Analytical Techniques in Polymer Material Science

1. DMA (Dynamic Mechanical Analysis)

Introduction:

Dynamic Mechanical Analysis (DMA), also known as DMTA for Dynamic Mechanical Thermal Analysis,
is a widely used technique to characterize a material's properties as a function of various parameters,
including time, temperature, frequency, and others. This analytical method is particularly valuable for
characterizing the viscoelastic behavior of materials, providing information about their stiffness, damping,
and energy dissipation.

Characterization:

DMA works by applying a sinusoidal deformation to a sample of known geometry. The sample can be
subjected by a controlled stress or a controlled strain, allowing the measurement of its stiffness and
damping. These measurements are then reported as modulus (storage modulus and loss modulus) and tan
delta.
• The storage modulus, either E’ or G’, is the measure of the sample’s elastic behavior.
• The loss modulus, either E’’ or G’’, is the measure of the sample’s viscous behavior.
• Tan delta represents the ratio of the loss modulus to the storage modulus and is a measure of the
energy dissipated by the material during deformation.

Figure 1: Modulus values change with temperature and transitions in

materials.

One of the most useful material properties measured during DMA testing is the loss factor, tan delta. A low
tan delta is correlated to low rolling resistance, making it important for materials used in tires and other
applications where minimizing energy loss is crucial. Conversely, a high tan delta indicates good traction
characteristics, desirable for materials used in footwear and other applications where grip is essential.
Instrumentation:

Figure 2 : Schematic diagram of DMA

Strengths and Limitations:

Strengths of Dynamic Mechanical Analysis (DMA):

• Small sample geometry
• Offers wide range of programmable frequencies, force and temperature parameters
• Two types of force alterations: oscillating and linear
• Programmable temperature: (1) heating and cooling ramps, (2) isothermal

Limitations of Dynamic Mechanical Analysis (DMA):

• Geometrically uniform test specimens
Examples: rectangular specimens with maximum dimensions L = 60 mm; W ≤ 15 mm; T = ≤ 5
mm
• Films size range: rectangular specimens with max. dimensions L = 30 mm; W ≤ 8 mm; T ≤ 2mm;,
also adaptive for analyzing small diameter flexible tubing (e.g. medical grade).
• Fiber size range: dimensions L = 30 mm; W = 5 denier; Dia. ≤ 0.8 mm
Technical Specifications:

• Temperature operation from -150 – 600°C

• Temperature ramp (Heating/Cooling) 0.1 – 10°C/minute
• Force Range: 0.0001 to 18 N
• Frequency Range: 0.01 – 200 Hz
• Dynamic Sample Deformation Range: ±0.5 to 10,000 micrometer

How DMA helps to understand the rubbers and polymers:

1. Understanding Viscoelasticity:

Rubbers and polymers exhibit both elastic and viscous properties. DMA measures both storage modulus
(E'), which represents stiffness and resistance to deformation, and loss modulus (E''), indicating energy
dissipation as heat. This provides a comprehensive picture of how these materials respond to stress.

2. Identifying Glass Transition Temperature (Tg):

DMA is particularly adept at pinpointing the glass transition temperature (Tg), a crucial point where a
polymer changes from a glassy, rigid state to a rubbery, flexible state. This crucial information helps predict
material performance at different temperatures and optimize processing conditions.

3. Characterizing Damping:

The tan delta (δ) value, the ratio of E'' to E', reveals a material's damping characteristics. High δ indicates
high energy dissipation, making the material ideal for shock absorption and vibration damping. This is
crucial for applications like tires and gaskets.

4. Optimizing Formulations and Design:

By understanding the viscoelastic behavior of different polymer blends and additives, DMA helps
researchers optimize material formulations for specific applications. This can lead to improved
performance, durability, and lifespan of products made from rubbers and polymers.

5. Quality Control and Failure Analysis:

DMA can be used to identify inconsistencies and defects in rubber and polymer products. By comparing
test results with established benchmarks, manufacturers can ensure quality and avoid failures. In case of
failure, DMA can help analyze the material's properties at different temperatures and stress levels to
understand the cause and prevent future occurrences.
 2. DSC (Differential Scanning Calorimetry)

Introduction:

Differential Scanning Calorimetry, or DSC, is a thermal analysis technique that looks at how a material’s
heat capacity (Cp) is changed by temperature. A sample of known mass is heated or cooled and the changes
in its heat capacity are tracked as changes in the heat flow. This allows the detection of transitions such as
melts, glass transitions, phase changes, and curing.
Two types of DSC systems commonly used.
1. Heat-flux DSC
A technique in which the temperature of the sample unit, formed by a sample and reference material,
is varied in a specified program, and the temperature difference between the sample and the
reference material is measured as a function of temperature.
2. Power-compensation DSC
A technique in which difference of thermal energy that is applied to the sample and the reference
material per unit of time is measured as a function of the temperature to equalize their temperature,
while temperature of the sample unit, formed by the sample and reference material, is varied in a
specified program.

Characterization:

Differential Scanning Calorimetry (DSC) is a powerful technique for characterizing the thermal behavior
of polymers. It provides valuable information about the thermodynamic properties of polymers, including:

• Glass transition temperature (Tg): The temperature at which the polymer changes from a glassy
state to a rubbery state.
• Melting temperature: The temperature at which the crystalline phase of the polymer melts.
• Crystallization temperature (Tc): The temperature at which the polymer crystallizes.
• Degree of crystallinity (Xc): The percentage of the polymer that is crystalline.
• Enthalpy of transitions: The amount of heat absorbed or released during a thermal transition.

DSC experiments are typically performed by heating a small sample of the polymer at a controlled rate
and measuring the heat flow into or out of the sample. The resulting DSC curve shows the heat flow as a
function of temperature.
 Figure 3 : DSC curve of PET

• The Tg can be determined from the midpoint of the change in heat flow that occurs at the glass
transition.
• The Tm can be determined from the peak of the endothermic peak that occurs at the melting point.
• The Tc can be determined from the peak of the exothermic peak that occurs at the crystallization
temperature.
• The Xc can be calculated from the area of the melting peak using the following equation:

Xc = (ΔH / ΔHm) * 100%

where:
ΔH is the enthalpy of melting of the sample.
ΔHm is the enthalpy of melting of 100% crystalline polymer.
Instrumentation:

Figure 4: Schematic diagram of a heat flux DSC system

1. Heaters

2. Platinum sensors

S - Pan with sample substance

R - Pan with reference

Figure 5 : Schematic of a power compensated DSC system.

Heat Flux DSC Power Compensation DSC

Sample Holder platinum, aluminum platinum, aluminum, and stainless

and stainless Steel Steel
Sensors Temperature sensors. Usually, Platinum resistance thermocouple.
thermocouples which are same for Separate sensors and heaters for both
both sample and reference. reference and sample.
Furnace One block for both reference and Separate block for both reference and
sample cell sample cell
 Figure 6 : DSC curve of PET (macromolecule)

This DSC curve shows a shift of the baseline around 77°C, indicating "glass transition". Also, an exothermic
peak is observed around 130°C, indicating an exothermic reaction caused by crystallization. The
endothermic peak observed at around 250°C refers to an endothermic reaction by "melting". Crystallization
after glass transition and subsequent melting were observed, indicating that the sample was in an amorphous
state with little crystallization by quenching after heating.

Strengths and Limitations:

Strengths of Differential Scanning Calorimetry (DSC):

• Small sample size
• Highly accurate measurement of phase transitions and heat capacities
• Very precise temperature control
• Sensitive measurement of subtle or weak phase transitions
• Ability to separate overlapping thermal transitions (Modulated DSC option)

Limitations of Differential Scanning Calorimetry (DSC):

• Small sample size
• Highly accurate measurement of phase transitions and heat capacities
• Very precise temperature control
• Sensitive measurement of subtle or weak phase transitions
• Ability to separate overlapping thermal transitions (Modulated DSC option)
Technical Specifications:

• Temperature range: -180°C – 725°C

• Controlled heating rates: 0.01 to 200 °C/minute
• Temperature accuracy: +/- 0.1°C
• Temperature precision: +/- 0.01°C

How DSC helps to understand the rubbers and polymers:

1. Glass Transition Temperature (Tg):

This crucial point marks the transition from a glassy, hard state to a rubbery, flexible state. DSC pinpoints
the Tg by detecting the characteristic heat flow change associated with this transformation. This information
is essential for:

• Predicting material behavior at different temperatures: Knowing the Tg helps us understand how a
material will respond to temperature changes in various applications, from tires to adhesives.
• Optimizing processing conditions: By identifying the Tg, we can tailor processing parameters like
temperature and time to achieve desired properties.

2. Crystallization and Melting:

For crystalline polymers, DSC reveals the heat flow changes associated with crystallization (solidification)
and melting. This information helps us understand:

• Polymer structure and morphology: The presence and size of crystalline regions influence a
polymer's properties like strength and stiffness.
• Processing and performance: Optimizing crystallization conditions can enhance a material's
performance and stability.

3. Curing and Crosslinking:

Curing involves the formation of chemical bonds between polymer chains, leading to increased strength
and rigidity. DSC monitors the heat flow associated with this reaction, providing insights into:

• Curing kinetics: Analyzing the heat flow curve helps us understand the rate and extent of curing,
allowing for optimized processing conditions.
• Crosslink density: The amount of heat released during curing can be related to the degree of
crosslinking, which influences a material's mechanical properties.

4. Thermal Decompositions:

High temperatures can cause materials to break down. DSC detects the onset and extent of thermal
decomposition by measuring the heat flow associated with this process. This information is crucial for:

• Material selection: Understanding the thermal stability of a material helps us choose the right one
for high-temperature applications.
 • Setting safe processing conditions: Knowing the decomposition temperature allows for setting safe
processing parameters to avoid material degradation.

5. Specific Interactions:

DSC can be used to study interactions between different components in a polymer blend or between a
polymer and an additive. By analyzing the heat flow changes associated with these interactions, we can
gain insights into:

• Compatibility of different materials: This is crucial for designing blends with desired properties.
• Effectiveness of additives: DSC can help us evaluate the performance of additives like flame
retardants or plasticizers.

3. TGA (Thermo-Gravimetric Analysis)

Introduction:

TGA measures the amount and rate of change in the mass of a sample as a function of temperature or time
in a controlled atmosphere. The measurements are used primarily to determine the thermal and/or oxidative
stabilities of materials as well as their compositional properties. The technique can analyze materials that
exhibit either mass loss or gain due to decomposition, oxidation or loss of volatiles (such as moisture). It is
especially useful for the study of polymeric materials, including thermoplastics, thermosets, elastomers,
composites, films, fibers, coatings, and paints.

Characterization:

Thermo-Gravimetric Analysis (TGA) is a powerful technique for characterizing the thermal stability and
degradation behavior of polymers. This provides valuable information about the thermal decomposition of
the polymer, including:

• Compositional analysis of multi-component materials or blends

• Thermal stabilities
• Oxidative stabilities
• Estimation of product lifetimes
• Decomposition kinetics
• Effects of reactive atmospheres on materials
• Filler content of materials
• Moisture and volatiles content
Mechanisms of weight change in TGA
• Weight loss
Decomposition: The breaking apart of chemical bonds.
Evaporation: The loss of volatiles with elevated temperature.
Reduction: Interaction of sample to a reducing atmosphere.

Figure 7 : Weight loss TGA curve

• Weight gain
Oxidation: Interaction of the sample with an oxidizing atmosphere.

Figure 8 : Weight gain TGA curve

Classification of TGA curves

A: No mass change over entire range of temperature.

B: Desorption/Drying. Mass loss is large followed by mass

plateau.

C: Single Stage Decomposition

D: Multistage Decomposition

E: Atmospheric Reaction, Increase in mass, reactions like

surface oxidation.

Instrumentation:

Figure 9 : Schematic diagram of the TGA

Strengths and Limitations:
Strengths of Thermo-Gravimetric Analysis (TGA):
• Small sample size
• Analysis of solids and liquids with minimal sample preparation
• Qualitative or quantitative analysis
• Detection of multiple mass loss thermal events from physical and chemical changes of materials
• Separation of overlapping mass loss thermal events (High Resolution TGA)

Limitations of Thermo-Gravimetric Analysis (TGA):

• Evolved products are identified only when the TGA is connected to a spectrophotometer (e.g.
TGA/MS or TGA/FTIR). This technique is available at EAG Laboratories in some supporting
locations.

Technical Specifications:

• Signal Detected: Mass change and temperature.

• Maximum Sample Weight: 1 gram
• Temperature Range: Ambient to 1000°C (1100°C available at some supporting locations TG-
DTA)
• Controlled Heating Rate: 0.01 to 100°C/minute
• Weighing Precision: +/-0.01%

How TGA helps to understand the rubbers and polymers:

1. Composition:
•Identification and quantification of fillers: Different fillers (e.g., carbon black, silica) have distinct
decomposition profiles, allowing their presence and amount to be determined.
•Polymer type identification: Unique thermal decomposition patterns of different polymers can help
identify the type of present in a sample.
•Presence of volatile additives: TGA can detect and quantify the presence of volatile additives like
plasticizers, antioxidants, and flame retardants.

2. Thermal Stability:
•Temperature of onset of degradation (TOD): This crucial parameter indicates the temperature at
which significant weight loss begins, providing insights into the material's safe operating range and lifetime.
•Oxidative stability: Comparing weight loss in air vs. inert atmospheres like nitrogen reveals the
material's resistance to degradation under oxygen exposure.
•Glass transition temperature (Tg): While not directly measured by TGA, changes in the slope of
the weight loss curve can sometimes indicate the Tg of the polymer.
3. Degradation Behavior:
•Extent of crosslinking: The weight loss profile during curing can be used to estimate the degree of
crosslinking in a rubber or polymer, influencing its mechanical properties.
•Decomposition mechanism: Analyzing the evolved gases from the sample using coupled
techniques like TGA-MS can reveal the chemical reactions involved in the degradation process.
•Identification of degradation products: Understanding the breakdown products helps predict the
potential hazards or environmental impact of material degradation.

4. Additional properties:
•Moisture content: TGA can quantify the amount of moisture absorbed by a polymer, which can
affect its dimensional stability and mechanical properties.
•Inhomogeneities and defects: Inconsistencies in the material can be revealed by deviations from
the expected weight loss profile.

4. FTIR (Fourier Transform Infrared Spectroscopy)

Introduction:
Fourier transform infrared spectroscopy (FTIR) is an incredibly versatile materials analysis technique,
helping identify organic and some inorganic materials that could be the source of product contamination or
cause a malfunction. TIR analysis is used to identify molecular compounds. It works by measuring the
absorbance of infrared radiation by a sample. The resulting spectrum can then be used to identify the
functional groups present in the compound. FTIR spectroscopy can be used on solid, liquid, and gaseous
samples. Usually, the amount of material required for a viable analysis is very small and most analyses can
be done relatively quickly with little sample preparation.

Characterization:
Different functional groups within the polymer molecule vibrate at specific frequencies when exposed to
infrared light, and these vibrations show up as peaks in the FTIR spectrum. By analyzing the positions
and intensities of these peaks, we can gain a wealth of information about the polymer, including:

1.Polymer identification: Different types of polymers have unique FTIR spectra, which can be used to
identify unknown materials or to confirm the identity of a known polymer.

2.Functional group analysis: FTIR spectroscopy can identify the specific functional groups present in a
polymer, such as C-H, O-H, N-H, C=O, and C-N. This information is essential for understanding the
polymer's properties and behavior.

3.Chemical bonding: FTIR spectroscopy can provide information about the types of chemical bonds
present in a polymer, such as single bonds, double bonds, and triple bonds. This information can be used
to study the polymer's strength, flexibility, and other properties.
4.Degree of crystallinity: FTIR spectroscopy can be used to measure the degree of crystallinity in a
polymer. Crystalline regions in a polymer have a more ordered structure than amorphous regions, and this
difference is reflected in the FTIR spectrum.

5.Polymer blend analysis: FTIR spectroscopy can be used to analyze the composition of polymer blends.
This technique can be used to determine the ratio of different polymers in a blend and to study the
interactions between the different components.

6.Polymer degradation: FTIR spectroscopy can be used to monitor the degradation of polymers over time.
Degradation can lead to changes in the polymer's chemical structure, which can be detected by FTIR
spectroscopy.

7.Quantitative analysis: In some cases, FTIR spectroscopy can be used to quantitatively measure the
concentration of specific functional groups or components in a polymer. This requires careful calibration
of the FTIR instrument and the development of appropriate analytical methods.

Figure 10: FTIR graphs of different materials

Instrumentation:

Figure 11: Schematic diagram of the FTIR

FTIR analysis measures a sample’s absorbance of infrared light at various wavelengths to determine the
material’s molecular composition and structure. The Fourier transform spectrometer works to convert the
raw data from the broad-band light source to actually obtain the absorbance level at each wavelength.
The mid-IR spectrum is divided into four regions:
(i) the single bond region (2500-4000 cm-1)
(ii) the triple bond region (2000-2500 cm-1)
(iii) the double bond region (1500-2000 cm-1)
(iv) the fingerprint region (600-1500 cm-1)
 Figure 12: Four regions of the FTIR graph

Strengths and Limitations:

Strengths of Fourier transform infrared spectroscopy (FTIR):

• Capable of identifying organic functional groups and often specific organic compounds
• Extensive spectral libraries for compound and mixture identifications
• Ambient conditions (vacuum is not necessary; applicable for semi-volatile compounds)
• Minimum (limit of detection) analysis area: ~15-50 µm. Rule-of-thumb: if you can see the
sample by eye, it most likely can be analyzed.
• Can be quantitative with appropriate standards and uniform sample thicknesses
• Complementary to Raman spectroscopy

Limitations of Fourier transform infrared spectroscopy (FTIR):

• Firstly, limited surface sensitivity (typical limit of detection is a film thickness of 100 nm)
• Only specific inorganic species exhibit an FTIR spectrum (for example: yes: silicates,
carbonates, nitrates and sulfates; no: titinia, oxides, etc.)
• Sample quantitation requires the use of standards
• Glass absorbs infrared light and is not an appropriate substrate for FTIR analysis
• Water also strongly absorbs infrared light and may interfere with the analysis of dissolved,
suspended or wet samples
 • Simple cations and anions, e.g., Na+ and Cl–, do not absorb FTIR light and hence cannot
be detected by FTIR. Identification of mixtures/multiple sample components may require
additional laboratory preparations and analyses.
• Lastly, FTIR cannot analyze metals that reflect light

Technical Specifications:

• Signal Detected: Infrared absorption.

• Elements Detected: Molecular functional groups (NOT elements)
• Detection Limits: 1-10 wt% (quantification of known components); 5-20 % (identification
of unknown components)
• ATR Depth Resolution: ~0.1-1 micron
• Transmission FTIR: Infrared light passes through the entire sample.
• Imaging: No mapping for FTIR
• Lateral Resolution/Probe Size: > 15-50 µm

How FTIR helps to understand the rubbers and polymers:

1. Identifying Functional Groups:

FTIR analyzes the infrared radiation absorbed by a sample. Different functional groups within the
polymer chain vibrate at specific frequencies, creating a unique fingerprint on the spectrum. This
fingerprint allows scientists to identify the types of functional groups present, such as alkanes, carbonyls,
and hydroxyls. Imagine the spectrum as a barcode for the polymer, revealing its building blocks.

2. Determining Polymer Type:

By comparing the fingerprint of the unknown polymer to a library of known polymer spectra, scientists
can identify the type of polymer present in the sample. This is like matching the barcode to a database to
find the product's name.

3. Monitoring Curing and Degradation:

FTIR can track the progress of curing in rubbers by monitoring the disappearance of specific functional
groups involved in the crosslinking process. Similarly, it can detect polymer degradation by observing the
appearance of new functional groups associated with breakdown products. Think of it as watching the
barcode change as the polymer undergoes chemical transformations.

4. Quantifying Additives and Fillers:

FTIR can be used to quantify the amount of certain additives and fillers in rubber and polymer blends. By
measuring the intensity of specific peaks associated with these components, scientists can determine their
relative concentrations. This helps in optimizing the formulation of materials with desired properties.
5. Studying Morphology and Crystallinity:

FTIR can provide information about the morphology and crystallinity of polymers. The presence of
broad, diffuse peaks can indicate an amorphous structure, while sharper peaks suggest a more ordered,
crystalline structure. This information is crucial for understanding the mechanical and physical properties
of the material.

6. Analyzing Surface Chemistry:

Techniques like Attenuated Total Reflectance (ATR) allow FTIR to analyze the surface chemistry of
rubbers and polymers. This is particularly useful for studying coatings, adhesives, and other surface-
modified materials.