CNMR Athlone Institute of Technology

Thermal and
Mechanical Analysis
Alan Murphy
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Introduction
Plastic materials are tested throughout their life:

Monomer / Reactants
Polymer / Raw Material & Additives
Product / Design
Product / Research & Development
Processing / Quality Control
Product / Service
Product / End of Life
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Introduction
A knowledge of available test methods is useful to:

Identify Research & Development requirements

Control incoming raw material quality
Quantify product specifications
Understand material data sheets
Correct manufacturing problems
Investigate customer complaints
Continuously improve the product
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Introduction
Raw Material Testing

Control of raw material helps to assure consistent

processing and end product characteristics.

Melt Flow Rate and Density are the most common raw
material tests but other raw material tests may be
specified if warranted by the product.
Eg.1 Impact test for safety glasses.
Eg.2 GPC for molecular weight control
Eg 3. TGA to measure % glass content
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Introduction
Testing during processing

QC tests, such as weight or moisture content

Troubleshooting tests, such as investigating :

Why a component is cracking during assembly

Why an extruded tube is shrinking after manufacture
Where contamination is coming from & what type
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Introduction
Testing during service

Research and Development tests, such as comparison

of alternative materials or property loss with time.

Customer complaints.
eg Why has the product failed after 3 months use ?
Why has the product embrittled ?
Why has discolouration occurred ?
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Thermal Analysis
ANALYTICAL TECHNIQUES
Differential Scanning Calorimetry (DSC)
Dynamic Mechanical Thermal Analysis (DMTA)
Thermogravimetric Analysis (TGA)
Melt Flow Rheology (MFI)
Gel Permeation Chromatography (GPC)
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Thermal Analysis
Differential Scanning Calorimetry (DSC)
DSC is a thermal method of analysis to study the thermal
behaviour and thermal properties of materials (typically
polymers). The material is sealed in a sample pan and
subjected to a controlled temperature programme.

The resulting thermograph can yield much valuable

information about the properties of the material analysed.

Main use of DSC: Material Identification (Tm and DHf)

based on IS EN ISO 3146:2000; Method C2
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Thermal Analysis
Differential Scanning Calorimetry (DSC)
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Thermal Analysis
Differential Scanning Calorimetry (DSC)
Other uses of DSC:
% Crystallinity determination by DSC (based on IS EN ISO
3146:2000; Method C2).

Purity and Polymorphism analysis by DSC.

Thermal Stability of materials (e.g. oxidative induction

time (OiT) of materials) by DSC.
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Thermal Analysis
Differential Scanning Calorimetry (DSC)
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Thermal Analysis
Dynamic Mechanical Thermal Analysis (DMTA)
Dynamic Mechanical Thermal Analysis (DMTA) records the
temperature-dependent visco-elastic properties and determines the
modulus of elasticity and the damping values by applying an
oscillating force to the sample.

Thermal method of analysis used to determine thermo-mechanical

properties of materials (i.e. Glass Transition Temperature Tg).
Used as an alternative to DSC which is typically estimating Tg.

Used to more accurately determine the Tg value, strength and

temperature-dependant elongation of a material. in several modes
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Thermal Analysis
Thermogravimetric Analysis (TGA)
TGA measures the weight of a substance heated at a
controlled rate as a function of temperature or time.

All materials ultimately decompose on heating, and the

decomposition temperature and profile is a characteristic
property of each material.

Main use of TGA: Inorganic Content of Material

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Thermal Analysis
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Thermal Analysis
Thermogravimetric Analysis (TGA)
Other uses of TGA:

Material Thermal Stability.

Moisture and Volatiles Content (TG-IR).

Composition of Multi-Component Systems.

Shelf-Life Studies and Decomposition Kinetics.

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Thermal Analysis
Thermogravimetric Analysis (TGA)
% Polymer = 64.4%

% Carbon Black = 3.4%

% Glass Fibre = 32.2%

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Rheological Analysis
Melt Flow Rate (MFR) to ISO 1133.

Grams of material that flow through a simple die in 10

minutes using a loaded piston and a set temperature.

Is a measure of Shear Viscosity and is directly

proportional to the average molecular weight.

Uses: Raw material control; processing quality; regrind

studies; useful troubleshooting test
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Rheological Analysis
Capillary Rheometry: uses motor driven pistons to
produce high pressures and two barrels with dies to
measure shear viscosity and elongational viscosity.

Mimics processing conditions; gives information on

average molecular weight and molecular weight
distribution.

Uses: mould and die design; new material validation;

troubleshooting; raw material control
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Mechanical Analysis
Tensile Testing to ISO 527

Measures the strength of a material and its flexibility

(elongation).

Also used to measure peel strength, bond strength,

weld strength.

Carried out on dumbbell specimens or actual product.

Uses: QC control for material or product

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Impact Analysis
Izod and Charpy Impact Testing to ISO 179/180.

These are pendulum impact tests generally done on test

bars but can be adapted for small products.

Usually notched, testing can be done at ambient or sub-

zero temperatures.

Uses: QC test, material comparison, notch sensitivity

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Aging Studies
Use of elevated temperatures to accelerate the aging
process of plastic products.

Based on a 10C rise in environmental temperature

produces a twofold increase in the degradation rate.

Humidity can be applied too if considered a factor.

Uses: shelf-life studies; product data; regrind analysis

and the affect of other influences on product lifespan
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Chemical Analysis
Gel Permeation Chromatography (GPC)
GPC causes separation by various pore sizes in the
column packing material, separating on the basis of
molecular size, not molecular weight.

Main use of GPC (or SEC): Measuring average molecular

weight (Mp) and molecular weight distribution (Mw) of a
material.

Typical Detection methods used are UV-vis and Refractive

Index.
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Chemical Analysis
Gel Permeation Chromatography (GPC)
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Case Study A
Contamination Issue:
The client sent one sample of their product with
particulate on the bottom of the container.
How was it resolved?

Specimens were isolated and cleaned in Class

100 Cabinet

FTIR and DSC were applied to determine

the material types
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Case Study A
Contamination Issue:

%T

4000.0 3000 2000 1500 1000 650.0

1/cm

Isolated White Particulate Matter: FTIR Polytetrafluoroethylene (PTFE)

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Case Study A
Contamination Issue:

Isolated White Particulate Matter: DSC Tm = 329oC

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Case Study A
Outcome:
The client checked their materials list and
equipment associated with this product.
The PTFE Source was determined to have come
from a stirring bar used during manufacture of
the solution.
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Case Study B
Processing Issue:
A batch of parts were cracking in service after normal
pressure was put on the end of the part.

How was it resolved?

GPC was used to

compare both good
and bad samples.
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Case Study B
Processing Issue:
Therefore we looked at the process and decided
to look at the moisture content of the pre-
processed material:
Using Karl Fischer Coulometry we determined that the
material had not been dried sufficiently.

This then led to the materials molecular weight being

affected during processing causing the material in the
part to be weakened.
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Case Study C
Recycling Issue:
A manufacturer using regrind polyethylene material
experienced difficulties with contamination of screen
plates within an extruder.

The problem was thought to be caused by

contamination of the regrind feedstock. CNMR were
requested to:
(1) Identify the contaminant;
(2) Determine the source of contamination if
possible;
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Case Study C
Recycling Issue:
Debris from the screen plates was
examined under an optical microscope. It
was determined that the contamination
was not compatible with the matrix and
could be removed easily.

FTIR determined that the

materials present were PET-based.

PET
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Case Study C
Recycling Issue:
DSC confirmed that the contamination had a Tm at ca. 250oC. This is
typical of the melting characteristics demonstrated by PET.

Material from two silos were

analysed. The granules were
separated simply according to
density.
Only one material from one of
the silos was found to contain
dense particles.
These particles had the same
thermal characteristics as the
contaminant.
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THANK YOU...
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Contact Details
Mr. Mark Atterbury Mr. Alan Murphy
Senior Research Officer Senior Research Officer
Tel: 00353 9064 83070 00353 9064 42575
Email: [email protected] [email protected]