Thermal Analysis

Technique Abbreviation Measurement

Thermogravimetry TG Mass change

Differential thermal analysis DTA Temperature difference

Differential scanning calorimetry DSC Heat flow

Thermomechanical analysis TMA Deformation

Dynamic mechanical analysis DMA Deformation

Thermal events during heating of a solid in an inert atmosphere
(constant pressure)
Thermal Event Reaction Heat Flow (H) Mass Change in Solid

Solid phase transformation 1 A (solid )  A (solid ) + or - no

Glass transition 2 A (glass)  A (rubber) no no

Melting A (solid)  A (liquid) + no

Sublimation A (solid)  A (gas) + yes

Thermal decomposition A (solid)  B (solid) + C + or - yes

(gas)
Enthalpy Change
• Constant pressure
• 1st Law of Thermodynamics

Internal energy change of a system U  Q  W

Heat flow into a system Work done by the system

• Heat: energy transfer between a system and its surrounding due to temperature
differences.
• Work: all types of energy transfer other than heat.
 Thermogravimetric Analysis (TGA)
 Measures change in mass (m) of sample as a function of temperature or time
(isothermal).
 Application:
 Decomposition of material
 Thermal stability of material
 Degradation temperature of polymeric material
 Residual solvent level
 Absorbed moisture content
 Amount of inorganic (noncombustible) filler in polymer or composite material
compositions
 Determination of evaporation rate, water content and Curie temperature of magnetic
material
Interpretation
Seven classification of TG curves
(i) No decomposition with loss of volatile products.
(ii) Rapid initial mass loss characteristic of
desorption or drying.
(iii) decomposition in single stage.
(iv) multi-stage decomposition.
(v) multi-stage decomposition but no stable
intermediates.
(vi) Gain in mass as a result of sample reaction.
(vii) reaction product decompose again.
 A
A
B

C
B

total %W lost at this point is the sum of the two steps, 12.3 + 19.2 = 31.5%

%W lost from the original compound is (44/146) 100 = 30.1%

total mass loss is the sum of all three steps: 12.3 + 19.2 + 30.1 = 61.6%
quantitative analysis of Ca2+, Sr2+ and Ba2+ in aqueous solution is possible by TGA

The separation of these ions is carried out with ammonium oxalate to give mixed metal oxalate hydrates which are
decomposed on the thermobalance

(E)
PVC, polyvinylchloride; PMMA, polymethylmethacrylate; HDPE, high-density
polyethylene; PTFE, polytetrafluoroethylene; PI, polyimide
TGA (solid line) and DTG (dotted line) thermal curves of a pure hydrated sodium
silicate. The TGA mass loss from 50–150 C
TGA (solid line) and DTG (dotted line) thermal curves of polyvinylchloride polymer heated
under nitrogen
 DIFFERENTIAL THERMAL ANALYSIS

Differential thermal analysis (DTA) is a technique in which the difference in temperature,

T, between the sample and an inert reference material is measured as a function of temperature
Endothermic:

Phase changes such as melting (fusion), vaporization, sublimation transitions between two
different crystal structures for a material.
Chemical reactions: dehydration, decomposition, oxidation–reduction, and solid–state reactions

Exothermic:
Phase changes such as freezing (crystallization), some transitions between different crystal
structures
Chemical reactions: decomposition, oxidation–reduction, and chemisorption can be exothermic

Physical changes:
Adsorption and desorption of gases from surfaces and glass transitions in amorphous glasses and
some polymers
 Exothermic changes are plotted as positive, and the peaks point up, while endothermic changes
are plotted as negative, and the peaks point down

The peak area in DTA is related to the enthalpy change, H, to the mass of sample used, m, and to a large
number of factors like sample geometry and thermal conductivity. A, being related to the mass and H by an
empirically determined calibration constant, K:
A = K(m)(H)
Glass transition temperature is represented by Tg and is a property of the amorphous materials or the amorphous
portion of a semicrystalline materials. When the ambient temperature is below Tg, the molecular chains of
amorphous materials are frozen in place and behave like solid glass.

Glass transition temperature is the temperature, below which the physical properties of plastics change to those of a
glassy or crystalline state. Above Tg they behave like rubbery materials. Below the Tg a plastic’s molecules have
relatively little mobility. Tg is usually applicable to wholly or partially amorphous plastics.
 Differential Scanning Calorimetry

The differences in heat flow into a reference and sample are measured vs. the temperature of the sample
 same furnace heats both the sample and the reference

The temperature is changed in a linear manner while the differential heat

flow into the sample and reference is measured.

The sample and reference pans sit on the heated thermoelectric disk, made of
a Cu/Ni alloy.

The differential heat flow to the sample and reference is monitored by area
thermocouples attached to the bottom of the sample and reference positions
on the thermoelectric disk.

The differential heat flow into the pans is directly proportional to the
Heat flux DSC
difference in the thermocouple signals
 two separate heating elements are used for the sample (marked P and R)
and the reference

A change in temperature between the sample and the reference serves as

the signal to “turn on” one of the heaters so that the sample and the
reference stay at the same temperature

Power compensation provides high calorimetric accuracy, precision, and

sensitivity

Power compensated DSC

DSC of PET
% crystallinity = heat of melting – heat of crystallization x 100
Specific heat of melting
Signal and noise XPS
• S/N ratio, LOD, sensitivity • basics, surface survey scan,… binding energy
• Different types of noise • Stepped background
Atomic spectroscopy • Sharp peak – core shell
• AAS, AES, AFS • Spin-orbit splitting
• HCL • Multiplet splitting
• Interference • Satellites – shake-up and shake-off
• Background correction • Auger
X-ray Fluorescence • Plasmon
• X-ray generation, continuum, X-ray source
• Diagram lines AES
• Forbidden lines • XRF vs AES competitive-complimentary
• Satellite lines • Kinetic energy
• Selection rule
• XRF for low atomic number Electron microscope
• Energy and wavelength dispersive SEM
TEM
Thermal analysis
TGA, DTA, DSC