4/2/2019
TA Instruments – Waters LLC
Materials Characterization by Rheological Methods
Gregory W Kamykowski PhD Senior Applications Scientist for Rheology TA Instruments – US West [email protected]
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Rheology: An Introduction
Rheology: The study of the flow and deformation of matter. Rheological behavior affects every aspect of our lives.
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Rheology: The study of the flow and deformation of matter
Flow: Fluid Behavior; Viscous Nature F F = F(v); F ≠≠≠ F(x)
Deformation: Solid Behavior F Elastic Nature
F = F(x); F ≠≠≠ F(v)
0 1 2 3 x
Viscoelastic Materials: Force F Maxwell depends on both Deformation and Rate of Deformation and vice versa.
Kelvin, F Voigt
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Basic Material Behaviors
Egg Polymer Ceramic Water Oil Soap Metal white Melt ?
Flow Flow & Deformation Deformation
Elastic Solids Viscous Liquids Visco elastic Stress Stress Modulus = Viscosity = Strain Strain Rate
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Rheological Testing - Rotational
2 Basic Rheological Methods 1. Apply Force (Torque)and measure Deformation and/or Deformation Rate (Angular Displacement, Angular Velocity) - Controlled Force, Controlled Rate Shear Angular Velocity, Velocity, Angular Stress Torque, Shear Stress
2. Control Deformation and/or Angular Displacement, Deformation Rate and measure Force needed (Controlled Strain Displacement or Rotation, Controlled Strain or Shear Rate) Torque, Stress Torque,
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Steady Simple Shear Flow
Top Plate Velocity = V 0; Area = A; Force = F
H y Bottom Plate Velocity = 0 x
vx = (y/H)*V 0
. -1 γγγ = dv x/dy = V 0/H Shear Rate, sec σσσ = F/A Shear Stress, Pascals . ηηη = σσσ/γγγ Viscosity, Pa-sec These are the fundamental flow parameters. Shear rate is always a change in velocity with respect to distance.
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Parallel Plate Shear Flow
Stress σσσ Force or torque Strain γγγ Linear or angular displacement
Strain Linear or angular velocity Rate
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SHEAR RATE CALCULATIONS IN EXTRUSION
. Extruder: γγγ = πππDN/(60*h)
D = Diameter; N = rpm; h = gap
. 3 Q = Output rate; Circular, Rod: γγγ = 32Q/( πππD ) D = orifice diameter compounding, cable . Rectangular, Slit: γγγ = 6Q/(wh 2) Q = Output rate; w = width cast film, sheet h = gap
. Annulus: γγγ = 12Q/( πππ(D1+D2)h 2) Q = Output rate; D1 = Inner diameter blown film, blow molding D2 = Outer diameter h = gap
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Representative Flow Curve
1.E+05
Newtonian Pseudoplastic Region Behavior 1.E+04 0 < n < 1 (Newtonian)
1.E+03 Transition Power Law ηηη = ηηη0 Region Region
1.E+02
Viscosity Viscosity (Pa-sec) 1.E+01 . ηηη = m* γγγ (n-1) 1.E+00 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 M 3.4 -1 ηηη0 ∝∝∝ W Shear Rate (sec )
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Idealized Flow Curve
Often we try to correlate our rheology data with actual applications. However, differences between similar materials are accentuated at the low shear 1) Sedimentation rates, where rotational rheometers excel. 2) Leveling, Sagging So, even if one does not get to high shear 3) Draining under gravity
η rates, the rheology data are still useful. 4) Chewing and swallowing 5) Dip coating
log 6) Mixing and stirring 7) Pipe flow 8) Spraying and brushing 9) Rubbing 10) Milling pigments in fluid base 11) High Speed coating
4 5
6 8 9 1 2 3 7 10 11
1.00E-5 1.00E-4 1.00E-3 0.0100 0.100 1.00 10.00 100.00 1000.00 1.00E4 1.00E5 1.00E6
shear rate (1/s)
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Simple Shear Deformation
Top Plate Displacement = X 0; Area = A; Force = F
H y Bottom Plate x Displacement = 0
x = (y/H)*X 0
γγγ = dx x/dy = X 0/H Shear Strain, unitless σσσ = F/A Shear Stress, Pascals G = σσσ/γγγ Modulus, Pa These are the fundamental deformation parameters. Shear strain is always a change in displacement with respect to distance.
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Stress Relaxation
Stress Relaxation of Soy Flour, Overlay
10 9
• Instantaneous Strain • Note the decrease in the modulus as a
) function of time.
10 8 G(t) ( G(t) [Pa] F
G(t) T=20°C T=30°C T=40°C T=50°C 10 7 10 0 10 1 10 2 10 3 time [s]
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Rheological Parameters
FLUIDS TESTING
Parameter Shear Elongation Units . . Rate γγγ ε Seconds -1
Stress σσσ τττ Pascals . . Viscosity ηηη = σσσ/γγγ ηηηE = τττ/εεε Pascal-seconds
SOLIDS TESTING
Parameter Shear Elongation Units
Strain γγγ ε Unitless
Stress σσσ τττ Pascals
Modulus G(t) = σσσ/γγγ E = τττ/εεε Pascals
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Rheological Parameters
CREEP TESTING
Parameter Shear Elongation Units
Stress σσσ τττ Pascals
Strain γγγ ε Unitless
Compliance J = γγγ /σσσ D = ε/τε/τε/τ 1/Pascals
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Creep Testing
Stress is held constant. Strain is the measured variable. Compliance = Strain/Stress 3x10 -3
HDPE
2x10 -3 Viscoelastic
1x10 -3 Fluid Compliance (1/Pa) Solid
0x10 0 0 5 10 15 20 Step time (min) Viscosity = 1/Stress is held constant. Strain is Slope in steady flow regime. Intercept = non-recoverable Compliance
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GEOMETRIES
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Geometry Options
Concentric Cone and Parallel Torsion Cylinders Plate Plate Rectangular
Very Low Very Low Very Low Solids to Medium to High Viscosity Viscosity Viscosity to Soft Solids Water to Steel
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Converting Machine to Rheological Parameters in Rotational Rheometry
Machine Parameters M x Kσ σ M: Torque = =η ΩΩΩ : Angular Velocity ΩxK γ• θθθ : Angular Displacement γ Conversion Factors
Kσσσ : Stress Conversion Factor Kγγγ : Strain (Rate) Conversion Factor MxK σ Rheological Parameters σ σσσ : Shear Stress (Pa) • = =G γγγ : Shear Rate (sec -1) ηηη : Viscosity (Pa-sec) xK γγγ : Shear Strain θ γ γ G : Shear Modulus (Pa)
The conversion factors, K σσσ and K γγγ, will depend on the following: Geometry of the system – concentric cylinder, cone and plate, parallel plate, and torsion rectangular Dimensions – gap, cone angle, diameter, thickness, etc.
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Shear Rate and Shear Stress Calculations
Geometry Couette Cone & Plate Parallel Plates Conversion Factor
Kγγγ Ravg /(R o-Ri) 111/βββ R/h
2 3 3 Kσσσ 1/(2* πππRi L) 3/(2 πππR ) 2/( πππR )
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Choosing a Geometry Size
Assess the ‘viscosity’ of your sample When a variety of cones and plates are available, select diameter appropriate for viscosity of sample Low viscosity (milk) - 60mm geometry Medium viscosity (honey) - 40mm geometry High viscosity (caramel) – 20 or 25mm geometry Examine data in terms of absolute instrument variables torque /displacemen t/speed and modify geometry choice to move into optimum working range You may need to reconsider your selection after the first run!
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Geometry Options
With the variety of cones, plates, cups and rotors available, select a geometry based on desired experimental parameters and the material properties
Cones and Plates No Solvent Trap With Solvent With Solvent Trap (NST) Trap and Heat Break (HB)
Smooth, Sandblasted, and Cross hatched
Concentric Cylinders (or Cups) and Rotors (or Bobs)
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When to use Cone and Plate
Very Low to High Viscosity Liquids High Shear Rate measurements Normal Stress Growth Unfilled Samples Isothermal Tests Small Sample Volume
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Shear Rate is Normalized across a Cone
The cone shape produces a smaller gap height closer to the inside, so the shear on the sample is constant