear rate slit viscometer.

Picture: Voith Orientation and

straightening
in accelerating flow

Picture: www.aca.fi

63
Pele Oy
Flow pattern in blade coating exit

 Flow is contracted after the blade about 50% which means that the average flow
speed after the blade is doubled.

Picture: Douglas W. Bousfield

64
Pele Oy
Slit in high shear measurement

 Slit geometry is comparable with blade coating geometry. With rigid blade the angle is
about 45º and gap is 15-25 µm (contraction after blade about 50%).
 Slit is just two blades against each other. Because the length is only 0,5 mm the delay
time in the measurement is very short, similar to blade coating.
 The problem with rotating viscometers is long measurement time and heating of the
dispersion. Thixotropy has effect on the measurement.

BLADE
SLIT

0.5 mm
~ 0.5 mm Coating Color

80 µm
~ 20 µm

Base paper
www.aca.fi

65
Pele Oy
Capillary and slit correlation to runnability

 Blade coating runnability was followed and ultrahigh shear viscosity measured.
Correlation of slit viscosity to runnability was superior compared to capillary viscosity.

Capillary measurement, 0.5 Mill. 1/s Slit measurement, 3 Mill. 1/s

and poor correlation and good correlation
www.aca.fi
66
 Practical shear rate ranges of viscometers
Pele Oy

ACAV A2

ACAV A4

Eklund

Hercules

Haake

Brookfield

0 1 2 3 4 5 6 7 8 9 10
Shear Rate x 106 (1/s) www.aca.fi

67
 Comparison of shearing times
Pele Oy

Shearing
Viscometer Compared to process
time

Brookfield 1s Tens of thousand times

Rotational 1s Tens of thousand times

ACAV Capillar 1 ms About 30 times longer

ACAV SLIT 30 µs Same as under blade

www.aca.fi

68
Pele Oy

Rheology of Paper Coatings

Pele Oy
Viscosity of fine and coarse pigments

 Pigment type has effect on reachable viscosity and solids content of the pigment slurry
and coating color.
 Coarse and platy clay has lowest possible solids and GCC with broad particle size
distribution highest.

Picture: Omya

70
Pele Oy
Effect of aspect ratio on pigment slurry solids

 It is important to know the aspect ratios of clays to predict the effect on possible solids
content and gloss.

Picture: Omya

71
Pele Oy
Gloss and surface strength

 Adding GCC with broad particle size distribution to high glossing clay increases
solids content and surface strength but decreases sheet gloss.

Picture: Omya

72
 Effective solids and ultrahigh shear viscosity
Pele Oy

Picture: Omya

73
Pele Oy
Coater speed and clay content

 Share of clay in carbonate coating reduces solids content and maximum coating speed.
Critical speed is defined with visual examination of stalagmites or coating scratches.

TAPPI 1999

Blade

74
Pele Oy
Window for ideal solids

 Window for ideal solids is very narrow. Too high solids results in runnability problems
and too low solids in quality problems. Process variations should be minimized to be
able to run close to the maximum solids.

Picture: Omya

75
Pele Oy
Coarse and fine clay in topcoating color

 Viscosity of coarse and platy clay is considerably higher than with fine clay. Reduced
amount (15%) of coarse clay in the formulation gives almost same ultrahigh shear
viscosity as 25% fine clay. The main pigment here is fine GCC.
 Higher ultrahigh shear viscosity means that blade load in real coating is higher.

Viscosity / Shear rate

120
Coarse clay 25%
100

80
Coarse clay 15%
Viscosity, mPas

60
Fine clay 25%
40

20

0
0 200000 400000 600000 800000 1000000 1200000

Shear rate, 1/s

76
Pele Oy
Double coated papers

 There is less platy clay on the left coating formula in precoating. Solids content and
coating coverage are lower.
 On the right, more platy particles can give relatively better water retention,
smoothness, print gloss, coating coverage, ink holdout, print density, paper stiffness
and bulk.

Fine clay Coarse clay

Picture: Kenji Hirai

77
Pele Oy
Water retention principles

 Water retention is an important

factor in coating coverage.
 Two principles have effect: color
viscosity and shape factor of
particles.
 Low shear viscosity has effect on
Low viscosity,
capillary penetration and ultra- High viscosity,
fast penetration
high shear viscosity under the slow penetration
blade or rod.

Low aspect ratio, High aspect ratio,

fast penetration slow penetration

Picture: Kenji Hirai

78
Pele Oy
Water and coating penetration

 When speed is low, capillary penetration is high from application up to immobilization

of coating. Platy particles decrease penetration.
 When drying is slow and far from the blade, capillary penetration continues long way
after the blade.

Blade

79
Pele Oy
Filter cake formation and water retention

 Capillary absorption forces are working before and after the blade pressure.
 Pressure penetration is most effective under the blade.
 Filter cake formation decreases the effective coating layer gap under the blade.
This can increase shear rate (speed gradient) considerably.

80
Pele Oy
Rheology and water retention

GWR/HS viscosity; PCC/Clay 70/30, latex 12 pph

110
62.5%
Water retentio, g/m2

105 63.6%
Quality limits

62.5%
100 64.3%

95 Operating 65.1%

90 Laboratory Study
6
Window 64.3%
66.1%
66.0%

85 63.2%
80
75
Impact of new binders
65.2%

Runnability limits
66.9%

70
20 40 60 80 100 120

High shear viscosity @ 800 000 1/s , [mPas]

Latex 1 Latex 2 Latex 3 Latex 4 Picture: SMI

81
Pele Oy
Origins of blade coating scratches

 Base paper
 Particles bigger than 20 µm. Stickies, pitch, white pitch, filler,
fiber bundles, fiber vessels/ray cells, sand, coated broke,
chemical agglomerates, wet end chemistry problems.
 Loose fibers on top layer or filler layer, poor surface sizing,
size agglomerates or retrogradation, paper pieces in size
circulation, poor screening in size circulation.
 Coating color
 Screening of pigment/color
 Hard pigment particles
 Too high solids or low water retention, dilatancy in high
shear rate
 Poor dosage of dispersion agent or dispersion stability
 Air in coating color leads to higher viscosity
 Poor mixing of pigment/coating color
 Fibers in color
 Air in color

82
Pele Oy
Effect of solids and latex on color rheology

 GCC here is of NPSD-type or has narrow particle size distribution.

Pictures: Omya

83
Pele Oy
Effect of latex particle size on rheology

Picture: Omnova
84
Pele Oy
Effect of latex on ultrahigh shear viscosity

 Even if the latex in the formulation was only 12 parts (pigments 100 parts), it had great
effect on viscosity when narrow particle size distribution PCC was included. PCC was
70% and fine clay 30% of the pigments. Conventional formulation was with GCC.

Picture: Dow
85
Pele Oy
Relaxation-induced dilatancy

 The numerical simulations carried out suggest that the non-​hydrodynamic interactions
between particles are able to store energy when the coating layer is being compressed
e.g. by the pressure pulse of a coating blade.
 Relaxation of the stored energy has a potential to expand the system volume and
induce dilatancy under conditions of water loss.
 Correct formulation improves visco-elasticity of coating colors, and controls occurrence
of bleeding as well as dynamic water retention under the blade.

Good formulation – no bleeding

Picture: Somar
86
Pele Oy
Detailed behavior of coating color

 Viscoelastic regions are subjected

during coating metering to high
compressive forces. Dissolved
material and fines are released
from the elastic regions similar to
the compression of a sponge.
 The released fluid inclusive
dissolved and dispersed matter is
accelerated along the directional
force of the pressure impulse, e.g.
perpendicular to the pressure
impulse.
 Solid and liquid phase of the
coating color are separated under
pressure. After pressure decay the
compressed regions expand again
and pick up of what free liquid
phase is still left in the wet film.

Picture: CTP
87
Pele Oy
Coating holdout and binder migration

 On the left picture there is good coating holdout and no binder migration.
 When water retention is poor, binder can migrate to the base paper during water
absorption and before immobilization point.
 Other type of migration is during drying to the paper surface (skinning).
 Both cause poor picking strength and mottled printing result.

Picture: Somar
88
Pele Oy
Working principle of rheology modifiers

Picture: Derrick Burrel, 2007 TAPPI Coating & Graphic Arts Conference

89
Pele Oy
Effects of associative rheology modifiers (RMs)

 Associative RMs thicken water phase with swelling and polymer network in the
suspension so that low shear viscosity increases but ultrahigh shear viscosity decreases
through breaking down this polymer network between suspension particles.
 RMs enhance orientation of high aspect ratio particles under ultrahigh shear rate and
thus increase critical volume solids. RMs also reduce friction between particles so that
particles can easier flow in a shear field over each other.
 They improve static and dynamic water retention.
 RMs also improve rheology after metering to reduce coating defects and to improve
leveling before fast immobilization.

Picture: Derrick Burrel

90
Pele Oy
Practical effects of rheology modifiers

 It seems that HASE (associative

rheology modifier) is best in all
other properties than in water
retention.
 If water retention is reached with
suitable pigments and binders,
HASE seems to be the best
rheology modifier.
 ASE seems to be most balanced
when improvement from cellulosic
water retention additives are
desired,

Picture: Derrick Burrel, 2007 TAPPI Coating & Graphic Arts Conference

91
Pele Oy
Ultrahigh shear rate viscosity of rheology modifiers

Picture: Derrick Burrel, 2007 TAPPI Coating & Graphic Arts Conference

92
Pele Oy
Effect of elasticity in coating

 Lubricants may turn the balance of a

viscoelastic coating color more viscous and less
elastic and thus enable easier flow of a coating Lubricants:
color still in very high coating solids. Together Coating
Lower
with higher coating solids and higher coating Additives friction
speeds also better paper quality may be
achieved.
 Lubricants may have ability to reduce friction Thickeners: Both:
and increase slip at the blade boundary thus Viscosity Rheology
preventing bleeding and dry stalagmite modification
formation. increase
 It must be remembered that base paper under
the blade is compressed and behaves more
elastic than wet coating layer. In addition,
thickness of base paper is several times the
thickness of coating layer.
 Sometimes base paper is not calendered at all.
This kind of base paper is much more
compressible than calendered base paper.

93
Pele Oy
Lubricants in coating

 Lubricants and release agents are used to

enhance smoothness and flow properties
of wet coating as well as the plasticity and
gloss of dried coating.
 Lubricants can also effect on color
rheology thus reducing build up of
stalagmites in blade coating.
 Lubricants are also used to reduce
calender picking and dusting by reducing
paper friction against calender rolls and
enhancing deformation of paper surface in
calender nips.
 Lubricant products are mostly calcium and
ammonium stearates. Wax emulsions are Lubricants reduce COF of coated paper
emulsions of paraffin waxes,
microcrystalline waxes or polyethylene
waxes.
Picture: Toshiharu Enomae

94
Pele Oy
Pigment packing effect on absorption

 To get good coating coverage it is important how porous and tortuous the base is.
 On the left picture base paper is not calendered or first coating is too open to get good
water retention and coating coverage. The same is valid for printing ink and the term is
normally ink hold out.

Open structure – Low tortuosity

High density and platy particles
High tortuosity

Picture: Daniel Matte

95
Pele Oy
Ultra high shear viscosity vs. coating scratches

 Slit viscosity correlates very well with scratch count in blade coating. Scratches are a
potential defect with high solids content and coarse platy pigments.

0% 0%

0,40 %

0,40 %

0,80 % 0,80 %

1,60 %

1,60 %

Results: TAPPI, 2001 Coating and Graphics Arts Conference and Trade Fair, pages 77 -86
Dr. Rajan R. Iyer, Ray Hollingsworth, Dr. David R. Skuse, Imerys, Sandersville,USA

96
Pele Oy
Conclusion on dispersant dose

Imerys researchers make the following conclusion:

 “Pilot coating data show a clear improvement in
scratch reduction upon higher dispersant dose
addition. There is a correlation between coating
color viscosity and the scratch counts observed on Brookfield
the machine.
Hercules
 Better correlation between coating color viscosity
and scratch counts is observed when the viscosity Real
is measured with a slit attachment to a capillary
viscometer.
 This may indicate that the slit attachment measures
viscosity of the coating under conditions similar to
the converging geometry obtained in blade coating
operations, or that the timescale of measurement in
this device is closer to that of blade coating.
 This implies that the elastic component of the color
rheology is important and this should be measured
in any future study.”

97
Pele Oy
Effect of dispersants and thickeners

 If the dispersant level is too high there can be problems in recirculating color stability
(left lower curves).
 For extensional viscosity interactive thickener seems to be most effective (right picture).

Pictures: Imerys

98
Pele Oy
Special latex - biolatex behavior

 Ultra-high shear viscosity measurements show that deforming soft latex particles
have higher low shear viscosity but lower ultra-high shear viscosity.
 Soft biolatex can deform, orientate and shrink under high shear.

Picture: Ecosynthetix

99
Pele Oy
Ultrahigh shear rate viscosity of three binders

Picture: Ecosynthetix
100
Pele Oy
Coating color development

 In coating developed the key question is to use relevant laboratory methods. The most
important ones are ultrahigh shear viscosity and dynamic water retention. The
following conclusion is from Ecosynthetix presentation in PaperCon2012 Conference.

 , PaperCon2012

101
Pele Oy

Dilatant sand – Quicksand

102