MATERIALS CHARACTERIZATION (MST613)

LAB REPORT (PART A)

SUBMITTED TO:
PROF MADYA DR NOOR NAJMI BONNIA

NAME:
NUR SYUHADA BINTI AHMAD TERMIZI

STUDENT ID:
2019813952

GROUP:
AS2404M2

DATE OF SUBMISSION:
27th of MAY 2021
 EXPERIMENT 1
DEGRADATION BEHAVIOR OF TERMOSET, TERMOPLASTIC, RUBBER AND
COMPOSITE USING THERMAL GRAVIMETRIC ANALYSER

Objectives:

1. To understand the use and function of thermal gravimetric analyzer.

2. To monitors changes in the mass of a sample as a function of time and temperature.

Methodology:
Sample is loaded onto clean and free from dust sample pan that is usually made up
from platinum due to its inertness. This sample pan is supported by precision balance and
resides in a furnace and is heated or cooled during the experiment. The sample is continually
weighted while heating, as an inert sample purge gas atmosphere is purged together which to
prevent oxidation or undesired reaction so that the sample only reacts to temperature during
decomposition. Analysis is carried out by raising the temperature gradually and plotting
weight against temperature.

TGA Analysis:
The principle of thermogravimetric analysis is including the measurement of
measurement of a material’s thermal stability, filler content in polymers, moisture and
residual solvent content, and the percent composition of components in a compound,
compositional analysis of multi-component materials or blends.

Figure 1: TGA for polymers and rubbers.

 For polymers and rubbers TGA thermal decomposition thermogram can be intpreted
into 4 steps. First step is the high volatility will weight loss first due to the loss of plasticizers
from the polymer. Second step is the low volatility will weight loss due to degradation of the
residual polymer. Third step is when the weight loss occurs due to combustion of compounds
such as residual carbon from polymer breakdown or burn off of carbon black filler. Last step
is where the residue value is the remaining ash due to inorganic filler materials that were
present in the material.

Figure 2: TGA results for epoxy-glass powder.

For example, figure 1 has shown the results for epoxy-glass powder. The epoxy resin
undergoes thermal degradation beginning at 440 C with a mass loss of 57.4%. At 650 C, the
purge gas flowing over the sample was automatically switched to oxygen and the carbon
residue was burned off at 655 C with a mass loss of 10.5%. The material remaining behind
after exposing the sample to oxygen is the inert glass filler, which the TGA shows comprises
31.8% of the mass of the epoxy resin.

In figure 2, the components in a tire

elastomer can be figured out and clearly identified
by TGA. These elastomers consist of a blend of polymer, oil4:extender,
Figure carbon black
TGA degradation and
for two fillers.
different
Figure 3: TGA results on separation of tyre
Figured 3 displays the TGA results on comparison the amount
HDPEofbottles
filler presence on two different high
elastomer components.
density polyethylene (HDPE) container.
Pre-Lab Questions:

a) State information can we get from TGA/DSC thermograms for polymer applications?
- TGA gives information only for substances which show a change in mass on
heating or cooling. TGA measurements provide valuable information that
can be used to select materials for certain end-use applications, predict
product performance and improve product quality such as determine
characteristics of materials (polymers), to determine degradation
temperatures, absorbed moisture content of materials, the level of inorganic
and organic components in materials, decomposition points of explosives, and
solvent residues.
b) Determine why the thermal decomposition must reach to high temperatures above
700°C to complete the degradation for hydrocarbon-based polymers?
- The thermal decomposition must reach to high temperatures above 700 C to
complete the degradation for hydrocarbon based polymers because the
strong interaction of the molecular structure of polymer. At high
temperature, the components of the long chain backbone of the polymer will
break and react with one another and then change the properties of the
polymer. The degradation at high temperature involves changes to the
molecular weight of the polymer which then lead to physical and optical
property changes.
c) Some additives containing inorganic components may need higher temperatures to
degrade completely. Name any filler or additives that may remain residue after 1000°
- Calcium carbonate (chalk)

EXPERIMENT 2
 DETERMINATION OF MELTING POINT, CRYSTALLINITY AND GLASS
TRANSITION TEMPERATURE OF THERMOSET, THERMOPLASTIC AND
COMPOSITE USING DIFFERENTIAL SCANNING CALORIMETER

Objectives:

1. To determine the heat capacity of the materials.

2. To detect the sample being had being cared properly or not.
3. To determine the glass transition temperature (Tg), melting temperature (Tm), and
crystallinity (Tc) of the samples.

Methodology:
Differential Scanning Calorimetry (DSC) is a thermal analysis technique to measure
the amount of heat is absorbed or released by a sample when it is heated, cooled as a function
of temperature or time, while the sample is exposed to a controlled temperature program.
DSC compares differences between the heat flow rate of the test sample and known
reference materials which determines variations in material composition, crystallinity and
oxidation. The DSC set-up is composed of a measurement chamber and a computer. Two
pans are heated in the measurement chamber. An empty sample pan is weighed before a
small amount of sample was loaded onto sample pan that usually made from alumina, gold or
stainless steel and placed into a temperature-controlled DSC cell after weighing again.
Another pan without sample was used as a reference. The sample purge gas such as helium or
nitrogen is applied to get rid moisture from the sample. DSC run involves heating or cooling
the sample at a controlled steady rate, and monitoring the heat flow to characterize the phase
transitions and cure reactions as a function of temperature.

Operational Principle and Data Analysis:

When the sample evolves heat through some thermal process, the DSC plot will show
an increase in heat flow that indicates of an exothermic event because the temperature
registered by the sample is higher than that sensed by the reference. If the sample is
undergoing a thermal event that causes it to absorb more heat than the reference does such as
melting process, DSC plot will show a decrease in heat flow and indicates an endothermic
event where the temperature sensor measures a lower temperature for the sample compared to
the reference.
 Figure 5: DSC plot of PET sample showing a glass transition, crystallization peak and melting
peak

The first transition this sample of PET undergoes is seen at 78 °C, and is known as the glass
transition temperature (Tg). At this transition, the polymer changes from a relatively hard,
glassy solid, to a softer, more flexible or rubbery material. This shows the increasing in the
heat capacity of the polymer. Polymers usually have higher heat capacity above its glass
transition temperature. Thus, DSC will detect the polymer’s glass transition temperature. The
glass transition temperature n does not occur suddenly at one unique temperature but rather
over a range of temperatures. The second transition, occurring at 144 °C, is the crystallization
point. For crystallinity (Tc), the polymer gives off heat when it crystallizes that is called an
exothermic event as results in a decrease in the recorded heat flow. The latent heat (enthalpy)
of crystallization is determined from the area under the curve. Polymer chains have higher
mobility above the glass transition temperature. Hence, the chains have enough energy to
form ordered arrangements and crystallize at temperatures above Tg. Finally, as the heat is
continued to increase, the PET melt point is reached. For melting (Tm), the polymer crystals
started to melt, then the absorption of heat is occurred and indicates the endothermic event.
When the heating process is passed the Tc, it will reach and hit the polymer's melting
temperature, or Tm, and those polymer crystals begin to fall apart. The chains will break of
their ordered arrangements, and begin to move around freely. The extra heat flow during
melting shows up as a big peak on DSC plot happen due to a lot of heat into the polymer
under the sample pan in order to both melt the crystals and keep the temperature rising at the
same rate as that of the reference

Figure 6: DSC Scan for Epoxy-Amine Partially Cured Thermoset

Figure 7: DSC first run curves of neat epoxy and epoxy matrix composites reinforced with giant
bamboo fibers.
Pre-Lab Questions:
1. Explain the difference between first order and order transition.
- First order transition is transitions like melting and crystallization, which do
have latent heat where the heat exchange is required. For the second order
transition, there is a change in heat capacity, but there is no latent heat
involved like the glass transition.
2. Define glass transition temperature. State factors affecting glass transition
temperature.
- The temperature below which the polymer becomes hard, brittle and glassy
and above which it is softener and flexible. The factors that affecting glass
transition temperature are intermolecular forces, plasticizers, pendant
groups, presence of cross-linking and Chain Stiffness-Stiffening groups.
3. State whether the following enthalpies are exothermic or endothermic reaction.
 Melting of fusion (Endothermic)
 Oxidation (Exothermic)
 Crosslinking (Exothermic)
 Degradation (Endothermic)
 Crystallization (Exothermic)
4. State the requirement for measuring low temperature glass transition for elastomers or
rubbers.
- Rubber or elastomers are used above their Tg, that is, in the rubbery state,
where they are soft and flexible and the crosslinking prevents free flow of
their molecules, thus endowing rubber with a set shape at room temperature
 EXPERIMENT 3
DYNAMIC MECHANICAL ANALYSIS (DMA) OF POLYMER

Objectives:
1. To determine the storage, loss and tan delta of sample.
2. To differentiate the modulus value of 3 types of polymer sample.

Methodology:
Sample is prepared and cutting the sample by following the dimension that is required and
recommended by specific sample prep for the DMA (length, width and thickness). The
sample is clamped in the measurement head of the DMA instrument. A sinusoidal force is
applied to the sample through the probe during measurement. The relationship between the
deformation and the applied force is calculated after the deformation induced by the
sinusoidal force is detected. The applied stress and strain plotted as a function of temperature
or time are used to measure properties like elasticity and viscosity. Different deformation
modes are used to test various types of polymer materials with DMA. Tension, compression,
dual cantilever bending, 3-point bending, and shear modes are available, and depending on
the sample form, modulus, and measurement intent, the most appropriate type should be
chosen.

Data Analysis and Operational Principle:

Generally, DMA applies an oscillatory force at a set frequency to the sample and
reports changes in stiffness and damping. DMA operates by deforming a known-geometry
sample with a sinusoidal deformation. A controlled stress or a controlled strain may be
applied to the sample. The sample would then deform a certain amount for a known stress.
The deformation is related to its stiffness. A force motor is used to generate the sinusoidal
wave and this is transmitted to the sample via a drive shaft. DMA calculates stiffness and
damping, which are expressed as modulus and tan delta, respectively. The modulus is
expressed as an in-phase component, the storage modulus, and an out-of-phase component,
the loss modulus, since sinusoidal force is applied. The storage modulus, either E’ or G’, is
the measure of the sample’s elastic behavior while the loss modulus (E”) is a measure of
viscous response of a material. The ratio of the loss to the storage is the tan delta and is often
called damping that should range 0°and 90°. As delta approaches 0° indicates purely elastic
behaviour and while 90° shows it is purely viscous behaviour.

Figure 9: DMA Thermal Scan shows storage modulus E’, loss modulus E” and a measure of
“damping” or loss tangent.
Pre-Lab Questions:
1. Define DMA.
- DMA is a technique that used to study the viscoelastic behaviour of polymers
the which the sample's kinetic properties are analyzed by measuring the
strain or stress that is generated as a result of strain or stress, varies
(oscillate) with time, applied to the sample.
2. Define “damping”.
- Damping is a reduction in the amplitude of an oscillation as a result energy
being drained from the system to overcome other resistive force.
3. State information could obtain from
• Storage Modulus (E’) → material’s stiffness property
• Loss Modulus (E’’) → material’s damping property
4. Draw a region of viscoelastic behavior graph.
 EXPERIMENT 4
GAS-CHROMATOGRAPHY MASS SPECTROSCOPY (GC-MS)
Objectives:
1. To prepare sample for GC-MS.
2. To learn how does the GC-MS works.
3. To determine information could be obtained from GCMS.

Methodology:
The sample is injected into GC inlet which is heated to up to 300° C where the
material is then volatilized and separated into its various components using a capillary
column coated with a stationary (liquid or solid) phase. The compounds are being swept onto
the column by an inert carrier gas such as helium, hydrogen or nitrogen. Then, the separated
sample component emerge from column and flowing into capillary column that connecting
the GC to MS. The computer drived the MS, records the data, and converts the electrical
impulses into visual displays and hard copy displays.

Operational Principle of GS-MS:

Gas Chromatography Mass Spectroscopy is an instrument that allow to separate

individual component from a mixture compounds by the GC chromatography then the
component is identified by mass spectroscopy. During GC-MS analysis been carried out,, a
sample is first injected into a gas chromatograph, where components are separated according
to size and/or polarity. Sample components that are more volatile and smaller in size will
travel through the column more faster than others. Once the components leave the GC
column, they are ionized and fragmented by the mass spectrometer using electron or chemical
ionization sources. The components are blasted with electrons, causing them to break up and
turn into positively charged ions. Each charged fragment will have a certain mass. The mass
of the fragment divided by the charge is called the mass to charge ratio (m/z). The fragments
then go through a process of acceleration and deflection whilst traveling through a short
tunnel and being exposed to a magnetic field. Then, the ions are sent to analysis section
where in this section the ions are separated by mass number (m/z). Lastly, the ions hit a
detection plate at the end of the tunnel, where the mass to charge ratio (m/z) and relative
abundance that present in the sample is calculated. When a complex sample is separated by
GC-MS, it will produce many different peaks in the gas chromatogram and each peak
generates a unique mass spectrum used for compound identification.

Pre-Lab Questions:
1. Why does the information on compounds in a sample obtained from gas
chromatography (GC) usually needed to be further analyzed by mass spectroscopy
(MS)?
- When a complex sample is separated by GC-MS, it will produce many
different peaks in the gas chromatogram and each peak generates a unique
mass spectrum used for compound identification. Thus, mass spectroscopy
(MS) can measure the characteristic of individual molecules and elemental
composition of the sample. The MS also can determine the molecular mass
and molecular formula of organic compound.
2. List several precautions that should not be ignored in handling GCMS.
- The precautions that can be taken might be the first as to heat the fiber at
least 10 minutes. This is to ensure the purity of the fibre. Furthermore, the
needle should be in straight condition when withdraw the fiber. Lastly, the
sample used must be not dissolve in water.
3. What are the limitations of GCMS?
- The limitations of GCMS are it is limited to thermally stable and volatile
compounds. Some problems with GC-MS originate in improper conditions in
the GC portion of the analysis. If the GC instrument does not separate the
specimen's compounds completely, the MS feed is impure. This usually
results in background "noise" in the mass spectrum. If the carrier gas in the
GC process is not correctly deflected from entering the MS instrument,
contamination may occur. Despite, it is a destructive analytical technique.
 EXPERIMENT 5
NUCLEAR MAGNETIC RESONANCE (NMR) SPECTROSCOPY

Objectives:
1. To learn how to operate the NMR instrument using the standard procedure.
2. To prepare the sample for analysis using an NMR spectrometer.
3. To determine the type of proton and carbon by using chemical shift value in the NMR
spectrum.
4. To elucidate and predict the chemical structure of the samples.

Methodology and Sample Preparation:

Firstly, sample is weighed approximately according to the requirements needed for

the experiment and placed in NMR tube. The most common solvent used for NMR analysis is
deuterated chloroform (CDCl3) is transferred using clean, dry Pasteur pipet into the sample
and inverted it to help the sample dissolved completely. The solution in the NMR tube should
be about 5cm in height and the tube is cap tightly before running the sample.

Operational Principle and Technique:

When molecules are placed in a strong magnetic field, the nuclei of some atoms will
begin to behave like small magnets. If a broad spectrum of radio frequency waves are applied
to the sample, the nuclei will being to resonate at their own specific frequencies. When a
radio frequency with a varying magnetic field is applied to a molecule, the hydrogen’s spin
state align themselves either with or against the magnetic field. This alignment of the
hydrogen absorbs energy. This energy comes from the absorption of radiation from the radio
frequency being applied. This absorption, or chemical shift, makes a spectrum. The resonant
frequencies of the nuclei are then measured and converted into an NMR spectrum that
displays all of the right frequencies as peaks on a graph. The height of each peak represents
the number of nuclei that resonates at each specific frequency. This is known as the intensity
of signal. The more resonating nuclei, the higher the intensity. The location of peaks and the
height of the peaks indicate the type of hydrogen atoms has shown and the number of
hydrogen atoms are present respectively.

Pre-Lab Questions:

1. Describe briefly the phenomenon of particle charge while magnetic field applied in
NMR.
- When an atom is placed in a magnetic field, its electrons circulate about the
direction of the applied magnetic field. This circulation causes a small
magnetic field at the nucleus which opposes the externally applied field.
2. Why the deuterated solvent is used to dissolve the sample for NMR analysis?
i. To avoid swamping by the solvent signal.
ii. To avoid the huge solvent absorption as there is always much more
solvent than substance of interest in the sample to be investigated
iii. To stabilize the magnetic field strength.
3. Determine the function of H-NMR and C-NMR spectroscopy.
- The main difference between 1H NMR and 13C NMR is that 1H NMR is
used to determine the types and number of hydrogen atoms present in a
molecule whereas 13C NMR is used to determine the type and number of
carbon atoms in a molecule.
4. Define chemical shift and state the factors affecting it.
- Chemical shift is a the precise resonant frequency of the energy transition is
dependent on the effective magnetic field at the nucleus. Factors that
affecting the chemical shifts are electronegativity of nearby atoms,
hybridization of adjacent atoms, diamagnetic effects, paramagnetic effects
and solvent effect.
REFERENCES:
THERMAL GRAVIMETRIC ANALYSIS (TGA):
Ng, H. M., Saidi, N. M., Omar, F. S., Ramesh, K., Ramesh, S., & Bashir, S. (2018).
Thermogravimetric Analysis of Polymers. In Encyclopedia of Polymer Science and
Technology (pp. 1-29). https://doi.org/10.1002/0471440264.pst667

Z.N. Azwa & B.F. Yousif (2013). Thermal Degradation Study Of Kenaf Fibre/Epoxy
Composites Using Thermo Gravimetric Analysis. In: 3rd Malaysian Postgraduate
Conference (MPC 2013) (pp. 256-264). https://eprints.usq.edu.au/24001/

Perkin Elmer (2011). Characterization of Polymers Using TGA. Retrieved from

https://www.perkinelmer.com/labsolutions/resources/docs/APP_CharacterizationofPo
lymersUsingTGA.pdf

DIFFERENTIAL SCANNING CALORIMETER (DSC):

Eurofins Material Science (2017). Characterization of Polymers Using Differential Scanning

Calorimeter. Retrieved from https://www.eag.com/white-paper-characterization-of-
polymers-using-differential-scanning-calorimetry-dsc-m-012816/

Schindler, A., Doedt, M., Gezgin, Ş., Menzel, J., & Schmölzer, S. (2017). Identification of
polymers by means of DSC, TG, STA and computer-assisted database search.
Journal of Thermal Analysis and Calorimetry, 129(2), 833–842. doi:10.1007/s10973-
017-6208-5 
Humboldt Universitat Zu Berlin (n.d). Investigation of Polymers with Differential Scanning
Calorimetry. Retrieved from https://polymerscience.physik.hu
berlin.de/docs/manuals/DSC.pdf

Nijman, D.F (2011). Principles of Differential Scanning Calorimetry (DSC). European

Pharmaceautical Review. Retrieved from
https://www.europeanpharmaceuticalreview.com/webinar/35056/dsc-is-the-most-
frequently-used-thermal-analysis-technique/

DYNAMIC MECHANINCAL ANALYSIS (DMA):

Patra,. S, Ajayan, P.M, Narayanan, T.N. (2021). Dynamic mechanical analysis in materials
science: The Novice’s Tale. Retrieved from
https://academic.oup.com/ooms/articlepdf/1/1/itaa001/34473755/itaa001.pdf

Perkin Elmer (2018). Dynamic Mechanical Analysis (DMA): A Beginner's Guide. Retrieved
fromhttps://www.perkinelmer.com/CMSResources/Images/4474546GDE_IntroductionToDM
A.pdf

Hitachi high-tech Global. (n.d.). Principle of Dynamic Mechanical Analysis (DMA) : Hitachi
High-Tech GLOBAL. Retrieved from
https://www.hitachihightech.com/global/products/science/tech/ana/thermal/descriptions/dma.
html

GAS CHROMATOGRAPHY MASS SPECTROSCOPY (GC-MS):

Turner, D. (2021). Gas Chromatography – How a Gas Chromatography Machine Works,

How To Read a Chromatograph and GCxGC. Retrieved from
https://www.technologynetworks.com/analysis/articles/gas-chromatography-how-a-gas-
chromatography-machine-works-how-to-read-a-chromatograph-and-gcxgc-335168

Mathias, J.(2014). How Stuff Works: GC/MS Analysis. Retrieved from

https://www.innovatechlabs.com/newsroom/642/stuff-works-gcms-analysis/

EL-Science. (2017). How Does a GC-MS Work?. Retrieved from https://elscience.co.uk/our-

lab/gcms-work/
NUCLEAR MAGNETIC RESONANCE (NMR):

Zinkel, B. (2019). What is NMR spectroscopy and How Does it Work? Nanalysis. Retrieved
from https://www.nanalysis.com/nmready-blog/2019/6/26/what-is-nmr-spectrography-
andhow-does-it-work

Byjus. (n.d). NMR Spectroscopy (Nuclear Magnetic Resonance). Retrieved from

https://byjus.com/chemistry/nmr-spectroscopy/

MSU Chemistry (n.d). Retrieved from

https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/spectrpy/nmr/nmr1.htm