Beruflich Dokumente
Kultur Dokumente
= (/1+)
processing conditions
Shear
Why?
12 11 10 9 8 7 6 5 4 3 20 mm
Log E
1 mm 5 mm
20 mm
Lo
L-Lo = L
The different definitions of tensile strain become equivalent at very small deformations.
slope = k
Limiting Modulus
1.0
Hookean Behavior
7)
0.8
Stress (Pa x 10
0.2
0.0
Real behavior
8.0 Strain (%) 12.0 16.0 KPM PERKIN-ELMER 7 Series ThermalAnalysis System Thu Apr 14 16:34:38 1994
4.0
TEMP1: 20.0 C TIME1: 5.3 min
s lope =
The speed at wh the f id f ich lu lows th rough the ho ( s ra ra ) les the t in te i reases wi nc th ! s ress!! t
Viscosity Effects
Newtonian behavior is linear and the viscosity is independent of rate. Pseudoplastic fluids get thinner as shear increases. Dilatant Fluids increase their viscosity as shear rates increase. Plastic Fluids have a yield point with pseudoplastic behavior. Thixotrophic and rheopectic fluids show viscosity-time nonlinear behavior. For example, the former shear thin and then reform its gel structure.
Log
nonlinear region
yield point (y, y) The area under the curve to this line is the energy needed to break the material
d = d
L L
2500.0 0.0025 2250.0 2000.0 0.0020 1750.0 1500.0 0.0015 1250.0 1000.0 0.0010 750.0 500.0 0.0005 250.0 0.0 0.0000 0.0
TEMP1: -15.0 C TIME1:
Strain (%)
-250.0 1.0
7.0 min
2.0
3.0
4.0
5.0
6.0
7.0
Time (minutes)
DMA7 APPLICATIONS LAB PERKIN-ELMER 7 Series Thermal Analysis System Thu Apr 28 20:32:20 1994
Force (mN)
Dynamic Stress
Force (dynamic)
Force
F (static)
Time
Stress =FA
material response
Phase angle =
Stress
Time
E ~ elastic response
6)
7) s x 10 Viscosity (Pa
Slope 6297938.16 Pa/%
4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 Slope 1274361.04 Pa/% 0.0 0.2 0.4 Strain (%) 0.6 0.8 1.0
0.2
TEMP1: 10.5 C TIME1: -1.2 min
0.6
0.8
1.0
TEMP1: 10.5 C
KPM PERKIN-ELMER 7 Series Thermal nalysis System A Thu Apr 28 20:28:00 1994
Penetration (mm)
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 50.0 75.0
RATE1: 10.0 C/min
125.0
150.0
175.0
TIME1:
0.0 min
2.00
Free Volume
Cx 2.195 x 10 -2 /C
Expansion (mm)
1.95 1.90
1.85
1.70
-5
/C 90.0 Temperature ( C)
Onset 105.53
Tg
110.0
Occupied Volume
80.0
100.0
Extension (mm)
100.0 Temperature (
150.0 C)
200.0 Tech.Support Lab/K.Menard PERKIN-ELMER 7 Series Thermal Analysis System Tue Feb 21 12:29:39 1995
250.0
He/20psi/H/Chiller
TEMP1: 30.0 C TEMP2: 250.0 C
In more detail...
Log Modulus (Pa)
11 10 9 8 7 6 5 4 3
F E D C
Cross-linked
A
Glassy
Temperature
Secondary Dispersion Localized Motion
F E D C
Rubbery
B A
Hookean Behavior
(gamma)
Second Transition
(beta)
Primary Transition
(alpha)
Flow
(melt)
Side Groups
Chain Slipping
Increasing
R. Seymour, 1971
E tan
3.5
2.5
tan
0.8 0.6
Onset 83.29
2.0
Onset 107.82
1.0
100.0 Temperature ( C)
300.0
Analysis System
Modulus (Pa x 10
3.0
or in PP fishing line.
Curve 1: DMA Temp/Time Scan in Extension File info: 1116942 Wed Nov 16 13:20:39 1994 Frequency: 1.00 Hz Dynamic Stress: 200.0mN fishing line Static Stress: 300.0mN # 1 fishing line:1116942 -1 tan (x 10 ) # 2 Storage Modulus (Pa x 10 2.5 9 ) 8.0 7.0 2.0 6.0 5.0 4.0
tan
(x 10
1.5
1.0
0.5
-50.0
RATE1: 10.0 C/min
0.0
50.0 Temperature ( C)
100.0
150.0
200.0
Modulus (Pa x 10
-1
) 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0.0 heavy xlink
TEMP1: 30.0 C TEMP2: 250.0 C TIME1: 0.0 min RATE1: 10.0 C/min
Modulus (Pa x 10
50.0
100.0 Temperature (
150.0 C)
250.0
Analysis System
tan
as well as in blends.
Curve 1: DMA Temp/Time Scan in 3 Point Bending File info: sbr14 Thu Feb 15 10:45:19 1990 Frequency: 1.00 Hz Dynamic Stress: 2.00e+05Pa STYRENE BUTADIENE RUBBE Tension: 110.000% #1
#2
1.0 0.9
10 9
0.8 0.7
Modulus (Pa)
10 7
-50.0
5.0 C/min
0.0 Temperature (
50.0 C)
100.0
150.0
200.0
APPLICATION LABORATORY PERKIN-ELMER 7 Series Thermal Analysis System Sun Nov 26 20:54:43 1995
tan
0.6
) 3.0
2.5
2.5
2.0
Modulus (Pa x 10
1.5 1.5
1.0
Tg or Alpha
1.0
0.5
T*
0.0 Temperature ( C) 50.0 KPM PERKIN-ELMER 7 Series Thermal Sun Nov 26 20:58:36 1995 100.0
0.5
0.0
-100.0
RATE1: 5.0 C/min
-50.0
Analysis System
tan
(x 10
-1
2.0
3.5
3.0
Modulus (Pa x 10
1.5
1.0
0.5
0.0 -100.0
RATE1: 5.0 C/min
-50.0
0.0 Temperature (
50.0 C)
150.0
Analysis System
tan
2.0
(x 10
2.5
-1
10
3.5 0.7 3.0 0.6 0.5 0.4 0.3 0.2 0.1 0.0 -100.0 0.0 Temperature ( C) 100.0 200.0 PE DMA7 R&D LAB PERKIN-ELMER 7 Series Thermal Analysis System Sun Nov 26 20:13:53 1995 2.5 2.0 1.5 1.0 0.5 0.0
Modulus (Pa x 10
TIME1:
0.0 min
4.0
3.5 10 10 9 8 7 6 5 4 3 2 2.0
3.0
-1 )
Modulus (Pa)
2.5
(x 10
1.5
Tg or T T T
Stress Relief
-50.0 0.0 Temperature (
RATE1: 4.0 C/min RATE2: 2.0 C/min
1.0
0.5
0.0 50.0 C) 100.0 B.Cassel PERKIN-ELMER 7 Series Thermal Sun Nov 26 20:59:14 1995 150.0 200.0
-150.0
-100.0
Analysis System
tan
Curing of Thermosets
can be studied at constant temperature or by a temperature ramp can get minimum viscosity, gelation point (time), vitrification point, and activation energies from DMA curve can adapt instrument to do simultaneous DEADMA to follow cure to completion cure studies are not limited to polymeric systems but include food products like cakes and cookies
Modulus
10 5 10 4 10 3 10 2 10 1 10 0 50.0
E E
vitrification point
Curing Minimum Viscosity (time, length, temperature )
90.0 110.0 130.0 150.0
Melting
70.0
2.0 1.5
good
125.0 150.0
Frequency Scans
hold temperature constant and vary frequency allows one to look at trends in material can estimate changes in MW and MWD looks at both tack-like and peel-like behavior can use data for Time Temperature Superposition to extend frequency range or predict age life.
10 6
10 6
s)
Modulus (Pa)
10 5
10 5
10 4
10 4
Flow dominates
10 3 10 -2 10 -1 Frequency (Hz) 10 0
Elastic dominates
10 3 10 1
Viscosity (Pa
10 7
bad
10 7
10 6
10 6
10 5
10 5
10 4
10 4
good
10 3 10 3 10 2 10 2
10 -4
10 -3
10 -2
10 -1
10 0
10 1
2500.0 0.0025 2250.0 2000.0 0.0020 1750.0 1500.0 0.0015 1250.0 1000.0 0.0010 750.0 500.0 0.0005 250.0 0.0 0.0000 0.0
TEMP1: -15.0 C TIME1: 7.0 min
Strain (%)
-250.0 1.0 2.0 3.0 Time (minutes) 4.0 5.0 6.0 7.0
DMA7 APPLICATIONS LAB PERKIN-ELMER 7 Series Thermal Analysis System Thu Apr 28 20:32:20 1994
Force (mN)
Good
% Strain
40.0 35.0 30.0 25.0 20.0 15.0 10.0 5.0 0.0 0.0 1.0 2.0 3.0 4.0 5.0
Bad
6.0
Time in minutes
1750.0 1500.0 1250.0 1000.0 750.0 500.0 250.0 0.0 -250.0 0.0 25.0
TIME1: TIME2: TIME3: TIME4: 11.0 15.0 15.0 75.0 min min min min RATE1: 10.0 C/min RATE2: 10.0 C/min RATE3: 10.0 C/min
Strain (%)
14.0 12.0 10.0 8.0 6.0 4.0 2.0 0.0 50.0 Time (minutes) 75.0 100.0 125.0 KPM PERKIN-ELMER 7 Series Thermal Analysis System Sun Nov 26 20:41:31 1995
1/T
Stress Relaxation
By exploiting the special controls of the DMA-7e, we can run stress relaxation experiments. These look at how the force change for a sample kept at a set distortion as a function of time or temperature.
Experiment Starts
Time
Position
Stress Scans
can do either static or dynamic ramps static scans calculate Youngs modulus and stress-strain curves dynamic scans give material response to increasing oscillatory forces:
get complex viscosity and modulus for each data point can look at changes in elasticity (E) and lag (phase angle) with increasing stress
Both methods are fast tests for QC applications after the material has been fully characterized by other DMA modes.
PP fibers in solvent
200.0 175.0 150.0
Force in mN
Temperature in C
Mater l ia
Behavior
Conclusions
DMA allows you to preform a wide range of tests from sensitive probes of molecular structure to model studies. the DMA-7e allows operation as six different instruments to maximize flexibility. Data can be overlayed with DSC, TGA, TMA, and DTA for easier analysis.
References: Books
Menard, DMA: Introduction to the Technique, Its Applications and Theory, CRC Press, 1999. Brostow et a., Failure of Plastics, Hanser, 1986. Ferry, Viscoelastic Properties of Polymers, Wiley, 1980. Gordon et al., Computer Programs for Rheologists, Hanser, 1995. Gol'dman, Prediction of Deformation Properties of Polymeric and Composite Materials,, ACS, 1994. Mascosko, Rheology, VCH, 1993. Matsouka, Relaxation Phenomena in Polymers, Hanser, 1993. McCrum et al, Anelastic and Dielectric Properties of Polymeric Solids, Dover, 1992 (reprint of 1967 edition). Nielsen et al., Mechanical Properties of Polymers and Composites, Dekker, 1994. Sperling, Introduction to Physical Polymer Science, Academic Press, 1994. Ward et al., Introduction to Mechanical Properties of Solid Polymers, Wiley, 1993.