Suhas + AK PreMidsem

Certainly! Let's transform your handwritten notes on Thermogravimetric Analysis (TGA)

into a comprehensive, well-structured, and Obsidian-Markdown-ready study guide.
Thermogravimetric Analysis (TGA)
1. Introduction to TGA
Definition: Thermogravimetric Analysis (TGA) is a technique that involves the heating
measurement of mass. It determines the change in mass of a substance as a function
of temperature or time under a controlled atmosphere.
Mass Change Determination:
Function of Temperature/Time: TGA is primarily used to determine the mass
change as a function of temperature or time. This is typically done with a linear
temperature ramp (dynamic TGA).
Constant Temperature (Isothermal TGA): Measurements can also be performed
at a constant temperature to study the kinetics of reactions or degradation at a
specific temperature.
Types of Mass Change:
Mass Loss: Reactant → Product + gas (most common in TGA, indicating
decomposition, volatilization, etc.)
Mass Gain: Gas + reactant → Product (less common, usually related to oxidation
or corrosion processes). Mass gain due to corrosion is rare in typical TGA but can
happen.
Material Behavior:
Aromatic vs. Aliphatic: Aromatic compounds tend to be more thermally stable
and stay for a longer time at higher temperatures compared to aliphatic
compounds, which melt faster.
Moisture and Density Changes: TGA can indirectly measure changes in moisture
content and density of materials by observing mass changes related to water loss or
structural changes.
Magnetic Susceptibility: Magnetic properties can also be measured during TGA,
especially with surface modifications of materials.
Ceramics and Polymers:
Mixing Challenges: Ceramics and polymers generally do not mix well due to their
inherent differences in bonding and structure.
Surface Modification: Surface modification of ceramics or polymers is often
necessary to make them compatible and create composite materials.
 Protein Characterization: TGA can provide information about the types of proteins
present in a sample.
Sample Considerations:
Non-reactivity: The mass being measured should ideally not have any reactivity
with the sample holder or the atmosphere except for the intended thermal events.
Balance: The balance is crucial and must accurately weigh the sample holder and
sample throughout the experiment.
2. Instrumentation and Components
Balance: Accurately measures the mass of the sample and holder.
Sample Holder/Pans:
Materials: Typically made of materials like:
Aluminum (Al)
Titanium (Ti)
Polymer-based materials
Teflon-based materials
Calcium Oxalate Monohydrate Example: Calcium oxalate monohydrate (
CaC O ⋅ H O) is a common calibration standard in TGA.
Sample Pans - Material Types and Effects:
2 4 2

Aluminum (Al) Sample Pans:

Powder, lumps, solids: Suitable for various sample forms.
Surface Area: Modification of surface area affects heat absorption.
Heat Absorption: More volume leads to more heat required.
Profiles: Different sample forms and volumes will yield different TGA
profiles.
Weight Consistency: It's essential to maintain the same weight of the
sample for comparative analysis.
3. Applications and Interpretation
Degradation Kinetics and Corrosion Behavior: TGA is effective in studying
degradation kinetics and corrosion behavior of materials by monitoring mass loss or
gain as temperature changes.
Interpretation of (v) Notation: In TGA profiles, '(v)' often denotes that different
product evolutions occur in between specific temperature ranges.
Effect of Acetate Content in Polymers (e.g., PVAc - Polyvinyl Acetate):
Linear Degradation: If degradation occurs in a single step (acetate loss), the
TGA curve might appear relatively linear in the degradation region.
Amorphous Behavior: If more than 50% acetate is present, the polymer might
exhibit amorphous characteristics in its thermal degradation profile.
 Semi-Crystalline Behavior: If less than 50% acetate is present, the polymer may
show semi-crystalline behavior.
Polymer Degradation Temperature:
General Polymer Degradation: Most polymers start to degrade above 500 C.∘

Onset Degradation: The onset of degradation (initial mass loss) usually starts
around 300 − 350 C.
∘

Chain Scission: Degradation often occurs due to changes in the polymer chain
structure (chain scission/breakage).
Acetate Content and Thermal Stability:
Top Curve (Less Acetate): Shows higher thermal stability.
Middle Curve: Intermediate acetate content, intermediate thermal stability.
Last Curve (More Acetate): Shows lower thermal stability.
Semi-crystalline Nature: Higher acetate content may lead to more semi-
crystalline behavior.
Ceramics in TGA:
Slow Degradation: Ceramics do not degrade easily.
Residual Mass: The final mass remaining at the end of a TGA run is often due to
the ceramic component (e.g., around 5% or more).
Silver Nitrate (AgNO ) Example:
Stability: AgNO is stable up to around 420 C.
3
∘

Ceramic Residue: Any remaining mass after heating AgNO to high

3

temperatures is likely due to ceramic residue.

3

Polymer and Ceramic Composites:

Two-Step Degradation: In a polymer-ceramic composite, TGA might show two
main steps:
1. Polymer degradation (mass loss).
2. Remaining ceramic mass (residual mass).
Quantification: By analyzing the mass loss steps, one can calculate the
proportions of polymer and ceramic in the composite.
Reaching Zero Mass: In an ideal scenario with only a polymer sample, the mass
should ideally reach zero if the polymer completely decomposes and volatilizes.
Calcium Carbonate Monohydrate (CaCO ⋅ H O) Example:
Heating Rate Dependence: TGA results are dependent on the heating rate
4 2

provided.
PD (Polymer Degradation): Represents polymer degradation.
Better Thermal Stability: Higher thermal stability is generally desired.
Melting Point: Some polymers might melt around 500 C before degradation.
∘

Aromatic Polymers: Aromatic polymers generally have higher thermal

stability.
PTFE (Polytetrafluoroethylene - Teflon):
 Teflon Based Pans: Teflon pans can be used for TGA.
High Intermolecular Forces: PTFE has strong intermolecular forces
contributing to its thermal stability.
Better Properties: Teflon has good thermal and chemical resistance.
Carbon Black Quantification:
Calculating Carbon Black in Sample: TGA can be used to quantify the amount of
carbon black in a sample (e.g., in tires).
Ceramics Band/Graph: Analyzing the TGA curve (often called a "ceramics band"
or graph) can help quantify carbon black.
Carbon Black Residue: The residual mass after polymer degradation can be
attributed to carbon black and ceramic fillers.
PET (Polyethylene Terephthalate) Matrix: In a PET matrix composite with
carbon black and ceramics, TGA can differentiate and quantify these
components.
4. Polymer Specific Degradation Patterns
Polyurethane (PU):
Single Step Degradation: PU often shows a single-step degradation in TGA.
Soft and Hard Segments: PU is made of soft and hard segments, and their ratio
influences thermal behavior.
Engineering Polymers: PUs are considered engineering polymers due to their
versatile properties.
Conventional Polymers (vs. Engineering Polymers):
Earlier Degradation: Conventional polymers may show degradation happening
earlier at lower temperatures compared to engineering polymers.
Lower Thermal Stability: Generally have lower thermal stability than engineering
polymers.
Glycol Oligomers:
Complete Decomposition: Glycol oligomers usually decompose completely at
high temperatures.
Residue: Minimal residue (around 2-5%) might remain.
Biopolymers:
Less Thermal Stability: Biopolymers generally have less thermal stability
compared to synthetic polymers.
Decomposition Earlier: They tend to decompose earlier at lower temperatures.
Cellulose:
Water Loss around 150 C: Cellulose often shows a mass loss around 150 C due
to dehydration/dehydration reactions.
∘ ∘

Pore Structure: Pore structure in cellulose can affect its thermal behavior.
PTFE (Polytetrafluoroethylene) Analysis:
 Bore Resistance: PTFE is known for its bore (chemical) resistance.
Based Properties: Its thermal stability is based on its inherent polymer
properties.
Formulation and Processing:
Preferred Formulation: Certain formulations are preferred to enhance thermal
properties.
Epoxy-Based Formulation: Epoxy-based formulations often use a curing system.
Dispersion and Distribution in Composites:
Poor Dispersion: Inadequate mixing leads to poor dispersion of components,
resulting in uneven properties.
Good Dispersion: Well-mixed composites show good dispersion and uniform
distribution of components, leading to enhanced and consistent properties.
Scaffolds and Composites: In scaffold-based composites, uniform dispersion of
materials is crucial for performance.
Bore Composition and Scaffolds:
Bore (Pore) Size: Pore size is important in scaffold applications.
Suffolds (Scaffolds): Scaffolds are used in tissue engineering and biomedical
applications.
About Pore/Cave: Pore characteristics are critical for cell infiltration and tissue
growth.
5. Precipitation Methods in Material Synthesis (Related to TGA
context - e.g., for precursor synthesis)
Saffold (Scaffold) for Bone: Scaffolds can be used to create bone-like structures.
By Doonyapatile (Doping?) - Polars: Doping processes might involve polar materials.
Polymer-Bonded Composites:
Bonding: Polymers can be used to bond composite components.
Bone-Like Composites: Aim is to create composites that mimic bone properties.
Decomposition Temperatures: Different components will decompose at
different temperatures in TGA.
Silver Nitrate (AgNO ) Precipitation:
Ag Ions: AgNO is a source of silver ions (Ag ).
3
+ +

Super Saturation: Precipitation often involves supersaturation conditions.

3

Inorganic Components: Inorganic components might be precipitated.

Form Precipitate: Precipitation reactions lead to the formation of solid
precipitates.
Precipitation Types:
Ex-situ Precipitation: Precipitation occurs outside the main reaction environment
and then the precipitate is introduced.
 In-situ Precipitation: Precipitation occurs directly within the reaction
environment.
In-situ Example:
Prospect (Precursor?)
Inorganic Precursor: An inorganic salt solution can be used as a precursor.
Protein Solution (10:1): Protein solution can be mixed with the inorganic
precursor solution (e.g., in a 10:1 ratio).
Inorganic Salts: Inorganic salts are often used as precursors in material synthesis.
Ceramics: Ceramics can be synthesized via precipitation methods.
Hydroxyapatite (HA) Example:
Nano Hydroxyapatite: Nano-sized hydroxyapatite (HA) can be synthesized.
Ca (P O ) (OH) Formula: Chemical formula of hydroxyapatite.
Made of Amino Acid Sequences: Proteins are made up of amino acid sequences
10 4 6 2

(not HA itself, but in context of protein-HA composites).

Repeating Units: Amino acid sequences are repeating units in proteins.
N-terminal and C-terminal: Proteins have an N-terminal and a C-terminal end.
In-chain: Amino acids are linked in a chain.
Orientation: Orientation of protein chains is important.
How They Affect? Protein orientation and structure can affect material
properties.
Precipitation Temperature: Precipitation reactions can be carried out at specific
temperatures, e.g., 85 C.
∘

Calibration of TGA: Calibration is essential for accurate TGA measurements.

6. Comparison of In-situ vs. Ex-situ Precipitation
Fix-Situ (Ex-situ):
Prepared Filter First: A filter is prepared first.
Then Mixed in Solution: The precipitate is then mixed into a solution.
In-situ Precipitation Process:
G + Phosphate → Precipitation: Reaction between a metal salt (G) and
phosphate leads to precipitation.
Occurs at...: Precipitation occurs directly in the reaction medium.
Protein Stability:
Proteins are Not Stable: Proteins are generally less thermally stable than
inorganic materials.
Amount of Interaction:
In-situ (Physical Interaction): In-situ precipitation often leads to less
physical interaction between protein and inorganic phase.
Ex-situ (Polymer/Environment Interaction): Ex-situ might have more
environmental interaction and potentially better polymer-inorganic
 interaction.
Big Affects Structure: The precipitation method can significantly affect the
structure of the protein-inorganic composite.
In-situ vs. Ex-situ Comparison Summary:
In-situ > Ex-situ: In some contexts, in-situ precipitation might be preferred for
better control or properties.
Better Properties: In-situ might lead to better properties in certain applications.
Stability of Interface: In-situ methods can influence the stability of the interface
between organic and inorganic components.
Inorganic Polymer Example - TEA (Triethanolamine):
C=C-C=C-C=C-TEA: Example of a polymeric structure involving carbon chains
and triethanolamine.
Gall (Gel): Gel formation can occur during synthesis.
Inorganic/Organic Components: Hybrid materials containing both inorganic and
organic components.
PVC (Polyvinyl Chloride) Example:
Benzene + HCl: PVC can be synthesized or modified using benzene and HCl.
LDPE (Low-Density Polyethylene): Thermoplastic and linear polymer.
PMMA (Polymethylmethacrylate): Branching, amorphous polymer.
PVC: Dehydrochlorination can occur in PVC upon heating.
MW (Molecular Weight) and Stability: Molecular weight and stability are related
polymer properties.
Aromatic Polymers: Aromatic polymers generally have higher thermal stability.
PI (Polyimide) and PTFE (Polytetrafluoroethylene): PI and PTFE are examples of
thermoset polymers known for their high thermal resistance.
Crystallinity in Polymers:
Crystalline > Syndiotactic > Atactic: Order of crystallinity in polymers, from
highest to lowest: Crystalline > Syndiotactic > Atactic.
Corrosion Behavior:
2nd Heating: Corrosion behavior can be studied by heating the sample a second
time after an initial TGA run.
Coded Down & Then Heated: The sample might be cooled down and then
reheated to assess corrosion effects.
7. Oil Content and Plasticizers
Antimicrobial Properties: Some additives might impart antimicrobial properties.
Oil Content/Plasticizer Role:
Through Heating/Mechanical Shearing: Heating and mechanical shearing can
cause disentanglement of polymer chains.
 Facilitate Friction: To facilitate friction between polymer chains, which aids in
disentanglement.
Lower Temperature Disentanglement: Disentanglement can be achieved at a
lower temperature with the help of plasticizers or oil content.
Rubber and Oil Compatibility:
Polar Rubber: If rubber is polar, use polar-based oils as plasticizers.
Aromatic Oil: Aromatic oils can be used as plasticizers.
Paraffinic Oil: Paraffinic oils lead to crystalline and aliphatic characteristics.
Naphthenic Oil: Naphthenic oils introduce more enthalpy and benzene groups,
making them bulkier and potentially decomposing at very low temperatures.
8. Oxidative Stability and Heating Rate
Oxidative Stability: Oxidative stability refers to the material's resistance to
degradation in an oxidizing environment. It degrades at high temperatures in oxidative
conditions.
Heating Rate in TGA:
Based on Sample and Instrument: Heating rate selection depends on the
sample characteristics and instrument capabilities.
As Heating Rate ↑, Rate of Degradation ↑?: Generally, a higher heating rate can
lead to a seemingly faster rate of degradation in TGA profiles, but it can also
affect the resolution of degradation steps.
Finding Annealing Temperature:
Gel Temperature: Can be determined using TGA.
Ferromagnetic to Paramagnetic Transition: TGA can sometimes detect magnetic
transitions.
Loss of Complete Magnetic Nature: Magnetic materials might lose their magnetic
nature at certain temperatures.
Weight of Material Changes: Mass changes are the primary measurement in TGA.
Nitride Metal Example: Nitride metals might be stable up to around 350 C.∘

Quantifying Organic Compounds: TGA is suitable for quantifying organic

components in a material.
Acetate Group Detection: TGA can help identify the presence of acetate groups
based on their decomposition temperatures.
Branched Polymers: TGA can be used to study the degradation behavior of branched
polymers.
Branching and Decomposition: Branching in polymers affects their decomposition
behavior. Branching decomposes first, then the main chain decomposes, eventually
leaving ash (carbonaceous residue).
Phase Transformation Calculation:
 Calculate Phase Transformation: TGA can be used to calculate phase
transformation temperatures and kinetics.
Graph Analysis: Analyzing the TGA graph helps in determining phase
transformations.
Example: CaCO ⋅ H O → CaO + CO + H O: Decomposition of calcium
carbonate monohydrate.
4 2 2 2

Formula for Calculation:

Molar weight of Ag...
Sol% = × 100
Molar weight of AgNO 3

(This formula seems to be related to calculating the percentage of silver in silver

nitrate, possibly for compositional analysis using TGA).
9. Sample Preparation and Calibration
Sample Preparation:
10-20 mg Sample Size: Typically, 10-20 mg of sample is sufficient for most TGA
applications.
Rate of Heat and Decomposition: Rate of heating and decomposition are
affected by how the sample is prepared.
Sample Presentation: Whether the sample is spread out or stored in a compact
way affects heat transfer and decomposition.
TGA Temperature Calibration:
Empty Pan - Inert Material: Run TGA with an empty pan or inert reference
material.
No Decomposition at 2000 C: Ensure the empty pan or inert material shows no
decomposition or mass change up to 2000 C (or the maximum operating
∘

temperature of the TGA).

∘

Magnetic Material and Pan:

Keep Magnetic Material Below Pan: For magnetic samples, place the magnetic
material below the sample pan to avoid interference with balance measurements.
Heat up to Curie Temperature: Heat the sample up to its Curie temperature to
observe magnetic transitions.
Mass Change After Curie Temperature: After the Curie point, any mass change
should not be due to magnetic effects.
Weight Change Not Proper: If weight change is not properly accounted for, it
can lead to inaccurate TGA results.
Particular Temperature: Calibration needs to be precise for each temperature
range.
By Shifting Temperature: Temperature calibration might involve shifting or
correcting temperature readings.
 Then Calibration is Done: Calibration is confirmed when temperature readings
are accurate.
10. Tire Composition Analysis using TGA
Tire Components:
Bromine? (Possibly referring to bromobutyl rubber or halogenated rubber in
tires).
Rubber Compound: Main rubber matrix in tires.
Plasticizer: Used to improve flexibility.
Fiber, Carbon Black: Reinforcing fillers.
Ceramic Particles: Fillers like silica or clay.
Ceramic Particle Modification:
Modified by Surfactants: Ceramic particles in composites are often surface-
modified with surfactants to improve dispersion and compatibility with the
polymer matrix.
Varied Surfactant Chain Length: Surfactants with different chain lengths can be
used to optimize particle dispersion and interaction.
Surfactant Chain Length and Thermal Stability:
Oleic Acid Example: Oleic acid can be used as a surfactant.
Disperse/Distribute: Surfactants aid in dispersing and distributing ceramic
particles uniformly.
Minimum Energy Required: Surfactants help reduce the energy needed for
dispersion.
MW is More, Work Space: Higher molecular weight surfactants might create
more "work space" or steric hindrance, affecting particle interaction.
80% (Example): A surfactant concentration of 80% (this number seems
indicative, needs context) might be optimal for thermal stability.
More Thermally Stable: Proper surfactant modification enhances thermal
stability.
Structure Also Depends: Final composite structure depends on surfactant type
and concentration.
Conjugated Structure: Conjugated surfactant structures might lead to highly
thermally stable composites.
Drugs (Example): Drug molecules can be embedded or conjugated to the
surfactant-modified particles.
Chemically Drug is Embedded: Chemical embedding of drugs can further
enhance thermal stability and functionality.
11. Differential Thermal Analysis (DTA)
 Definition: Differential Thermal Analysis (DTA) measures the temperature difference
between a sample and a reference material as a function of temperature, while both
are subjected to identical temperature programs.
Comparing Sample with Inert Samples: DTA compares the thermal behavior of a
sample against a reference sample that is inert (thermally inactive) in the temperature
range of interest.
Reference Sample: A reference sample is needed for DTA.
Heating and Cooling Regularly: DTA involves heating and cooling the sample and
reference regularly to observe thermal events.
Observe Reaction Type (Exo, Endo): DTA helps identify whether a reaction or thermal
event is exothermic (heat releasing) or endothermic (heat absorbing).
Segmental Motion and T : DTA can detect glass transitions (T ) associated with
segmental motion in polymers.
g g

Thermoplastics and Exothermic Events:

Alignment of Molecules: In thermoplastics, upon heating, alignment of polymer
molecules can occur.
Crystallization Takes Place: Crystallization is often an exothermic process.
Exo (Exothermic): Crystallization is detected as an exothermic peak in DTA.
12. Phase Transformations and DSC
Phase Transformations in DTA/DSC: DTA and DSC are powerful for studying phase
transformations.
70% of Sample: For a given sample size (e.g., 70%), temperature difference is
measured accurately.
Temperature Difference Will Be Well Defined: Phase transitions result in well-defined
temperature differences between sample and reference.
During That Event: Temperature difference is observed during the phase
transformation.
Heat Released/Absorbed: Phase transformations involve either release (exothermic,
e.g., crystallization) or absorption (endothermic, e.g., melting) of heat.
Crystallization During Cooling: Crystallization in polymers often occurs during the
cooling phase.
"Che: In Thermoplastic": Crystallization in thermoplastics is a common thermal
event.
Combinatorial Techniques: DTA/DSC are often used in combination with other
techniques like TGA (combinatorial thermal analysis).
DTA/DSC Curve:
Time (or Temperature) vs. Heat Flow: DTA/DSC curves typically plot time or
temperature on the x-axis and heat flow or temperature difference on the y-axis.
Weight (Mass) vs. Temperature (TGA): In contrast, TGA curves plot weight or
mass change against temperature or time.
 Heat Flow Peaks: Peaks in a DTA/DSC curve indicate thermal events (exo- or
endothermic).
13. Differential Scanning Calorimetry (DSC)
Difference Between Calorimeters: DSC is a type of differential calorimeter. It
measures the heat flow difference between a sample and a reference.
Measure Heat of Sample vs. Reference: DSC directly measures the heat flow into or
out of a sample compared to a reference material.
Check Crystalline/Amorphous Nature: DSC is used to determine if a sample is
crystalline, amorphous, or semi-crystalline, and to quantify the degree of crystallinity.
Crystalline vs. Amorphous Determination by DSC: DSC is a primary technique to
distinguish and quantify crystallinity and amorphous content in materials.
DSC Equation (Simplified):
dH dT dH/dt
= Cp ⋅ ⇒ Cp =
dt dt dT /dt

Where:
is the heat flow rate.
dT /dt is the heating rate.
dH/dt

C is the specific heat capacity.

Calibration Constant (K): A calibration constant might be needed for accurate DSC
p

measurements.
Pans in DSC and TGA - Differences and Why: Pans in DSC and TGA might be
different based on the measurement principle and temperature ranges. DSC pans
often need to facilitate better heat transfer.
Adjust Heat Flow in DSC: DSC instruments adjust heat flow to maintain the sample
and reference at the same temperature (heat-flux DSC) or measure the power
difference needed to keep them at the same temperature (power-compensated DSC).
Place Sample in Pan: Sample is placed in a DSC pan.
Ensure No Empty Space: Ensure good thermal contact between the sample and pan,
and minimize empty space to improve heat transfer.
Crystallization Temperature (T ) Determination: DSC is used to determine
crystallization temperature.
c

How to Calculate Energy from DSC:

Area Under Curve: The area under a DSC peak is proportional to the enthalpy
change (ΔH) associated with a thermal event (e.g., heat of fusion, heat of
crystallization).
Formula: ΔH = K × Area, where K is a calibration constant.
14. Applications of DSC
 Applications of DSC:
Composition Analysis: DSC can help in analyzing the composition of mixtures by
identifying thermal events characteristic of each component.
Crystallinity Percentage: DSC is used to quantify the percentage of crystallinity
in polymers and other materials.
Good Matrix and Filler Interaction (in Composites):
DSC for Composite Analysis: DSC can assess the interaction between the matrix
and filler in composite materials.
In Composites: Useful for characterizing composite thermal behavior.
Check Using Microscopy: Microscopy (e.g., optical, electron microscopy) is
often used in conjunction with DSC to understand material structure and
morphology related to thermal properties.
Crystallization/Melting Group: DSC peaks indicate crystallization and melting
temperatures, which are crucial for material processing and application.
Crystallinity Percentage Calculation: DSC is a direct method to measure crystallinity
percentage.
Starts to Move Towards High Temperature: Crystalline materials typically have
sharper and more defined melting transitions at higher temperatures compared to
amorphous materials.
15. EVAc Copolymer Analysis (Ethylene-Vinyl Acetate)
EVACO (Ethylene-Vinyl Acetate Copolymer):
Softening Temperature (T ): EVAc copolymers have a softening temperature
rather than a sharp melting point.
soft

Amorphous Polymers and T : Amorphous polymers generally do not have a

distinct melting temperature (T ).
m

T (Glass Transition Temperature) Determination:

m

T ≈ 100.1 C (Example): Example value of T for a specific EVAc copolymer.

g
∘

Based on Vinyl Acetate Content: T of EVAc copolymers is influenced by the

g g

vinyl acetate content.

g

Semi-Crystalline/Amorphous Nature: The ratio of ethylene to vinyl acetate units

determines the crystallinity or amorphous nature of the copolymer.
Vinyl Acetate Content Influence: Higher vinyl acetate content tends to decrease
crystallinity and T .
PVC (Polyvinyl Chloride) Analysis:
g

When PVC is ↑, E (Storage Modulus?) ↑?: In PVC, as crystallinity or stiffness

increases, the storage modulus might increase.
s

Area Under Curve ↓?: The area under a DSC curve related to a thermal transition
might decrease or change shape based on PVC properties.
Structure Analysis: DSC is used for polymer structure analysis.
Nylon 6,6 (Example):
Aylon Polyanide Bices (Nylon Polyamide Fibers?): Nylon 6,6 is a polyamide.
Binadal's/Monomadid PA6 (Bimodal/Monomodal Polyamide 6?): Different
types of polyamide 6 (PA6) might exist (bimodal or monomodal molecular weight
distribution).
3.44 Crystalline Layer Formed: Nylon 6,6 can form crystalline layers.
Uniform Crystallinity: Uniform crystallinity is often desired for consistent
properties.
Based on Area (DSC Peak Area): DSC peak area is used for quantitative analysis.
Different Compounds in Mixture:
Present of Different Melting Points (MP): If a mixture contains compounds with
different melting points, DSC will show multiple melting peaks.
At Particular Temperatures: Each component will melt at its characteristic
temperature.
One of Them Can Melt Early & Decompose: In a mixture, some components
might melt earlier and potentially start to decompose before others.
Ethylene-Linear Vinyl Acetate (EVACO):
Crystalline/Crystallites: EVAc copolymers can have crystalline regions or
crystallites.
Has Branched Structure: EVAc can have branched structures depending on
synthesis.
Plastic + Rubber Properties: EVAc copolymers combine plastic and rubber-like
properties.
Co-polymer: EVAc is a copolymer.
Miscible Polymer Blend:
Miscible: Miscibility refers to the ability of two or more polymers to blend
together to form a homogeneous mixture.
Wetting Temperature (T ): Miscible blends might have a wetting
temperature related to their miscibility.
wetting

T Same: A miscible polymer blend often shows a single, composition-dependent

glass transition temperature (T ).
g

Curing and Thermal Stability:

g

More the Curing → More Thermal Stability: Increased curing generally leads to
higher thermal stability in thermoset polymers.
Curing Process:
No Melting Present: In curing of thermosets, melting is not typically
observed; instead, cross-linking reactions occur.
Involves Heating and Cooling: Curing cycles often involve heating and
cooling stages.
15 Minutes Curing: Example curing time of 15 minutes might lead to some
degree of crystallization.
 120 Minutes Curing: Longer curing time (e.g., 120 minutes) might result in
more complete crystallization or cross-linking.
Fusion of Samples at 40 C (Example): At a specific temperature (e.g., 40 C), fusion
∘ ∘

or melting of certain sample components might take place.

Thermal Residual Stress:
Can Be Removed During 2nd Heating: Thermal residual stresses induced during
processing can sometimes be relieved during a second heating cycle in DSC or
TGA.
Protein Conformation Study:
Protein Conformation Can Be Studied by DSC: DSC is used to study protein
denaturation and conformational changes.
Based on Intra/Inter Molecular Interactions: Protein conformation is determined
by intra- and intermolecular interactions.
α/β Sheet/Structure: Proteins can have secondary structures like alpha-helices (
α) and beta-sheets (β).
Cp (Specific Heat Capacity) - DSC: DSC measures heat capacity changes,
which are sensitive to protein conformational transitions.
16. Bimodel/Monomodal Polymers and Protein Interactions
Bimodal → Monomodal (Polymer Molecular Weight Distribution): Bimodal polymers
have two distinct molecular weight peaks, while monomodal polymers have a single
peak.
α/β (Protein Secondary Structure): Alpha-helix (α) and beta-sheet (β) are secondary
structures in proteins.
C - Typical File Protein (Example): C might refer to a 16-carbon chain fatty acid or
a protein with 16kDa molecular weight, used as an example.
16 16

Protein - Force (Weak?) vs. Starts to Interact with Biopolymers:

Force/Interaction: Proteins interact with biopolymers through various forces
(e.g., hydrogen bonds, hydrophobic interactions).
More Crystalline → More Energy to Melt/Decompose: More crystalline regions
in a polymer generally require more energy to melt or decompose.
P Area (Peak Area in DSC): Peak area in DSC is related to the energy of
transition.
17. Plasticizers and Polymer Behavior
Adding Plasticizers Effects: Plasticizers alter polymer properties, typically by
increasing flexibility and reducing T .
Completely Cross-linked Polymers:
g

Do Not Undergo Crystallization: Highly cross-linked polymers generally do not

crystallize.
 Stactics/Ansephony (Atactic/Amorphous?) Highly cross-linked polymers tend
to be amorphous (atactic).
Do Not Undergo Melting: Cross-linked polymers do not melt; they degrade upon
heating.
Peak - Monomodal (DSC Peak Shape): A single peak in DSC might indicate a
monomodal transition.
When Ceramics/Composites are Added to Protein:
Intra and Inter Molecular Changes: Adding ceramics or composites to proteins
can alter both intra- and intermolecular interactions in the protein structure.
Quaternary Structure (of Proteins):
Spatial Arrangement: Quaternary structure refers to the 3D arrangement of
multiple protein subunits.
Intense Physics/Spatial Arrangement: Quaternary structure is governed by
physical interactions and spatial arrangements of protein chains.
Gel-NH? (Gel Network?): Might refer to gel networks formed by proteins and
composites.
Oxidation Stability Curve:
Find Way to Increase Oxidation Stability: Research aims to enhance the
oxidation stability of materials.
No Change in Entropy, Latent Heat of Fusion: Oxidation might not involve
significant changes in entropy or latent heat of fusion, unlike phase transitions.
Only Happens on the Surface: Oxidation often starts at the material surface.
18. Biocompatibility and Polymer Blends
Polystyrene - Biocompatible?: Polystyrene is generally not considered biocompatible
for biomedical applications without modifications.
Through Physical Bonds (H-bonds): Physical bonds like hydrogen bonds (H-bonds)
can be used to incorporate drugs into polymer matrices.
Drug is Embedded: Drug molecules can be embedded within a polymer.
Functional Groups are More Important: Functional groups on polymers and drugs
play a crucial role in interactions and drug release.
Bond Between Drug & Polymer - Chemical Bond (Forceful): Stronger, chemical
bonds (e.g., covalent bonds) can be used to link drugs to polymers for controlled
release.
Thermoset - 1st & 2nd Heating: In thermosets, the first heating cycle leads to curing,
and subsequent heating cycles might show different thermal behaviors.
After Cooling - Undergo Crystallization: Some polymers might crystallize upon
cooling after initial heating.
Thermal Stress, Residual Stress: Processing can induce thermal and residual
stresses in materials.
 After Cooling and Sample is Ordered: After cooling, the sample might become more
ordered or crystalline.
Based on Type of Sample & Cooling Rate: Crystallization and thermal behavior are
influenced by the type of polymer and the cooling rate.
Gordered (Ordered Structure): Achieving an ordered structure is often desired for
specific material properties.
19. Grain Boundaries and Residual Stress
Residual Stress Formation: Residual stresses often form at grain boundaries in
polycrystalline materials.
1st Heating - Exothermic Nature: In the first heating cycle of some materials,
exothermic events (e.g., stress relief, crystallization) might be observed.
During Crystallization - Cannot Directly Say T : During crystallization, identifying
glass transition temperature (T ) directly might be challenging as crystallization events
g

can overlap or mask T .

g

Residual Stress - Men (Mean?) Temperature ↓ Below MP (Melting Point): Residual

g

stresses can be relieved by heating below the melting point.

Heated and During 2nd Heating - Residual Stress All Removed: A second heating
cycle can help in removing or reducing residual stresses.
Effect of Heating Rate: Heating rate influences thermal behavior and peak positions
in TGA/DSC.
Aliphatic is Aromatic (In context of heating rate effect?): This statement is unclear
without more context. Aliphatic and aromatic compounds behave differently thermally.
Soft Organic Material: Soft organic materials may degrade or melt at lower
temperatures.
Depth - Corresponding to Melting: Sample depth or thickness can affect heat
transfer and apparent melting behavior in thermal analysis.
Related to Graft Copolymers: Graft copolymers might show complex thermal
behavior due to different components.
More Chain Length → Amorphous: Longer polymer chains can sometimes lead to
more amorphous regions.
Graft - Semi-Crystalline: Grafting might influence the crystallinity of polymers,
potentially leading to semi-crystalline structures.
Dependence on Grafting: Thermal behavior depends on the extent and type of
grafting.
Efficiency of Grafting: Grafting efficiency affects material properties.
Formation of Different Crystalline Domains: Grafting can lead to the formation of
different crystalline domains within a polymer matrix.
20. Composites and Grafting Techniques
 Composites - Surface Should be Non-Polar: For good dispersion and compatibility in
composites, the filler surface is often modified to be non-polar or compatible with the
polymer matrix.
So Grafting & Other Techniques are Used: Surface modification techniques like
grafting are employed to improve composite properties.
Viscoelastic vs. Elastic/Plastic Behavior:
Viscoelastic: Materials exhibiting both viscous and elastic properties.
Elastic/Plastic: Materials showing primarily elastic or plastic deformation.
How do We Measure Yielding? - Yielding %: Yielding in materials can be quantified
as a percentage.
Research Paper Example - CNC-Br (Brominated Cellulose Nanocrystals?):
Biopolymer: Cellulose is a biopolymer.
Due to Presence of Nano Crystal: Nanocrystals (e.g., CNC) can enhance
material properties.
Been at High Temperature: Processing at high temperature might be involved in
composite fabrication.
Melt Time - More Grafting: Increased grafting might affect melt processing time.
More Thermal Stability: Grafting can enhance thermal stability.
Go Grafting → To Less Thermal Stability?: This statement seems contradictory.
Grafting is usually intended to improve or modify thermal stability, not reduce it.
Context is needed. Perhaps it means excessive or improper grafting might have
negative effects.
So Melt Early: If thermal stability is reduced, the material might melt earlier.
Even Some Amount of Weight is Remaining: Even after degradation, some residual
weight might remain, especially in composites with inorganic fillers or carbonaceous
char.
21. Degradation Mechanisms
Degradation - Chains Fragment/Break Down: Polymer degradation involves chain
scission and fragmentation.
Melting - Starts to Flow, De-entangled: Melting is a phase transition where the
material starts to flow as polymer chains become disentangled.
Thermo-Gravimetric Analysis Study - Corrosion (TGA and Corrosion): TGA is used
to study corrosion by monitoring mass changes due to oxidation or material loss.
Step 1 - Heat → Oxidized → Corrosion → Weight ↑ (Mass Gain? - Should be Mass
Loss for Corrosion due to Oxide Volatilization, Mass Gain if Oxide Layer is Stable):
This seems to have a typo. For most corrosion processes involving oxide volatilization,
mass loss is expected. Mass gain would occur if a stable oxide layer is formed and
retained.
Better Barrier Property → 2D Structure: 2D materials or layered structures can
provide better barrier properties against gas or moisture permeation.
 TGA - Determines Mass Change: TGA measures mass change as a function of
temperature/time.
Material Subjected to Controlled Temperature Program: TGA experiments involve
subjecting a material to a controlled temperature program in a specific atmosphere.
Analysis Atmosphere: The atmosphere (inert, oxidizing, reducing) in TGA is crucial
and needs to be controlled.
Why Moisture Content is Measured? - Due to Density Change: Moisture content
measurement is important because it affects material density and properties.
Pans Made of Al, Ti, Teflon - Easy Cleaning: Pans are made of these materials for
inertness and ease of cleaning.
To Check Degradation - Inert Atmosphere (N or Ar): To study thermal degradation
without oxidation, an inert atmosphere (N , Ar) is used.
2

Corrosion/Oxidation - O /N (Oxidizing Atmosphere): To study oxidation or

2

corrosion, an oxidizing atmosphere (e.g., air, O in N ) is used.

2 2

Ceramics - Don't Decompose Completely on Heating: Ceramics are thermally stable

2 2

and do not fully decompose in TGA, often leaving a residual mass.

AgNO Example (TGA Curve):
Weight % vs. Temperature Curve: TGA curve for AgNO .
3

40% of Weight Still Exists at MP (Melting Point): Even after heating to high
3

temperatures or melting point, a significant portion (e.g., 40%) of the initial

weight might remain, indicating ceramic residue or incomplete decomposition.
T → (Time or Temperature?) (°C): Temperature axis in degrees Celsius.
22. Effect of Epoxy Curing Temperature
Draw Effect of Epoxy Cured at Different Temperatures: TGA curves showing the
effect of epoxy curing temperature on thermal stability.
Curing Temperature ↑ → Thermal Stability ↑: Generally, higher curing temperatures
for epoxy resins lead to increased cross-linking density and thus higher thermal
stability.
TGA Curves for Different Curing Temperatures: TGA curves showing degradation
profiles for epoxy samples cured at different temperatures (e.g.,
100 C, 125 C, 165 C, 180 C, 200 C ).
∘ ∘ ∘ ∘ ∘

Curing Temperature on X-axis, Weight % on Y-axis: Standard TGA curve axes.

23. Dispersion and Distribution in Materials
Dispersion and Distribution (of Fillers in a Matrix): Uniform dispersion and
distribution of fillers in a matrix are crucial for composite properties.
Dispersion vs. Distribution Table/Diagram: Visual representation of good vs. poor
dispersion and distribution.
Poor Dispersion: Agglomerated fillers, uneven distribution.
 Good Dispersion: Uniformly distributed fillers.
Precipitation Methods:
Ex-situ and In-situ Precipitation: Methods for synthesizing materials, as
discussed earlier.
24. Corrosion Behavior of Steel
Corrosion Behavior of Steel: TGA can be used to study the corrosion behavior of
steel by heating it in different atmospheres and monitoring mass changes due to
oxidation.
25. Heating Rate Effect
Does Heating Rate Matter? YES! Heating rate is a critical parameter in TGA and
affects results.
26. Quantifying Organic Compounds
Quantifying Organic Compounds: TGA is useful for quantifying organic components
in materials.
27. Calibration of TGA
Calibration of TGA Methods:
Method 1: Take Pan and Heat: Baseline calibration by running TGA with an empty
pan.
Method 2: Magnetic Particles and Apply Magnetic Field: Using magnetic
materials for Curie point calibration to verify temperature accuracy.
28. Ceramic Particle Modification (Revisited)
Ceramic Particle Modified by Various Surfactants: Different surfactants with varying
chain lengths are used to modify ceramic particles.
Surfactant Chain Length and Thermal Stability: Surfactant chain length affects the
thermal stability and dispersion of ceramic particles in composites.
Most Thermally Stable - More Branching: Surfactants with more branched chains
might lead to better thermal stability (needs context).
More Molecular Weight (↑ Mol. Wt.): Higher molecular weight surfactants might
provide better steric stabilization.
Thermal Stability (↑ Thermal Stability): Proper surfactant modification enhances
thermal stability of the composite.
29. Differential Thermal Analysis (DTA) - Revisited
 Differential Thermal Analysis Definition: Measures the temperature difference
between a sample and a reference.
Measure Sample Temperature Relative to Reference: DTA is a differential technique.
For the Same Heat Transferred: Both sample and reference are subjected to the
same heating program.
Coupled with TGA: DTA is often used in conjunction with TGA to get comprehensive
thermal analysis data.
30. Differential Scanning Calorimetry (DSC) - Revisited
Differential Scanning Calorimetry Definition: Measures the heat flow in/out of a
sample compared to a reference.
Calorimeter - Measures Heat In/Out: DSC is a calorimetric technique.
Differential Calorimeter - Measures Heat Relative to Reference: DSC is also a
differential technique, measuring heat flow difference.
DSC Measures Heat Flow and Temperature: DSC provides data on heat flow as a
function of temperature.
31. Applications of Miscibility (DSC Application)
Applications - Miscibility of PVC-EVAc Blend: DSC is used to study the miscibility of
polymer blends like PVC-EVAc.
Semi-Crystalline Blend: PVC-EVAc blends can be semi-crystalline depending on
composition.
E10, E20, E90 (Example Compositions): Different ratios of PVC and EVAc (e.g., E10,
E20, E90 indicating EVAc content) will show different DSC profiles.
Area Under Curve → Amount of Heat Flow: The area under DSC peaks quantifies the
amount of heat absorbed or released during thermal transitions.
32. Sol-Gel States
Sol: Readily Dissolved in Aqueous Solution: Sol state is typically a liquid or colloidal
dispersion.
Gel: Not Dissolved: Gel state is a solid-like network structure, not dissolved.
33. Oxidative Stability - Revisited
Oxidative Stability: Resistance to degradation in an oxidizing environment.
34. Effect of Heating Rate - Revisited
Effect of Heating Rate: Heating rate is a crucial parameter affecting thermal analysis
results.
35. Graft Copolymer - Revisited
Graft Copolymer: Polymers with side chains of a different monomer type grafted onto
the main chain.
36. Dynamic Mechanical Analysis (DMA)
Dynamic Mechanical Analysis (DMA): Technique to study viscoelastic properties of
materials as a function of temperature, frequency, or time.
Viscoelasticity: Material behavior exhibiting both viscous and elastic characteristics.
Elastic Component: Represents the solid-like, energy-storage part of viscoelastic
behavior.
Viscous Component: Represents the liquid-like, energy-dissipating part of
viscoelastic behavior.
Use: Studying Viscoelastic Behavior of Polymers: DMA is primarily used to
characterize the viscoelastic behavior of polymers.
Application: Bridges (Example): DMA data is important for structural applications like
bridges, where materials are subjected to dynamic loading.
Dynamic Loading: Loads that vary with time, like vibrations or oscillations.
Finding T (Glass Transition Temperature) by DMA: DMA is a sensitive technique for
determining T .
g

Damping Property (by DMA): DMA measures damping properties, which are related
g

to energy dissipation.
DMA Curve - Damping Peak: DMA curves often show a damping peak around the
glass transition temperature.
Area 1 (Peak Area): The area under the damping peak relates to energy dissipation.
Bump (Damping Peak): The peak itself is the damping peak.
Temperature (°C) on X-axis: Temperature is typically plotted on the x-axis in DMA
curves.
(Temperature at Peak Area?): Temperature at which the damping peak area is
measured.
TArea

Total Damping (Area): Total damping is related to the area under the damping peak.
↓ Damping (Decrease in Damping): Lower damping indicates less energy dissipation.
Immiscible Polymer Blend Example (DMA): DMA is effective in characterizing
immiscible polymer blends, which often show multiple T s or broadened transitions.
Tan δ (Loss Tangent):
g

E ′′ E dissipated
tan δ = ′ =
E E stored

: Loss tangent, a measure of damping.

E : Loss modulus (viscous component).
tan δ
′′

E : Storage modulus (elastic component).

′
 tan δ is the ratio of energy dissipated to energy stored per cycle of deformation.
37. Quiz 1 - Questions and Concepts
Quiz 1 Questions: (These are questions from your notes, converted to a more
standard question format)
1. VAc (Vinyl Acetate) Content Calculation: Calculate the percentage of vinyl acetate
(VAc) in a copolymer blend.
mass of acetic acid Molar Mass of VAc
VAc% = ×
mass of sample Molar Mass of Acetic Acid

Example Calculation: If the result is ≈ 23% and ≈ 33, then VAc % $\approx 33 - 23
86.2

= 10% $ (This calculation needs clarification as it seems incomplete or context-

69

dependent in your notes).

2. Atomic Force Microscope (AFM) vs. Electron Microscope (SEM/TEM): Compare
Atomic Force Microscopy (AFM) to Electron Microscopy (SEM/TEM) in terms of
sample preparation and penetration.
Camera: AFM can be considered like a camera at the nanoscale.
Electron Microscopy (SEM/TEM): Require sample preparation and electron beam
penetration.
Sample Preparation for AFM: Simpler sample preparation for AFM compared to
SEM/TEM.
Penetration: AFM is a surface technique, while TEM can probe internal structures.
3. Polymer/Material Identification using Atomic Force Microscopy: How to determine
polymer or material type based on Atomic Force Microscopy?
Atomic Force Microscopy (AFM): Can provide information about surface
morphology, roughness, and mechanical properties, which can help identify
materials.
TEM/SEM: Need high voltage to generate electrons.
High Energy Electrons: TEM/SEM use high energy electrons.
AFM Doesn't Need Electrons: AFM does not require electron beams.
No Specimen Preparation Required (Less Preparation): AFM often requires
minimal sample preparation compared to electron microscopy.
4. Density Difference and Distinguishability: Is density difference always
distinguishable using AFM?
Density Difference: Density differences alone may not be directly and easily
distinguishable using AFM. AFM is more sensitive to surface topography and
mechanical properties.
Cantilever Order - Nanometers: AFM cantilever tip is in the nanometer range.
5. Difference Between LDPE and HDPE and Miscibility Check: How to differentiate
between Low-Density Polyethylene (LDPE) and High-Density Polyethylene (HDPE) and
 check miscibility?
LDPE - Soft, HDPE - Hard: LDPE is softer and more flexible, HDPE is harder and
more rigid.
E Absorbed - High for LDPE, Low for HDPE: Energy absorbed (related to impact
strength or toughness) might be different for LDPE and HDPE.
Miscibility: Miscibility of blends can be assessed by thermal analysis (DSC, DMA)
or microscopy.
6. Interface Size and Mixing: How does interface size affect mixing in polymer blends?
Interface Size ↑ → Less Mixing: Larger interface size (or interfacial area) in
immiscible blends can indicate poorer mixing or phase separation.
7. Mechanical Stability and Scratch Resistance of Coatings: How to measure
mechanical stability and scratch resistance of coatings?
AFM (Atomic Force Microscopy): Can be used to assess mechanical properties
like stiffness, adhesion, and scratch resistance at the nanoscale.
Scratch Resistance: AFM-based nano-scratch tests can quantify scratch
resistance.
These notes should provide a very detailed and structured understanding of your
handwritten material on Thermogravimetric Analysis and related techniques. Let me know
if you have any specific questions or need further clarification on any section!