CNMR Athlone Institute of

Technology

Thermal and
Mechanical Analysis
Alan Murphy

CNMR

Athlone Institute of

Technology

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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Athlone Institute of

Technology

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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Athlone Institute of

Technology

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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Athlone Institute of

Technology

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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Athlone Institute of

Technology

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)

CNMR Athlone Institute of

Technology

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
Hf) based on IS EN ISO 3146:2000; Method C2

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Technology

Thermal Analysis

Differential Scanning Calorimetry (DSC)

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Technology

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.

CNMR Athlone Institute of

Technology

Thermal Analysis

Differential Scanning Calorimetry (DSC)

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Technology

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 thermomechanical 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

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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

CNMR Athlone Institute of

Technology

Thermal Analysis

CNMR Athlone Institute of

Technology

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.

CNMR Athlone Institute of

Technology

Thermal Analysis

Thermogravimetric Analysis (TGA)

% Polymer
=
64.4%
% Carbon Black =
3.4%
% Glass Fibre =
32.2%

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Athlone Institute of

Technology

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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Athlone Institute of Technology

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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Athlone Institute of Technology

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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Athlone Institute of Technology

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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Athlone Institute of Technology

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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Technology

Chemical Analysis

Gel Permeation Chromatography (GPC)

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Technology

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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Technology

Case Study A

Contamination Issue:

%T

4000.0

3000

2000

1500

1000

650.0

1/cm

Isolated White Particulate Matter: FTIR Polytetrafluoroethylene

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Technology

Case Study A

Contamination Issue:

Isolated White Particulate Matter: DSC Tm = 329oC

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Technology

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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Technology

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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Technology

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 PETbased.

PET

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Case Study C

Recycling Issue:
DSC confirmed that the contamination had a T m 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
same
characteristics

had the
thermal
as
the

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Technology

THANK YOU...

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Technology

Contact Details
Mr. Mark Atterbury
Senior Research Officer
Officer
Tel:
00353 9064 83070
Email: matterbury@ait.ie

Mr. Alan Murphy

Senior Research
00353 9064 42575
amurphy@ait.ie