Dynamic Mechanical Thermal Analysis DMTA V

Users Training Course Rheometric Scientific One Possumtown Rd. Piscataway NJ 08854

Dynamic Mechanical Thermal Analysis

Rheology - the study of flow of materials DMTA is Rheology on solids Also called Dynamic Mechanical Spectroscopy - it gives a spectrum of behavior of materials which are subjected to a dynamic or steady deformation.

Dynamic Mechanical Thermal Analysis

DMTA looks at how materials respond to an imposed stress. The stress deforms the materials. The DMTA measures the strain - how far the material moves, and calculates how much energy is stored or dissipated during the process.

Mechanical Testing
Dynamic (Oscillatory) - Deformation is applied as a sinusoidal function. Steady - Deformation is applied as a constant over a time period.

Review of terms
Stress- Force deforming the sample per unit area (or) = F/A

Strain- the distance sample moves in response relative to the sample length in shear: = X/ Y in tensile = L/Lo

Hookes Law
Describes the behavior of an ideal elastic solid. Relates the applied strain to the resultant stress (or visa versa). The proportionality factor is called the modulus of the material. Denoted as E or G

Review of terms
Youngs Modulus is the ratio of dynamic stress to strain, E* (measured in tensile or bending mode) E= / Shear Modulus is the ratio of dynamic shear stress to strain, G* G= / for most rubbery polymers: E=3G
assuming a Poisson ratio of 1/2 (Poissons ratio is the linear contraction relative to the extension in tensile)

Review of terms
Viscosity - the resistance of a material to flow. High viscosity materials need more force to make them flow than low viscosity materials. Shear thinning - materials that become thinner, lower viscosity, as you increase the stress deforming them.

Newtons Law
Describes the behavior of ideal fluids according to the stress and shear Proportionality factor is viscosity, . Ideal viscous fluids are linear with shear rate, no shear thinning = d/dt =

Newtonian And Non-Newtonian Behavior Of Viscous Fluids

Material Response To A Sinusoidal Deformation (Dynamic Mechanical Testing)

+ o + o

Strain

Strain Rate

Material Response To A Sinusoidal Deformation (Dynamic Testing)

Elastic Response Viscous Response (t) Time

*(t)

Time (t)

*(t)

Material Response To A Sinusoidal Deformation (Dynamic Mechanical Testing)

(t)
(t)

'

(t)

''

Review of terms
Storage Modulus, E - component in phase with the applied sinusoidal deformation; relates to stiffness of materials This is the elastic behavior of a materialthe solid-like properties it displays The storage modulus is a measure of how a material stores the energy of deformation, and allows material to regain shape after deformation

Review of terms
Loss Modulus, E- component out of phase with the applied sinusoidal deformation; relates to damping ability of material This is the viscous nature of the material its liquid-like behavior The loss modulus is an indication of how the material dissipates the energy used to deform it.

Modulus relationships
Loss (viscous) Modulus = E Liquid like behavior

Complex Modulus Phase angle tan = E/E Storage (Elastic) Modulus = E solid like behavior

Review of terms
tangent delta- E/E dimensionless, related to the damping characteristic. This is also called the loss tangent. A high tan delta means a greater ability to dissipates stress and behave more like a liquid.

Material Properties Dynamic Testing: shear or bending

Complex Modulus

Storage Modulus

G = 0 0 G'= ' = Gcos 0

G" = " = Gsin 0

Or E* = / Or E = / = (/)cos

Loss Modulus

Or E = / = (/)sin

Complex Viscosity

= G
tan = G/G or E/E

Loss tangent

Material Properties (Steady Testing)

V isco sity

= &

S tre ss R e la xa tio n M o d u lu s C o m p lia n ce

G ( t) = ( t)
( t) J(t) =

How does DMTA operate?

DMTA is a Controlled Stress Instrument
It generates data via a feedback loop: Strain is asked for in the method for stress is applied to the sample. Actual strain is measured, as is the applied stress to allow rheological data (E,E, tan delta) to be calculated.

Position sensor/ drive shaft movement

A current to the motor moves the drive shaft. Motion of the drive shaft is detected by a position sensor consisting of a static probe and a target attatched tot he drive shaft. Change in magnitude of gap between probe and target produces a current in the position sensor, which is converted into a distance measurement. All are thermally isolated from the furnace.

How a data point is calculated

The User defines the geometry; accurate measurements of the sample are CRUCIAL! Strain is multiplied by a geometrical constant to give an actual displacement that the DMTA will try to achieve. At the first data point 5% of the full scale allowable dynamic force is applied to the sample. Displacement is measured and the feed back loop takes over to control the force needed for the next data point.
Note: this initial 5% dynamic force can be changed in software with version 6.4.1 and higher via the measurement options section.

Achieving the strain desired...

Chosen strain is divided by actual strain and if ratio is between 0.85 and 1.15 (+/15% window,user selectable defaults) the measurement can be taken. If this ration is outside the window, the applied force is multiplied by this ration and again applied to the sample.

Achieving strain levels.

Once strain falls within the window the standard measurement process begins: 2048 points are taken for strain and force from 1 to >64 cycles depending on frequency. Strain and force are cross correlated to models of a Sine and Cosine representing a perfect solid and fluid. This yields two phasors representing normalized strain and force amplitudes and their respective phase angles. Effects of mass of drive shaft and tools are taken into account to give correct applied force.

Controlling the needed force...

For the next data point the previous force is applied and if necessary modified to achieve the chosen displacement. Movement of the drive shaft due to sample growth does not affect the measurement of displacement in dynamic motion.

Controlling temperature
Temp. is measured by a PRT in the radiant oven. PID loops adjust the line voltage to power the furnace to heat. If using LN2, a solenoid (with 3 user selectable control features in ver. 6.4.1 and higher) allows LN2 into a cooling container surround the furnace, no LN2 ever touches the sample! Oven and LN2 can only operate if oven lid is fully closed- for safety reasons.

Review of terms
Viscoelastic- Polymers display the behavior of both elastic solids and viscous liquids. Linear Viscoelasticity- Region where the modulus is independent of the applied deformation

Linear and Nonlinear StressStrain Behavior Of Elastic Solids

Linear Region Nonlinear Region

4 Sequence of Dynamic Strain Sweep Tests

10
7

0.5
E'

Linear Viscoelastic region determination

b A b B b C Test 1 of 3 Test 2 of 3 Test 3 of 3

0.4

tan_delta (b A []

0.3 106 0.2

E' (b A [Pa]

tan delta

0.1
Length = 5.0 mm Width = 10.42 mm Thickness = 2.45 mm Frequency = 1 Hz

10 -2 10

10

-1

10

0.0 1 10

Rheometric Scientific, Inc.

strain [%]

Important material behavior:

Materials that are stiff have a high storage modulus, E Soft materials have a high E tan delta gives the ratio of the two: E/E Materials change properties at the glass transition, stiffness (E),and ability to dissipate stress (E) change rapidly, thus the ratio (tan delta) gives a peak.

DMTA Modulus vs. Temp.

E = Storage Modulus = Elastic response tan = E/E
log Modulus

E = loss Modulus = Viscous Response

Temperature

Test Set up
Testing Options

DMTA testing modes

Dynamic
Single point - to set parameters Time sweep at constant freq. Dynamic strain sweep Frequency dependence Temperature dependence Combinations of freq./temp. dependence

DMTA testing modes

Transient
Static load - creep and TMA mode Constant strain - stress relaxation Strain rate testing- Stress vs. Strain Curves

Testing Conditions
Variables Deformation % strain Rate/Frequency in Hz or Rad/s Temperature ramp or step isothermal Time

Deformation Dependence (Dynamic Strain Sweep Testing)

or E

Frequency Dependence (Dynamic Testing)

Thermoplastic showing dramatic frequency dependance of E

9x108 0.16
8x108 0.14 7x108

6x108

5x108

4x10

E Storage Modulus increase with frequency. 0.12 Material will be stiffer at higher frequency.
0.1

tan_delta (b K []

E' (b I [Pa]

E" (b J [Pa]

3x108

2x10

0.08

1x108

0.0 10-2
H idden Information

10

-1

10

10

0.06 20.0

Freq [H z]

PDMS frequency dependance

10
5

10

Loss Modulus, G"

Modulus, G', G" [Pa]

10

Eta* [Pa.s]

104

103

Eta* [Pa.s] Storage Modulus, G'

10 -1 10

100
Rheometric Scientific

Frequency, rad/s

101

10 2 10

Temperature Dependence (Dynamic Testing)

or E Step testing or E Ramp

Frequency/Temperature testing
Frequency Temperature Ramp: Temperature ramps while frequencies are swept, two variables changing. Long frequencies or fast ramp rates will cause temperature to change before frequency sweep is complete Used only as a screening tool

Frequency/Temperature testing
Frequency Temperature Sweep: Isothermal Temperature steps at which frequencies are swept only one variable changes at a time Soak time used to allow thermal equilibration These are long runs, but clearly better data Used for Time Temperature Superpositioning (TTS)

Relationship Time And Temperature

Short Time / High Frequency(Rate) / Low Temperature Long Time / Low Frequency(Rate) / High Temperature

Relationship Time And Temperature

Relationship Frequency And Temperature

Time Temperature Superpositioning

Data taken at higher temperatures represents data taken at lower frequencies (long times) Data taken at lower temperatures represents the behavior at high frequencies (short times) Data can be shifted horizontally to create a Master Curve TTS Software package uses WLF, (Williams Landel Ferry) equations

Overlay of Frequency Temperature Sweep Data

107

10

G' Storage Modulus

105

104

10

102

101 -1 10

G' b J b E b F b G b H b I b D
10
0

280 260 240 220 200 170 160

c c c c c c c 10
2

Frequency [Hz]

10

Master Curve Data

10
7

10

G' Storage Modulus

10
6

105

G" Loss Modulus

101

104

103

tan delta G"/G'

100

102

10 -3 10

10-2

10-1

10 0

10 1

10 2

10 3

Frequency [Hz]

10-1 4 10

tan delta

G' or G" [Pa]

Material Response To A Step Change In Stress Deformation (Creep Testing)

Stress Elastic Response

Time 2

Time 2

Material Response To A Step Change In Stress Deformation (Creep Testing)

Stress Viscous Response

Time

Time 2

Material Response To A Change In Stress Deformation (Creep test)

Figure 1: Creep and Recovery Test

8.0
DMTA IV

6.0

Zone 1

Zone 2

Strain(t) (b Q [%]

Constant Strain: 4.26%

4.0

Recoverable Strain: 3.39%

2.0

Equilibrium Strain: 0.87%

0.0 0.0
60.0 120.0 180.0

240.0

Rheometric Scientific, Inc.

time [s]

TMA mode
Tensile or compression geometry Sample of a measured length is subjected to a temperature ramp A load may be placed on the sample, either in tension or compression Change in length of the specimen is measured Coefficient of thermal expansion can be calculated

encapsulated blowing agent

0.2

Sample in Compression
0.0

-0.2

Displacement (A ) [mm]

Linear Expansion
-0.4

-0.6

-0.8

Blowing agent "puffs" and collapses

-1.0

-1.2 0.0

50.0

100.0

150.0

200.0

250.0

300.0

Temp [C ]

Material Response To A Step Change In Strain Deformation (Stress relaxation Testing)

Material Response To A Step Change In Strain Deformation (Stress relaxation Testing)

Elastic Response Viscous Response

t1 Time

t1 Time

Material Response To A Step Change In Strain Deformation (Stress relaxation Testing)

Material Response To A Step Change In Strain Rate Deformation (Steady Testing)

Strain Strain Rate

t1

t2 Time

t1

t2 Time

Material Response To A Step Change In Strain Rate Deformation (Steady Testing)

Elastic Response Viscous Response

t1

t 2 Time

t1

t 2 Time

Material Response To A Step Change In Strain Rate Deformation (Steady Testing)

Viscoelastic Response

t1

t2

Time

Stress/Strain curves looking for linear regions

Strain Rate Test at -125C
6x105
5x105

4x105

stress(t) (b A [dyn/cm2]

3x10

2x105

1x105

0.0 0.0

0.5

1.0

1.5

2.0

2.5

3.0

strain(t) [%]

Geometries and Testing considerations

.

DMTA IV has six pure modes of deformation

Dual cantilever bending Single cantilever bending Three point bending Tensile Compression Shear sandwich

How the deformation is made in bending

Bending modes pull samples downward by a chosen amplitude then push up past zero to the same amplitude:
Clamp Zero position Zero position Clamp
Negative Strain amplitude Positive Strain amplitude

Sample moves X microns in negative direction, then X microns in the positive direction

Dual/Single Cantilever Bending

Adjustable lengths Three frame sizes For solid bars Coatings on substrates Layered materials For specimens >1 mm in thickness

Three Point Bending

Three frame sizes For solid samples Best geometry for very high modulus (rigid) samples Eliminates edge effects from clamping For samples that grow with temp.

How deformation is made in tensile geometry

In a dynamic run tensile force pulls downward then returns towards the starting position but not past the zero point
Area = w * t Stress = = F/A Lo Strain= = L/Lo Strain Amplitude L Stationary clamp Mobile clamp

Zero position

Tensile Geometry
Films and Fibers Elastomers TMA mode Auto-gap sets sample length reproducibly Pretension and autotension keeps sample taut during testing

Compression Geometry
Foams Gels Determines the resilience of foam structures Auto gap sets thickness

How deformation is made in shear sandwich geometry

Stress: Force per unit area Strain: Magnitude of deformation relative to sample geometry
A: Area y

Shear Sandwich
Pastes and gels Elastomers Best in horizontal orientation Useful for melts and viscous fluids

Sample types
Thermoplastic - can melt and reform into a solid without significant change Thermoset - heating will not melt it, material will cure/cross link and harden Elastomer - lightly cross linked, pliable, will not melt Polymer blend, Copolymer or Alloy

Samples physical states

Material may be a solid rectangular bar A solid film A fiber or bundles of fibers A polymer coating on a substrate Thick melts or viscous liquids Foams, wet or dry, soft or rigid Pastes or gels

Sample loading techniques

Clamping torque is important! Too much torque on the sample will create stresses radiating into the sample and distorting the data Too light clamping torque can cause sample to slip Re-clamping at lower temp. after contraction may be necessary

How to avoid clamping effects

Keep clamp tension reproducible -even if stress patterns affect absolute results, the run to run variations will be minimal Thicker specimens fare better Use of rubber grips between steel clamps and films improve results
sections of rubber bands can be used, without introducing creep effect

Sample measuring errors

When measurements on samples are inexact, the moduli values are affected. Specimens with uneven surfaces or geometries will not give consistent moduli. Bear in mind that moduli are usually plotted in log form, a slight change visually on the graph is a large change in data. Transition temperatures will not be affected.

Effect of incorrectly measured diameter on E of steel wire

Effect of incorrectly measured length on E of steel wire

How films and fibers differ from other sample types

Films and fibers are often more fragile requiring a gentle treatment in loading and testing Production often involves tremendous stresses on the material: drawing, orienting, annealing, extruding Internal stress causes rapid changes during and after Tg, measuring system must compensate rapidly

How films and fibers differ from other sample types

Uneven thickness are more problematic since aspect ratio is extreme Measuring the thickness of films and fibers can be imprecise Because of difficulty in loading, good lighting is important over work area

How films and fibers differ from other sample types

Deformation is in tensile, bending and compression generally not practical Sample length is more variable than bending modes: clamp geometry doesnt interfere with size. Autogap keeps sample length constant.

Using Multiple Fibers

In many cases, the testing needs to use bundled fibers to represent real life Evenly distribute or wind the bundles Avoid kinking that would make some fibers longer than others Approximate sample dimensions and do not use absolute modulus values: run to run variations may be large

Sample Loading considerations for films

Curling of films
Electrostatic effects on thin films can cause static attractions that make loading frustrating Small residual stresses in the film from processing can cause curling Thin brittle films are subject to cracking while trying to flatten for loading

Sample Loading considerations - buckling

Buckling during loading causes serious errors
Effective sample length is the shortest line of contact by clamps, so by measuring the whole width you will have large errors, the buckled areas will not feel the force or deformation Difficult to evenly smooth sample as you load You can stretch the sample while doing so, causing stresses in the material

Sample buckling
Smooth sample distributes stress evenly across sample width Even sample width Clamps Buckled sample has an effective width narrowed to only the region that is taut between the clamps, modulus values depend on correctly measured geometry Sample width is taut region only

How to avoid buckling

Wider samples are harder to load- buckling is more of a problem Thin film samples are more difficult to keep smooth Load the stationary grips first- this will give you a third hand as you align and smooth the sample, in case the mobile grips move during loading. Glance across the sample at an angle when loaded- do you see ripples?

Auto-tension during a run

The force needed to keep a specimen taut during a dynamic run can change Dimensional changes
as load remains on the sample it can creep as a sample softens during heating it will elongate, or shrinkage can occur as stress relaxation takes place

Stiffness changes
modulus values change dramatically at Tg

Avoiding Buckling during the run

This additional tensile force is additive to the dynamic force, one must take care not to exceed linear viscoelastic regions Dynamic +
Pre-tension Dynamic Force alone Linear region exceeded Strain

Stress

Auto-tension during a run

a static pre-tension will not keep specimen taut, buckling will occur if sample elongates static pretension alone can exceed plastic deformation if sample shrinks static pre-tension can exceed linear region as sample softens need to have tracking with autotension which can change the force with changing sample modulus

Tensile sample length

In tensile geometry where a sample is long:
care must be taken to avoid temperature gradients: heat rises run DMTA in horizontal orientation. Or you will see: these temperature gradients can cause a broadening or doublet in Tg Failure can occur at the top edge, necking

Residual Solvent content

Many materials contain residual solvent This acts as a plasticizer, lowering modulus and Tg Measuring systems must avoid changing the sample:
forced air convection furnaces dry-out specimens slow heating rates can also dry out and embrittle the sample

What happens on sample drying

Loss of moisture or residual solvent can raise the modulus of the material Without the plasticizer (or solvent) Tg is raised Embrittlement Draw ratio decreases Lower elongation at break

DMTA study of solvent or fluid effects on material behavior

Elastomer solvent swell Medical applications Leaching of plasticizers Destructive fluid interactions Fluid effects on creep