Seminar

Basics of Rheology
Markus Nemeth

very
welcome !

1
 Introduction
Viscoelastic Behavior

Rheology
to describe deformation and flow behavior of all kinds of materials.

_______________________________________

Each material under load is showing

viscoelastic behavior
(as a mixture of viscous and elastic behavior).

viscous  viscoelastic  elastic

2
 Introduction
Viscoelastic Behavior
Using a simple illustrative picture:

„The Rheology Road“

viscous  viscoelastic  elastic

ideally viscous viscoelastic viscoelastic ideally elastic

liquids liquids solids (rigid) solids
such as water, oils such as glues, such as pastes, such as stone, steel
Law of Newton shampoos gels, rubbers Law of Hooke

 rotational tests  |
 oscillatory tests 

3
 Simple Test Methods
Trowel Test and Finger Test

trowel test
- high-viscosity fluids: “thick“
- low-viscosity fluids: “thin“
e.g. for dispersions

finger test
- tacky: “long“
- less tacky: “short“
e.g. for adhesives,
offset-printing inks, dough

4
 Simple Test Methods
Bostwick Consistometers

flow due to gravity:

measurement of the flow path
in a preset time period.
Examples: foods such as ketchups and other kinds of fruit purees

View from above on a

Bostwick constistometer

1 sample container, max. V = 100 ml

2 outlet gate, to be opened using a spring
3 scaled flow path

5
 Simple Test Methods
Falling-Ball Viscometers

measurement of the time

measuring tube
for the ball to travel downwards
and ball
over a defined distance
thermometer

for testing transparent liquids

stand
according to ISO 12058
jacket, for
and DIN 53015
temperature
control

Example:
The Micro-Falling Ball Viscometer AMVn of Anton Paar for low-viscosity liquids  Movie
such as biological fluids ([Link] solutions), inks, polymer solutions, beer wort (motor oils)

6
 Simple Test Methods
Falling-Rod Viscometers

weight

measurement of the time

printing ink for the rod to travel downwards
over a defined distance

e.g. for testing

offset-printing inks (highly viscous)
and pastes

falling rod

falling rod viscometer,

e.g. type Laray

7
 Simple Test Methods
Bubble Viscometers

a gas bubble is rising

when the tube
is turned,
viscosity evaluation
by comparison
to standard oils

measurement of the time

for an air bubble to rise

for testing transparent liquids

according to ASTM D803 and D1545,
Example: oils

8
 Simple Test Methods
Flow Cups

water-clock (klepsýdra)
for time measurements

since about 3500 years used in Egypt,

and later e.g. at justice courts in Greece

For example:
A water container containing 5 l of water
with an outlet,
for a flow time of about 6 min

9
 Simple Test Methods
Flow Cups

measurement of the
flow time
of low-viscosity liquids

determination of the

kinematic viscosity
(weight-dependent viscosity !)

Examples: oils, solvent-based coatings,

gravure and flexo printing inks

10
 Simple Test Methods
Flow Cups

ISO
DIN
DIN Ford (ASTM)

Zahn
Engler
Shell
ISO

diverse designs of
viscosity flow cups
11
 Simple Test Methods
Glass Capillary Viscometers

measurement
of the
flow time
of transparent
liquids

determination
of the

kinematic
viscosity

Examples:
mineral oils,
diluted polymer
solutions

diverse designs of glass capillary viscometers

12
 Simple Test Methods
Stormer Rotational Viscometers

preset:
force (constant torque),
here using a free falling weight
(in grams)

measurement:
rotational speed
of the measuring system

Using the stirrer-like

Krebs measuring systems
(„paddles"),
relative values
are produced;
typical designation as
Krebs Units (KU)

13
 Simple Test Methods
Brookfield Rotational Viscometers
preset: rotational speed
measurement: torque

Using the typical spindles,

relative values
are produced.

- cylinders
- disks
- pins
- T-bars

14
 Simple Test Methods
further Systems for Relative Values

helix 1 helix 2 blade anchor

ball measuring system

All these kinds of stirrers are

relative measuring systems
stirrer for starch
building materials stirrer

15
 Rheometry
Rheometry
Absolute Measuring
Measuring Systems
Systems for Absolute Values
Measuring geometries for rotational and oscillatory rheometers
according to DIN 53019 (for all the 3 geometries), and ISO 3219 (only for CC and CP)

cone & plate, CP

for liquids;
for dispersions only for
parallel - plates, PP
a limitted particle size.
useful for
Example: For CP 25-1, gels, pastes,
with 2R = 25 mm soft solids,
and = 1°, polymer melts
concentric cylinders, CC typically a = 50 µm;
for low-viscosity liquids, and thus, for a max. particle
not for pastes (air bubbles) size of d  (a/10) = 5 µm
16
 Definitions
Shear Stress and Shear Rate
The two-plates model
shear stress  =
F
A
unit: 1 N / m2 = 1Pa


v
shear rate = (D) =
h
unit: 1 m / (sm) = 1/s = 1 s-1

Laminar flow with flowing layers

(in contrast to turbulent flow with vortices)

  dv  const.  const.  e-learning

(laminar, 2-P-M)
dh const.
 Movie  Movie
(„peas“) (turbulence)

17
 Application
Typical Shear Rates

Process Shear Rates (s-1)

sedimentation < 0.001 to 0.01
surface levelling 0.01 to 0.1
sagging 0.01 to 1
dip coating 1 to 100
pipe flow, pumping, filling into containers 1 to 10,000
coating, painting, brushing 100 to 10,000
spraying 1000 to 10,000
(high - speed) coating, blade coating 100,000 to 1 mio.

18
 Application
Sedimentation, Long-term Storage Stability
dispersions
Stability of dispersions
Example: salad dressings
in the beginning after 15 min

 Movie
Behavior in the low-shear range or at rest, respectively (sedimentation)

19
 Application
Levelling and Sagging after Coating
coatings
Levelling, brush marks, wet-layer thickness, sagging
example: brush paints

at very low shear rates between 0.01 and 1 s-1

(or at rest, respectively)
20
 Application
Coating, Painting, Brushing
coatings
Application example: painting

brush velocity
(v = 0.5 m/s)

wet layer
thickness
(h = 200 µm)

calculation of the shear rate: brushing, painting

at medium and
Δv
  
0.5 m
4
 2500 s1 high shear rates of
Δh 2  10 m  s between 100 and 10,000 s-1

21
 Application
Automotive Coating
coatings
a) Plastisols: seam sealing and under-body sealing
b) Coatings: dip coating, filler, base coat, clear coat
c) Waxes: cavity conservation

car body degreasing & phosphatizing electro dip coating

spraying, coating
at high shear rates
of 1000 to 10,000s-1
seam sealing underbody spraying

filler base coat and clear coat cavity conservation

22
 Application
Flow in Capillaries and Pipes
pastes
Application example: squeezing out a tooth paste
flowing volume V = 1cm3
flow time t = 1s
thus: flow rate V/t = 10-6 m3 / s
tube nozzle („pipe radius“, half diameter) d = 2R = 6mm, thus: R = 3  10-3m

calculation of the shear rate (formula of Hagen and Poiseuille):

 = (4  V) / (  R3  t) flow in pipes, capillaries
= (4 10-6 m3/s) / (  27 10-9 m3 ) at shear rates
= 47.2s-1 = about 50s-1 between 1 and 1000s-1

23
 Definitions
Viscosity Law

definition of the
(shear) viscosity

η τ  Pa 
1/s   Pas
γ  

unit: 1 Pa / (1/s) = 1 Pas = 1000 mPas

Isaac Newton (1643 to –1727)
(1643 1727) (pascal-seconds, milli-pascal-seconds)

previously used unit:

1 cP = 1 mPas
(centi-poises)
This is not an SI-unit !

24
 Application
Viscosity Values

Materials Viscosity 
Gases / air 0.01 to 0.02 / 0.018 mPas
Water at 20°C 1.0mPas
(at 0 / 40 / 60 / 80 / 100°C) (1.8 / 0.65 / 0.47 / 0.35 / 0.28)
Milk, coffee creams 2 to 10 mPas
Olive oils approx. 100 mPas
Motor oils (at T = RT) 50 to 1000mPas
SAE 10W-30, at +23 / +50 / +100°C 175 / 52 / 20 mPas
Polymer melts (at T= +150 to +300°C, 10 to 10,000 Pas
and at shear rates of 10 to 1000 s-1)
Polymer melts (zero-shear viscosity) 1 kPas to 1 MPas
Bitumen (at T = +80 / +60 / +40 200 Pas / 1 kPas / 20 kPas
/ +20 / 0°C) / 0.5 MPas / 1 MPas  e-learning
(visco-turtles)

25
 Application
Viscosity Values
printing inks
Viscosity values
ink fountain
should be measured under
application dependent
1 ink fountain roll conditions
2 metering roll
3 distributer rolls
Example:
4 vibrator rolls offset printing machine
5 ink form rolls 1) at rest
6 rider roll (in the ink container:
7 pan roll liquid or solid behavior ?)
8 slip roll 10
2) at high shear rates
9 dampener form roll
(film splitting defects by
10 plate cylinder
taking up dampener fluid,
11 blanket cylinder
11 decrease in color density ?)
3) first at a high,
and then at a low
paper web shear rate
11
(printing process and dot
sharpness, e.g. using two
test intervals for testing)
26
 Definitions
Kinematic Viscosity

kinematic viscosity 

unit: 1 mm2 / s
1 m2 / s = 106 mm2 / s

previously used unit: 1 cSt = 1 mm2/s (centi-stokes)

This is not an SI-unit !
unit of the density : 1 g/cm3 = 1000 kg/m3
The kinematic viscosity is measured
ever then , when
gravity
is the driving force
(or the weight of the sample, resp.),
for example, when using
flow cups or capillary viscometers

27
 Rheometry
Rotational Tests

Rotation CSR
test preset result
(controlled shear rate)

raw data rotational speed n [min-1] torque M [mNm]

rheological parameters shear rate  [s-1] shear stress  [Pa]

torque M: 1Nm = 1000mNm, rotational speed n: 1rpm = 1/min

Rotation CSS
test preset result
(controlled shear stress)

raw data torque M [mNm] rotational speed n [min-1]

rheological parameters shear stress  [Pa] shear rate  [s-1]

 Movie  e-learning
(merry-go-round) (rotation)

28
 Rheometry
Measured Parameters

Physical parameters: Rheological parameters:

raw data, calculated values,
disadvantage: dependent advantage: independent
on the measuring system of the measuring system

torque M [Nm] shear stress = CSS MPa

rotational speed n [min-1] shear rate  = CSR n s-1
deflection angle  or [rad] shear deformation = CSD  1 or %

For each individual measuring system

there are existing the following two
conversion factors
CSR and CSS

29
 Rheometry (Rotation)
Preset for Flow Curves

preset of the rotational speed preset of the torque

„shear rate ramp“, „shear stress ramp“,

usually in the form of a usually in the form of a
step-like funktion step-like funktion
„upstairs“ or „downstairs“ „upstairs“ or „downstairs“
(CSR: controlled shear rate) (CSS: controlled shear stress)

30
 Rheometry (Rotation)
ideally viscous Flow Behavior

Synonyms: ideally viscous or Newtonian flow behavior

 

 

flow curves viscosity curves

31
 Flow Behavior
Overview: Flow and Viscosity Curves

flow curves viscosity curves yield point

  

  

1 ideally viscous (Newtonian)

2 shear-thinning (pseudoplastic)
3 shear-thickening (dilatant)
4 without a yield point
5 with a yield point

32
 Flow Behavior
ideally viscous Behavior
mineral oils
80 80

mPas Pa

60 constant viscosity 60
viscosity shear stress
50 50

40 40
  mineral oil
30 30
CC 27
20 20
(concentric cylinders)
10 10
T = +50°C
0 0
0 200 400 600 s-1 1000

shear rate 
33 [Link]
 Flow Behavior
ideally viscous Behavior
polymers

10 1000

Pas Pa
constant viscosity
silicone oil
10
CP 50-2
lg  1
(cone-and-plate)
lg
T = +23°C
0.1

0.01

1 Advantage of diagrams on a
logarithmic scale :
0.001 0.01 0.1 1 10 s-1 100 here, also the range of very small
lg  values can be illustrated clearly.

34 [Link]
 Flow Behavior
ideally viscous Behavior

water
10 1000

mPa
mPas

10

lg  1
lg 
constant viscosity 1

0.1 DG 42
(double gap MS)
0.01 T = +20°C
0.1
1 10 s-1 100
lg 
Double-gap measuring systems are special systems designed  Movie
for low - viscosity liquids. (PIV: Taylor vortices)

35 [Link]
 Coffee Break

36
 Flow Behavior
Double-Tube Test

In the outlet capillary

are decreasing continuously :

- the acting weight force,

thus,
- the hydrostatic pressure,
and therefore,
- the shear stress

1) wall paper “paste“ (polymer solution, aqueous methylcellulose):

pressure or velocity-dependent viscosity, respectively
2) mineral oil:
constant viscosity
 Movie
(double tube)

37
 Flow Behavior
idealviscous and shear-thinning Behavior

2
direction of the double-tube test
Pas 
decreasing shear stress
1.5


mineral oil: ideally viscous
1 constant viscosity

shear-thinning
0.5
polymer solution:
viscosity is
velocity-dependent
0
0 100 200 300 400 s-1 500

shear rate 
38 [Link]
 Flow Behavior
Shear-thinning Behavior

 

1

2

γ 1 γ 2
 
flow curve viscosity curve      
1 1 2 2 
- shear-thinning
- pseudoplastic

39
 Flow Behavior
Shear-thinning Behavior
polymers
polymer molecules
chain-like makro-molecules

under shear:
deformation in shear direction,
state at rest: disentanglements
coiled,
entangled consequence:
shear-thinning flow behavior,
decreasing viscosity

40
 Flow Behavior

Take care of
degradation.

Therefore:
please
be patient ...

Loriot

41
 Flow Behavior
Shear-thinning Behavior
dispersions
at rest: under shear:
high viscosity decrease in viscosity

suspension
showing
needle-shaped
or
platelet-shaped
particles
The particles are The particles are
suspended randomly orientated in
(if there are no flow direction.
interaction forces).

consequence:
shear-thinning flow behavior,
decreasing viscosity

42
 Flow Behavior
Shear-thinning Behavior
dispersions
at rest: under shear:
high viscosity decrease in viscosity

agglomerated
particles

Agglomerates The agglomerates are

are formed which disintegrated into
are surrounding also primary particles.
a part of the dispersion
liquid immobilizing it.
consequence:
shear-thinning flow behavior,
decreasing viscosity

43
 Flow Behavior
Shear-thinning Behavior
dispersions
at rest: under shear:
high viscosity decrease in viscosity

emulsion

The dispersed droplets The droplets are deformed

are showing the shape and take on the shape of
of spheres. ellipsoides.

consequence:
shear-thinning flow behavior,
decreasing viscosity  Movie
(emulsion)

44
 Flow Behavior
Rheo - Microscopy
dispersions
emulsion: water in silicone oil

Size and shape

of the droplets
are depending
on the shear rate
and on the
lg  “shear history”.

45
 Rheometry
Rheo - Microscopy

sample

Peltier heated
glass plate

objective
with variable
magnification
(e.g. x5 to x50,
usually x20)

light source

digital camera
(CCD)

46
 Flow Behavior
Shear-thinning Behavior
polymers adhesives

0.5
150
Pas
wall paper paste
Pa
0.4
aqueous
100 methylcellulose
  solution
0.3

T = +23°C
50
0.2
The typical behavior
of polymer solutions:
0.1 0 showing continuously
0 200 400 600 s-1 1000 shear-thinning
shear rate 
47 [Link]
 Flow Behavior
Shear-thinning Behavior
dispersions cosmetics
1 300
1 300
Pa
Pa∙s
250
0.8 Pas
200 O/W Emulsion Pa
0.7
0.6 0.8 150 
 Viscosity O/W emulsion
  Shear Stress
1 undiluted
0.5
100 O/W Emulsion with 10% water
200
0.4  Viscosity
50
0.3
0.6  Shear Stress O/W300emulsion

0.2 0
1
 Pawith
0 200 400 600 1/s 1,000 Pa∙s 2 10%
250
Shear Rate 
.
0.8100 additional water
200 O/W Emulsion
0.7
0.4 1  Viscosity
 0.6 150 
 Shear Stress
0.5
100 O/W Emulsion with 10%
2 0.4 The typical behavior Viscosity
50
0.2 0.30 of dispersions:  Shear Stress
0 200 400 600 s-1 10000.2 initially strongly,
0 and then
0 200 400 600 1/s 1,000
less shear-thinning.

.
Shear Rate 
shear rate
48 [Link]
 Flow Behavior
Shear-thinning Behavior
printing inks
300 These 3 diluted
gravure printing inks
of the same pigment concentration
mPas are showing the same flow time binder 1
when using a flow cup. (the useful one)
200
|
binder 2
|
 |
| (spattering)
|
| binder 3
100 |
| (50/50 mix of 1 & 2)

Summary:
Using flow cups,
0 measurements
0 200 400 600 s-1 1000 are taking place
in a limited shear
shear rate  rate range only.
49 [Link]
 Flow Behavior of Unlinked Polymers
Zero-Shear Viscosity
polymers adhesives
1 1000
Pas ---- Pa
For  < 0,1 s-1 the 100 wall paper paste
polymer solution shows
the plateau of the aqueous
zero-shear viscosity. 10 methylcellulose
solution

lg  1 lg  T = +23°C

0.1

0.01
logarithmic scales
to evaluate the behavior
0.1 in the low-shear range
s-1
0.01 0.1 1 10 100 1000
lg 
50 [Link]
 Flow Behavior of Unlinked Polymers
Zero-Shear Viscosity
polymers
Superposition of two processes:
1) Orientation of the makromolecules
under shear load
 disentanglements
 here, the viscosity is decreasing

2) Re - coiling due to
visco - elastic behavior
 re - entanglements
 here, the viscosity is increasing

Result:
In the low-shear range there is no
change in the total viscosity value,
which is referred to as the 0 – value.
This low-shear range mostly occurs at  < 1 s-1

51
 Flow Behavior of Unlinked Polymers
Zero-Shear Viscosity
polymers

lg 

lg 

For unlinked polymers:

An increasing average molar mass M
Results in a higher zero-shear viscosity value.
(for a constant polymer concentration)
52
 Flow Behavior of Unlinked Polymers
Zero-Shear Viscosity
polymers

10

Pas
mineral oil
(ideally viscous)
1
polymer solution 1
lg  (wider MMD)

0.1 polymer solution 2

(narrower MMD)

0.01
0.01 0.1 1 s-1 100 MMD is the
molar mass distribution
lg 
53 [Link]
 Flow Behavior of Unlinked Polymers
Zero-Shear Viscosity
polymers

concentration
for solutions of unlinked polymers:
dependence of the low-shear viscosity on the concentration
diluted (with c < ccrit), showing ideally viscous flow behavior,
highly concentrated (with c > ccrit), showing zero-shear viscosity at rest

54
 Flow Behavior of Unlinked Polymers
Shear-thinning Behavior
polymers
lg 

a complete
viscosity function
of unlinked
polymers

lg 
"low - shear range" "flow range" "high - shear range"
shear-thinning
plateau of the flow behavior plateau of the
zero-shear viscosity infinite-shear viscosity

 0  lim   
 0

 
        lim   

    


55
 Flow Behavior
Shear-thickening Behavior

 

 
flow curve viscosity curve

- shear-thickening
- dilatant
 Movie
(starch dispersion)

56
 Flow Behavior
Shear-thickening Behavior
dispersions
suspensions
shear-thickening
of suspensions at

- high solid concentrations

- high shear loads

f ... volume fraction of solid particles

57
 Flow Behavior
Shear-thickening Behavior
dispersions
0.4 400

Pas Pa
 ceramic suspension
0.3 shear- thickening 300

0.2 200
 

0.1 100

0 0
0 200 400 600 s-1 1000

shear rate 
58 [Link]
 Flow Behavior
Shear-thickening Behavior
dispersions
Influence of the particle shape

sources: REM-Fotos, Universities of Karlsruhe & Bochum

Comparison of aqueous chalkstone suspensions

(left) cube-shaped particles (right) spherical particles

Both suspensions showing the same solid concentration,

for suspension (1) shear-thickening behavior is occurring
already at lower shear rates compared to suspension (2).
The reason is the difference in the required amount of volume,
since in flowing dispersions, the particles are rotating.
59
 Flow Behavior
Shear-thickening Behavior
polymers

4000

Pas
plastisol
3000
with a too small
 softener amount
2000


shear thickening problem:
1000 blocking of the
spray nozzle

0
0 100 200 300 400 s-1 500
 Movie
shear rate  (walk on water)

60 [Link]
 Flow Behavior
Yield Point

flow curves on a
The yield point as a linear scale
limiting value of the shear stress 
2
Break of the structure-at-rest.
There is a super-structure 1
due to a chemical-physical
network of interactive forces. y



1 without a yield point
2 showing a yield point y

61
 Flow Behavior
Yield Point

Yield Point determination

 via
mathematical curve fitting
of flow curves
on a linear scale
(approximation, "regression")


the Bingham model yield points are not
B ... “ yield point material constants,
according to Bingham “
B ... “ Bingham viscosity “ since they depend on the
measuring method
frequently used models: and on the
- Casson analysis method
- Herschel / Bulkley used.

62
 Flow Behavior
Yield Point
Yield point analysis
in the low-shear range of flow curves,
here on a logarithmic scale

lg 

y
y

lg 
Method 1: Method 2:
read off on the  - axis read off at a certain
low shear rate,
e.g.  = 0.01 s-1
63
 Flow Behavior
Yield Point, comparison lin / log diagrams (1)
food

flow curve
2500
on a linear scale
Pa
showing a
2000 yield point

1500
 ketchup
1000

500
The yield point can hardly be read-off
0
0 200 400 600 s-1 1000


64 [Link]
 Flow Behavior
Yield Point, comparison lin / log diagrams (2)
food

104

Flow curve
Pa
on a logarithmic scale
showing a
1000 Yield Point

lg 
ketchup
100

The yield point is y = 48 Pa

10
1 10 100 s-1 1000
lg 

65 [Link]
 Flow Behavior
Effect of Rheological Additives (1)
coatings dispersions
Example: comparison of flow behavior of a water-based dispersion with
1
additive 1, a „gellant“ e.g. clay
2 additive 2, a „viscosifier“ e.g. an associative thickener

flow curves on a linear scale flow curves on a logarithmic scale

300 1,000
Pa
Pa
240
220 2 50
100
1
200 Pa
45

180 40

160 35

140 10

 120
30


lg 
25

100
80
1 20

15
1
60 with yield point 10

2
40 5

20 0
0
0
5·10 1/s 10
1

0 0.1
0 100 200 300 400 500 600 700 800 1/s 1,000 0.1 1 10 100 1/s 1,000

Shear Rate 
.
 Rate .
lgShear
Gellant (Clay) Viscosifier (PUR) Gellant (Clay) Viscosifier (PUR)
Summary: The gellant shows is effective especially in the low-shear range
(or at rest, resp.), and the viscosifier in the high-shear range.
66 [Link]
 Flow Behavior
Effect of Rheological Additives (2)
coatings dispersions
Example: comparison of flow behavior of a water-based dispersion with
1
additive 1, as a „gellant“ e.g. clay,
2 additive 2, as a „viscosifier“ e.g. an associative thickener
1,000

Pa·s

100
1

10
viscosity curves on a
lg 
logarithmic
scale
1 2

0.1
0.1 1 10 100 1/s 1,000
lg  .
Shear Rate 
Gellant (Clay)
Summary: The gellant shows isViscosifier
effective(PUR)
especially in the low-shear range
(or at rest, resp.), and the viscosifier in the high-shear range (less spatters).

67 [Link]
 Flow Behavior
Effect of Rheological Additives (3)
coatings

1) How is the 2) What about the flow behavior when rolling or painting ?
appearance of the
emulsion paint after
opening the container 3) Checking leveling, 4) ... and how
- hopefully the coating is sagging, wet-layer is our
not to much demixed ?!? thickness, hiding power … appearance
finally ?
Seems here,
high-shear
viscosity was
a bit too low.

Consequence:
spatters

68
 Flow Behavior
Effect of Rheological Additives (4)
coatings dispersions

Different rheological
additives used as
(1) thickeners; example:
water-based coatings
(1) silica (clay),
inorganic gellant

(2) (2) cellulose derivative,

polymer solution
left side: right side:
when shearing (3a) unmodifiíed
at rest polymer dispersion
(3a) (3b) polymer dispersion
containing an
associative thickener
(3b)
(bar length: 100 nm = 0.1 µm)

Polymer dispersions may show lower viscosity, despite a higher molar mass of the polymer.
69 [Link]
 Flow Behavior
Effect of Rheological Additives (5)
coatings dispersions

Viscosity functions of
pigmented
water-based coatings
lg  containing different
rheological additives
1 as thickeners, in principle:

(1) silica (clay),

2
inorganic gellant
3b (2) cellulose derivative,
polymer solution
3a
low-shear lg  high-shear (3a) unmodifiíed
polymer dispersion
-1
0.01 0.1 1 10 100 1000 10,000 s
(3b) polymer dispersion
containing an
associative thickener

70 [Link]
Flow Behavior
Overview: Flow and Viscosity Curves (linear scale)

flow curves viscosity curves yield point

  

  
1 ideally viscous (Newtonian)
2 shear-thinning (pseudoplastic)
3 shear-thickening (dilatant)
4 without a yield point
5 with a yield point
 e-learning
(the stirring chefs)

71
 Flow Behavior
Overview: Flow and Viscosity Curves
polymers
lg 
viscosity function of
unlinked polymers
1 range of the
zero-shear viscosity 0
2 flow range
(shear-thinning)
3 range of the
lg  infinite-shear viscosity 

lg 
viscosity functions
of two samples

4 without a yield point, at rest liquid (viscous)

5 with a yield point, at rest solid, showing
a gel-like structure (viscoelastic behavior)
lg 

72
 Flow Behavior
Overview: Flow and Viscosity Curves
polymers dispersions

100
Pas showing the same
flow behavior,
but a totally different without a
lg  consistency zero-shear viscosity 0
when at rest (stability at rest)
10
with a
zero-shear viscosity 0
(self-levelling flow)

1
0.01 0.1 1 10 s-1 100

lg 
73 [Link]
 Flow Behavior
„Transient Viscosity Peak“
„transient viscosity peak“

in the low-shear range,

i.e., at  < 1 s-1
when presetting a too short
measuring point duration.
Reason:
At first in the shear gap,
the condition of a homogeneous
flow velocity (shear rate)
is not reached yet.

Examples:
1 ... tMP = 10 s (for all points)
2 ... tMP = 60 to 5 s
3 ... tMP = 120 to 5 s

rule of thumb: tMP = 1 / 

74
 Flow Behavior

Is this

Rheology

or

Art

Maurits Cornelis Escher:

Waterfall (1962)
75
 Flow Behavior
Time - dependent Structure Recovery

Sometimes
Sometimes
cats are very
cats are
stupid
very curious

Requirements for coatings: structure recovery just in the right time

1) not too fast, and thus, good levelling

2) not too slow, and thus, not too much sagging,
sufficient wet - layer thickness

76
 Flow Behavior
Time - dependent Structure Recovery
step test consisting of 3 intervals, as a rotational test
(measuring „thixotropic behavior“)


Preset:
1 low-shear conditions
2 high-shear conditions
3 low-shear conditions

Measuring result:
 1 state of rest
2 structural decomposition
3 structural regeneration

t
77
 Flow Behavior
Time - dependent Structure Recovery
Comparison of two coatings formulations: coatings
step test with 3 intervals
100
 = 0.1 s-1  = 0.1 s-1 using the „gellant“,
Pas structural recovery
is faster
10
- less sagging,
- high wet-layer thickness,
lg 
- but maybe poor leveling

1
structure recovery using the „thickener“,
structural recovery
is slower
 = 100 s-1 - good leveling,
0.1 - but maybe too much
0 100 200 300 400 500 600 700
s sagging
time t

78 [Link]
 Application
Sagging of Paints
coatings

Come on please,
but not like
THIS !

 e-learning
(brushing 3 paints )

79
 Flow Behavior
Time - dependent Hysteresis Area
“Thixotropy test“ (old - fashioned)
test consisting of 3 intervals: upward ramp, hold time, downward ramp
analysis: hysteresis area
Disadvantages:
 1) testing in a instationary state
2) no measurement of structural regeneration

preset:
shear rate profile

 evaluation of the hysteresis area

in between the flow curves
as a measure of structural decomposition

Summary:
This test method
is out-dated now.

80
 Flow Behavior
Time - dependent Curing
coatings polymers
20
at 160°C at 140°C at 120°C
kPas powder coating

15 at a constant shear rate of

  = 1 s-1

10
 Note: In principle,
isothermic complete curing processes
curing cannot be evaluated by
5
rotational tests, since when
curing, the viscosity values
are finally increasing to an
0 infinitely high value.
Therefore here,
0 200 400 600 s we are recommending
time t oscillatory tests.

81 [Link]
 Flow Behavior
Temperature - dependent Behavior

 softening and melting,

or solidification and crystallization

preset: constant shear conditions

(shear rate or shear stress)

result: viscosity / temperature curve

with steadily decreasing or increasing
T viscosity values, respectively

gel formation and curing


preset: constant shear conditions
(shear rate or shear stress)

min result: viscosity / temperature curve

showing a viscosity minimum
 e-learning
(honey)
T
82
 Flow Behavior
Temperature - dependent Behavior
polymers
100
The log  / lin T diagram often shows a
linear shape of the curve.
Pas

10

lg 
silicone oil
1


softening

0.1
-100 -50 0 50 °C 100
temperature T
83 [Link]
 Flow Behavior
Temperature Curves of Mineral Oils (1)
mineral oils
viscosity / temperature curve, analysis according to Arrhenius
100
oil
mPas analysis of the onset of
crystallization
of waxes and paraffines
during a cooling process
lg 

 
crystallization

10
10 15 20 25 30 35 °C 40
temperature T

crude oil Arrhenius, low T Arrhenius, high T

84 [Link]
 Flow Behavior
Temperature Curves of Mineral Oils (2)

viscosity / temperature curve, analysis according to Arrhenius mineral oils

100

mPas
here presented versus (1/T)

comparable to the
lg  pour point

 
crystallization

10
0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
1/K
1/temperature 1/T
crude oil Arrhenius high T Arrhenius low T

85 [Link]
 Flow Behavior
Temperature - dependent Behavior
food
10
Cooling process:
Pas
crystallization temperature
8 of
 cocoa butter

6
chocolate melt


4


2 crystallization

0  e-learning
20 25 30 35 °C 40 (choc cake)

temperature T  Movie
(choc-fountain)

86 [Link]
 Flow Behavior
Temperature - dependent Behavior
mineral oils
Comparison: basic oils for lubricating greases, at T = +20 and -40°C
105 Oil 1: partially synthetic
Oil 1 at -40°C:
Oil 2: fully synthetic
Pas inhomogeneous flow

103
lg  Oil 2 at -40°C: ideally viscous
Oil 1 (+20°C)
102 Oil 2 (+20°C)

101
Oil 1 (–40°C)
both oils at +20°C: ideally viscous pourpoint at –24°C,
100
showing the same viscosity pulp-like consistence
Oil 2 (–40°C)
pourpoint at –60°C,
10-1
still liquid
10-2 10-1 100 101 102 s-1 103

lg 
87
 Flow Behavior
Temperature - dependent Behavior
mineral oils

three-dimensional
(3D) diagram
0.2

temperature-dependent
viscosity curves of a
0.1
mineral oil
(Pas)

 0
0 
23
0  T (°C) at +23°C
50
 500  at +50°C
(s-1) 80 at +80°C
1000 100

88
 Flow Behavior
Pressure - dependent Behavior
mineral oils
used motor oil
600
viscosity increase
mPa·s
with
500
increasing pressure p

400


p = 95 bar ( = 9.5 MPa)
300
p = 60 bar ( = 6 MPa)
p p = 30 bar ( = 3 MPa)
p = 1 bar ( = 0.1 MPa)
 compression
200

100

at T = +23°C
0
10 100 lg  s-1 1000

89
 End of the Rotational Part

Never
give up !

90