Effect of Fabrication and Electrical Testing on

the Measured Performance of Thermoplastic

CNT Composites
Jane M. Spikowski
PolyOne Corporation
ACCE 2013
Novi, MI
September 11-13, 2013
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Measurement Challenges in CNT Composites

Multi-phase materials
Dispersion
Distribution
High sensitivity due to low filler concentration

Processing-dependent orientation of conductive particles

Injection molding vs. compression molding
Potential for large effect due to high aspect ratio of CNT

Dispersion
Processing
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Product
Forming

Categories of Electrical Testing Methods

1. Standardized methods reported on datasheets

Two ASTM D257 test configurations

MIL-DTL-83528C

2. Methods to understand electrical behavior mechanistically

3. Application-driven testing the true test of a materials performance

Page 4

Two-Probe vs. Four-Probe Measurement Techniques

Two-Probe

Four-Probe
Current Source

Resistance
Meter

Voltmeter

Contact
Resistance

Test Specimen

Page 5

Current flows through

measurement circuit

Current does not flow through

measurement circuit

Contact resistance and

measured resistance are not
independent

Contact resistance is
independent of measured
resistance

Two-Probe Silver Paint End Probe Method

Common variation of ASTM D4496

Best opportunity for current to travel through the entire cross-section of

the part

Purpose: Eliminate the potentially insulative skin layer from the electrical
circuit

Two-probe method susceptible to contact resistance

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Two-Probe Silver Paint Surface Probe Method

Available current path is not restricted to the surface of the part opportunity for an in-plane volume resistance measurement

MIL-DTL-83528C Basis for interpretation as a volume resistance

method (ASTM D257 assumes current travels across surface only)

Current must pass through insulative skin layer, if present

Same measurement area as end probe method

Current and
voltage electrodes

Effective measurement area

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Effective measurement area

(MIL-DTL-83528C)

Materials

Two formulations: 3% and 5% multi-walled CNT in PC

Compounded using 18mm co-rotating intermeshing twin-screw extruder

22 Factorial DOE based on previously identified key factors:

Melt temperature (as controlled by varying the barrel temperatures) Molding
temperature
Injection speed

Page 8

Injection molded into disk, rectangular bar, and tensile bar:

Two-Probe Silver Paint Surface vs. End Probe

Log(Volume Resistivity [-cm])

10
8

3% Surface
3% End
5% Surface
5% End

4
2
0

[Low, Low] [Low, High] [High, High] [High, Low]

Molding Condition Set [Temperature, Speed]

Page 9

Lowest resistivity at high temperature and low speed as measured by

both methods

Statistically significant difference between surface vs. end probe

measurements for 3% CNT molded using fast speed

Silver Paint Method Customization

Both silver paint electrode configurations can be used for bulk or localized
testing

Opportunity to reveal different features of electrical performance

Highly customizable test techniques applicable to complex parts

LOCALIZED

BULK

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Localized Silver Paint Electrode Results

FAST
Injection
Speed

Page 11

End vs. surface probe difference increases away from gate

As residence time in mold

Relaxation of shear induced stresses introduced by high injection speed

, uniformity in thickness direction

Localized Silver Paint Electrode Results

SLOW
Injection
Speed

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No significant difference between end vs. surface probes

Less sensitive to residence time effects due to lower shear-induced

stresses

Design Space Using Two-Probe Test Methods

From the same starting material, varying the molding conditions and test
method provides a wide range of measured properties:
Insulating

Anti-Static
109 1012
Static
Dissipative
106 109

Conductive
<102 106

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Effective specification requires more than just a target resistivity value

Formulation provides coarse tuning

Processing provides fine tuning

Conclusions:
Electrical Testing and Injection Molding Effects

Each test configuration revealed that increasing the melt temperature and
decreasing the injection speed minimizes the resistivity

Different methods can result in drastically different absolute

measurements of the same specimen

Using a combination of methods enables the detection of more detailed

features
Residence time effects
Variation in the thickness direction

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Silver paint electrode methods are highly customizable and compatible

with complex geometries

Secondary Heating (Annealing) Effects

Page 15

Annealing Effects Bulk Measurements

Bulk silver paint

surface resistance
method

Page 16

Heated injection molded parts above Tg using a press low-strain

For all molding conditions, resistance decreased as annealing time

increased

Annealing Effects Local Measurements

High Speed

Gate

Page 17

Low Speed

End

Annealing eliminated the discrepancy between surface and end probe

measurements enhancement of conductive CNT network

Suggests relaxation of molded-in strain and nano-scale rearrangement

Conclusions

Each forming process after initial compounding can affect conductive

network

Changes can occur in the quiescent state in the melt without additional
mixing or CNT dispersion
Relaxation of strains introduced before last cooling step
Nano-scale CNT rearrangement and association

Page 18

Heat history can have a significant effect on properties of thermoplastic

CNT composites

Acknowledgements and Contact Information

The authors would like to acknowledge:

Glenn Evans
Rachel Winkelman
Polymer Diagnostics, Inc.
Ohio Department of Development

Contact Information:
jane.spikowski@polyone.com
440.930.1127

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