Real-Time Monitoring of Polymer/Clay Compounding

Using Dielectric, Optical and Fluorescence Measurements

Anthony J. Bur
T Bur Associates
and
Yu-Hsin Lee, Steven C. Roth and Paul R. Start
NIST, Polymers Division
and
Paul H. Maupin
Office of Basic Energy Science, US Dept.of Energy
and
Michael McBrearty
T Bur Associates
 Outline

 The TBA Dielectric Slit Die

 Monitoring Nylon/Clay Nanocomposites Compounding
 Dielectric
 Optical transmission
 Outline

 The TBA Dielectric Slit Die

 Monitoring Nylon/Clay Nanocomposites Compounding
 Dielectric
 Optical transmission
 Model Development: Extent of Exfoliation
 Outline

 The TBA Dielectric Slit Die

 Monitoring Nylon/Clay Nanocomposites Compounding
 Dielectric
 Optical transmission
 Model Development: Extent of Exfoliation
 Fluorescence Monitoring
Outstanding Question:
What is an exfoliated clay nanocomposite?

Nylon 6/30B clay

 Building a Knowledge Base

Composite
Materials Property

Extent of Exfoliation
 Building a Knowledge Base

Composite
Materials Property

Scaling factors?
Functional relationships?

Extent of Exfoliation
 Building a Knowledge Base

Composite
Materials Property

Scaling factors?
Functional relationships?

Extent of Exfoliation

Measuring extent of exfoliation is prerequisite to controlling it.

 TEMs Nylon 11 with 15A and 30B
Compounded at 195 oC

Nylon 11/30B Nylon 11/15A

 The TBA Dielectric Slit Die

Instrument Concept:
A Slit Platform for Mounting Multiple Sensors
 The NIST Dielectric Slit Die

Advantage of the slit configuration:

• Constant geometry sample chamber can be
interrogated by multiple of sensors
• Has configuration of a slit die rheometer.
 Interdigitating Electrodes

ceramic substrate

Top View

Interdigitating electrodes

Side View

ceramic
resin
flow 2 mm slit

fringing field ceramic

 Experimental Setup for Extrusion

optical sensor
dielectric sensor

lock-in amplifier

optical fiber
computer

ε* = ε’ - iε”
light source

spectrometer
 Compounding Nylon/Clay Composites

Materials:
• nylon 6, 11 and 12
• montmorillonite clays (added at 4 % wt.)
 natural Na+ clay (aggregate composite)
 three organo modified clays
15A, 20A, 30B (partially exfoliated)

clay silicate layer

CH3
Ionic bond
N
CH3
organo surfactant 15A
clay silicate layer
Compounding Nylon/Clay Composites:
Dielectric Monitoring

nylon 11 at 195 oC
 Analyzing Dielectric Data

Data are fit with dispersion function:

i  o    j
     
 
*

1   i j 
1  j
 o j

DC conductivity Cole-Cole dielectric relaxation

 Analyzing Dielectric Data

5.5 nylon 12/20A at 195 oC

5.0
log dielectric loss
4.5
4.0
3.5
y = -0.9785x + 6.9787
3.0
2.5
1.0 1.5 2.0 2.5 3.0 3.5
log f Hz
 Analyzing Dielectric Data

5.5 nylon 12/20A at 195 oC

5.0
log dielectric loss
4.5
4.0
3.5
y = -0.9785x + 6.9787
3.0
2.5
1.0 1.5 2.0 2.5 3.0 3.5
log f Hz

Carry out non-linear regression curve fitting to

retrieve relaxation parameters:
i  o    j
     
 
*

1   i j 
1  j
 o j

DC conductivity Cole-Cole dielectric relaxation

 Maxwell Wagner Relaxation

nylon 11 at 195 oC
  Log fMW
1000
15 A Nylon 11 at 198 oC --

20 A
Nylon 11/Na+ 0.74
Dielectric Loss, "

800
30 B Nylon 11/30B 0.62
Na+
600 Nylon 11/20A 0.24
Nylon 11/15A 0.16
400 Increasing Degree
of Exfoliation Nylon 6 at 242 oC --

200 Nylon 6/15A 1.98

Maxwell-Wagner
Nylon 6/30B 1.10
-2 -1.5 -1 -0.5 0 0.5 1 1.5 2
Log Frequency (Hz)
 Maxwell Wagner Relaxation

Reflects RC Time Constant for Charging Polymer/Clay Interface

silicate nanolayer
RC   MW  (2f MW ) 1
- +
+
exfoliated -- +
+
- - + nylon R = resistance of nylon (constant)
C = capacitance of clay particle
clay particle
(increases with exfoliation)
- - ++ +
aggregate -- +
- nylon
+  MW large or fMW small
for exfoliated composite
 Compounding Nylon/Clay Composites
Developing an Extent of Exfoliation Scale

silicate nanolayer
- +
- + + exfoliated
-- +
- + nylon

time constant: RC   MW or    MW
drift velocity: bv  qE where b = 6πηa (Stokes)
Ohm’s law: nqv  E

n o C n o q 2  MW
Extent of Exfoliation: 
nC o 6 o a
 Compounding Nylon/Clay Composites
Developing an Extent of Exfoliation Scale

n o C n o q 2  MW
Extent of Exfoliation: 
nC o 6 o a

η is molecular viscosity – obtain from diffusion constant or

dielectric relaxation time

From dielectric measurements:

8a 3
r 
2kT
 Compounding Nylon/Clay Composites
Developing an Extent of Exfoliation Scale

8a 3
From dielectric measurements: r 
2kT
 An Extent of Exfoliation
Scale
Use τr from γ relaxation of nylons:

n o C 2n o q 2  MW a 2
Extent of Exfoliation: 
nC o 3 o kT r
 An Extent of Exfoliation
Scale
Use τr from γ relaxation of nylons:

n o C 2n o q 2  MW a 2
Extent of Exfoliation: 
nC o 3 o kT r

increasing exfoliation
1.6 30B 20A 15A
1.4 PA12
1.2 Na 30B 20A 15A
1 PA11
0.8
15A 20A 30B
0.6 PA6
0.4
0.2
-4000 -2000 0 2000 4000 6000 8000
0
Extent of Exfoliation
Compounding Nylon/Clay Composites:
Optical Monitoring

central fiber: 200 μm core

light source transmission

PMT #1

optical fibers
light source

filter
sensor beamsplitter

PMT #2

or
dielectric slit die
CCD spectrometer
 Compounding Nylon/Clay Composites:
Optical Monitoring

optical fiber Nylon 11 at 195 oC

lens

sapphire Is 2 mm slit
window Iw
 Compounding Nylon/Clay Composites:
Optical Monitoring

 
Nylon 11 at 195 oC It  I o e
= volume fraction of
aggregate
  (n2)
Na clay: 1.67
nylons: 1.53
organo clays: 1.43 – 1.46
 Compounding Nylon/Clay Composites:
Optical Monitoring

 
Nylon 11 at 195 oC It  I o e
= volume fraction of
aggregate
  (n2)
0.030
Vol. fraction aggregate

0.025
30B
0.020 Na+
20A
0.015 15A

0.010
neat
0.005

0.000
0 2000 4000 6000 8000 10000 12000
Time (s)
 Compounding Nylon/Clay Composites:
Optical Monitoring

0 .0 3 0 nylon 12

Vol. fraction aggregate

0 .0 2 5 Na
0 .0 2 0
20A 30B
0 .0 1 5 15A
 
It  I o e
0 .0 1 0
0 .0 0 5
ne at
0 .0 0 0
0 2000 4000 6000 8000
= volume fraction of
T im e (s )
aggregate
0.030
volume fraction aggregate

0.025 Na nylon 6
0.020
0.015 20A
15A 30B
0.010
0.005
neat
0.000
0 2000 4000 6000 8000
Time s
 Compounding Nylon/Clay Composites
Developing an Extent of Exfoliation Scale

Correlating Optical and Dielectric Measurements

optical fiber

lens

sapphire Is 2 mm slit
window Iw

30B 20A15A
1.6
1.4
1.2 PA12
1 Na 30B 20A 15A
0.8 PA11
0.6 15A 20A 30B
0.4 PA6
0.2
-4000 -2000 0 2000 4000 6000 8000
0
Extent of Exfoliation
 Correlating Optical and Dielectric Monitoring

14000
Extent of Exfoliation

12000
10000
8000
6000
4000
2000
0
0 0.004 0.008 0.012 0.016 0.02 0.024
Volume Fraction of Aggregate
 Compounding Nylon/Clay Composites:
Fluorescence Monitoring

clay silicate layer

Ionic bond
nile blue replaces NH 2 N
+ CH3 N
5% of surfactant CH3
organo surfactant 15A
by ion exchange clay silicate layer

concentration quenching
 Compounding Nylon 11/15A nile blue dye

T = 195 oC

batch mixer

light source m
i
x
spectrometer e
r

optical fiber
 Compounding Nylon 11/15A nile blue

twin screw compounding

TEM from extrusion

batch mixer

optical sensor
 Summary

• Continuous Monitoring Using Dielectric Slit Die

• Extent of Exfoliation from Dielectric, Light Transmission
and Fluorescence
 Volume fraction of aggregate (light transmission):
I  I o e  
 Extent of exfoliation scale (dielectric):
n o C n o q 2  MW

nC o 6 o a
• Measuring Extent of Exfoliation is a Prerequisite for
Controlling It and Building a Knowledge Base of
Materials Property Data
 Additional Information

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