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POLYMER COMPOSITES

Improved method for the measurement of the glass


transition temperature by Dynamic Mechanical Analysis
(DMA) a VAMAS international validation exercise
Gnaniah S.J.P, Sims G.D, Yong A.
National Physical Laboratory, Hampton Road, Teddington TWA 11 0LW, UK

Background to Tg measurement
Polymer composites - Tg is used as a measure of the
degree of cure for the material.
Tg is a key material parameter specified in material
qualification plans
Thermal analysis techniques DSC, DMA widely used
for the measurement. TMA is used when the thermal
expansion additionally required
Industry concerns about the wide variability in the
reported data

DSC
Uses small quantities of material specimens - not
necessarily representative of end product in service.
Good response for pure resin
Poor response for composite samples

DMA
Preferred technique for polymer composites
additionally indicates mechanical response as a
function of temperature.

Results of an interlaboratory trial by DSC and DMA


on the same polymeric material.

Measurement issues by DMA


Test options

Traceability
Temperature (K)
main interest.

Images courtesy of TA Instruments

Additionally load
and displacement
to consider.

Data analysis

SI

mol

cd

Thermal lag

m
kg

Impact

Wide choice of loading configurations

Lack of consistent calibration protocols and reference


materials

Wide choice of analysis points

The temperature sensor measures the oven temperature


rather than the specimen itself

Proposed solution

Standardised test mode

Development of reference specimens and artefacts

Standardised procedures and best practice guidance

New procedure for heating rate dependency resulting in


improved data generation.

Test parameters influencing DMA data

Other parameters: thickness, orientation, moisture, conditioning

Development of new international standard

Analysis option

Condition

Usage

Tg(0)

Value extrapolated to 0 C/min heating rate from


calibration curve based on multiple heating rate tests

Takes into account the thermal lag in the


system.

Tg(n)

Data generated at any heating rate n C/min

Suitable for QA purposes and can be tested at


a faster heating rate if needed.

ISO 6721: 11 DMA Analysis options


1000

[]LossModulus(MPa)

3C/min

ISO 6721: Part 11


Plastics - Determination of dynamic
mechanical properties - Part 11: Glass
transition temperature

DMA Multiple heating rate analysis Calibration curve

5C/min

800

10C/min

600

400

200
120

130

140

150

Temperature(C)

160

170

Indium melting point


transition measured at
different heating rates

180
UniversalV4.5ATAInstruments

Phase 1 validation international interlaboratory exercise


Outcome

Test material

Carbon fibre epoxy.

International Participation

37participants from 13countries

Instrumentation details

Data from 8instrument suppliers and 9different models

Test mode(s)

Data received included tests undertaken in single cantilever, 3point bend and torsion modes.

Temperature calibration

Disabled. Data assessed as a worst case scenario measurement in the current excercise.

Test protocol

3specimens tested at 3, 5 and 10C/min heating rate

Data analysis

All possible analysis points collected

Ongoing and Future Study

Data reporting

Excel spreadsheet template supplied to participants to minimise inconsistencies in data


reporting.

Next phase in the study will involve measurements of the


Indium embedded carbon fibre calibration specimen

Analysis point

Heating rate

Tg (Reference)

Maximum difference

(C/minute)

Tg Inflection

Inflection point in the storage modulus vs temperature


signal provided the most consistent data across test sites
Flow of inert atmosphere (e.g. nitrogen) during the test
gave a lower heating rate dependence
The extrapolated heating rate value (i.e. Tg reference)
provided the lowest variation across sites

An additional carbon fibre calibration specimen using


Tin as a reference material is to be manufactured (for
use at higher temperatures). This will enable a two point
temperature calibration of the equipment using both
indium and tin.

Standard deviation
C

15

3.1

0 (extrapolated)

1.7

Multiple heating rate data generated by participants using


different instrumentation

The traceability aspects of the reference specimen


measurements are in progress in collaboration with experts
in temperature measurement

Acknowledgements
The authors would like to thank the industry and academic
participants for their valuable input in the validation exercise
by testing and providing additional comments. The support
by the following is greatly acknowledged.
Anton Paar (Austria)
Atomic Weapons Establishment (UK)
BAE Systems (UK)
Commonwealth Scientific and Industrial
Research Organisation (Australia)

Exova (USA, UK, France and Sweden)


GE Aviation (UK)
Gearing Scientific (UK)
Hexcel (UK)
INMETRO (Brazil)
Intertek (USA)
Laboratrio Nacional de Engenharia Civil (Portugal)
Lacerta Technology (UK)
National Institute of Metrology (China)
National Composites Centre (UK)

National Measurement Institute of South Africa (South Africa)


Nottingham University (UK)
Norwegian Defence Research Establishment (Norway)
Oxford University (UK)
Red Composites (UK)
TA Instruments (UK)
Tencate Advanced Composites (UK)
Ulster University (Ireland)
Vestas (Denmark)

For more details, suggestions,


comments and offers
to participate in future
intercomparison work,
please contact:
Sam Gnaniah
e: sam.gnaniah@npl.co.uk
t: +44 20 8943 6174

www.npl.co.uk

NPL Management Limited, 2016. 11763/0816

VAMAS Interlaboratory trial Phase 1 Test protocol

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