TGA

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 Thermal Analysis
• A group of methods by which the physical & chemical
properties of a substance, mixture &/or reaction mixtures
are determined as a function of temperature and/or time,
while sample is subjected to a controlled temperature
program.
• Include heating or cooling (dynamic) or holding
temperature constant (isothermal), or combination.
• Thermogravimetry Analysis (TGA) – mass of substance
against temperature or time.
• Differential Scanning Calorimetry (DSC) – heat flow as a
function of temperature or time.
• Thermal Mechanical Analysis (TMA) – deformation
under static load vs T or time.
• Dynamic Mechanical Analysis (DMA) – substance under
oscillating load.
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 Thermogravimetric Analysis (TGA)
• Used to measure changes in weight (mass),
Δm, of sample as a function of T and/or
time.
• Commonly used to
– Determine polymer degradation temperature,
– Residual solvent level,
– Absorbed moisture content, and amount of
inorganic (noncombustible) filler in polymer
or composite material compositions.
– Decomposition temperature of
materials-impurities in ceramic etc 3
• Response ;
– Weight gain – adsorption (physical),
oxidation (chemical).
– Weight loss – vaporization (physical),
desorption (physical), oxidation (physical),
decomposition (chemical), dehydration &
desolvation (chemical).

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 Applications of TGA
• Can measure the fill materials added to some foods, such as silica gels
and titanium dioxide.
• Can determine the purity of a mineral, inorganic compound, or organic
material.
• Distinguishes different mineral compositions from broad mineral types,
such as borax, boric acid, and silica gels.
• Identify filler content, ash content by weight %.
• Characterize decomposition patterns, study degradation
mechanisms & kinetics.
• Prediction of lifetime (stability) at desirable time & temperature
conditions in desirable environment.
• Screening of additives (stabilizers, flame retardant, plasticizers, etc).
• Impurities analysis in materials.
• Compositional analysis of polymeric formulations
• Examine flame retardant & combustion properties.
• Magnetic transitions in metallic materials.

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Schematic thermobalance – sample heated at certain rate in a
controlled atm. Solid samples 1 mg to 100 mg but sometimes
up to 100 g.
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TGA

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 (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.
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Data Analysis

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Depending on polymer composition, reaction upon
heating will give their own characteristic TG curve.
Result can give thermal stability of material –
desorption, decomposition & oxidation information.
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Calcium oxalate monohydrate – 3 distinct weight losses.
CaC2O4.H2O CaC2O4 CaCO3 CaO 15
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Molded underfill material (flip chip application) – 3 degradation
stages ; moisture & volatiles in resin, weakly bonded
monomers, then breakage of cross-linked monomers.
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Multiple-stage reaction
: dehydration reaction
of hydroxide from
LiOH.H2O (exo).
4LiOH.H2O (solid) + O2
2Li2O + 4H2O
Then formation
reaction of Li2SnO3 due
to reaction between
Li2O with SnO2 in
mixture (exo).

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 • The sample was heated
from room temperature to
900°C at a rate of 5°C/min
in air.
•Polyester (71% of the
polymer),
•Polystyrene (29% of the
polymer),
• Fiberglass (22.9% of the
whole) and CaCO3 (49.3%
of the whole) were easily
identified by their different
temperatures of combustion
• Thermogravimetric analysis was used as one of or evaporation.
several complementary techniques in the identification
•The combustion of the
of an unknown polymer composite.
styrene polymer component
• TGA was then performed on the material to find the produced enough energy
weight percent of each material. that the temperature
momentarily increased
more than the programmed
rate. 19
Evolved Gas Analysis (EGA) using TGA and MS

• Attach a reasonably priced

(Quadrupole?) MS to a TGA
• While monitoring mass loss
with the TGA also examine
the gases present in the inert
background gas stream
• Allows the chemistry proposed based on mass
loss data to be confirmed via gas analyses

CHM 342
 Evolved Gas Analysis with FT-IR
• Attach a reasonably
priced FT-IR to a TGA
• While monitoring
mass loss with the
TGA also examine
the gases present in
the inert background
gas stream w/FT-IR
• Allows the chemistry proposed based on mass loss
data to be confirmed via gas analyses

CHM 342
 Thermogravimetric Analysis
• Factors affecting TG curve
– heating rate
– sample size
– particle size of sample
– the way it is packed
– crucible shape
– gas flow rate
• DTG – derivative of TG curve, often useful in revealing
extra detail.
• TG also often used with DTA (differential thermal
analysis).
• DTA – record difference in T (∆T) between sample and
reference material. Each DTA curve should be marked
with either endothermic or exothermic direction.
• Curve – peak represent exothermic or endothermic
reaction. 22
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