Thermogravimetry

definitions
. a technique in which the mass of a substance is measured as a function of temperature, while the substance is subjected to a controlled temperature programme.

Controlled temperature programme can mean:

heating and/or cooling at a linear rate (by far commonest) isothermal measurements combinations of heating, cooling and isothermal stages

other, more modern approaches, in which the temperature profile is modified according to the behaviour of the sample.

instrumentation
GAS IN WEIGHT

BALANCE CONTROLLER

GAS-TIGHT ENCLOSURE
SAMPLE

HEATER

SAMPLE TEMP.

POWER

FURNACE TEMP.

TEMPERATURE PROGRAMMER

balance/furnace configurations

example curve

Mass (%) in green, rate of mass loss (%/C) in blue.

physical limitations on the heating process

EXCHANGE OF GASES: REACTING GASES IN, PRODUCTS OUT

CONVECTION THROUGH SURROUNDING ATMOSPHERE

RADIATION FROM FURNACE WALL

CONDUCTION THROUGH SAMPLE PAN AND INSTRUMENT

INDICATION OF SAMPLE TEMPERATURE

factors that affect the results

A) INSTRUMENTAL
heating rate furnace atmosphere and flow-rate geometry of pan and furnace material of pan

B) SAMPLE-RELATED
mass particle size sample history/pre-treatment packing thermal conductivity heat of reaction

For a given instrument, careful standardisation of experimental procedures leads to highly reproducible results.

effect of heating rate

10 mg samples of PTFE, heated at 2.5, 5, 10 and 20 C/min in nitrogen

isoconversion kinetic treatment

lifetime prediction

effect of atmosphere

CaC2CO4.H2O in air and nitrogen

sources of error
A) MASS Classical buoyancy Effect temp. on balance convection and/or turbulence viscous drag on suspension NOISY OR ERRATIC RECORDS CAN ARISE FROM:

static
vibration pressure pulses in lab.

These are lumped together as the buoyancy uneven gas flow correction, and if significant, can be allowed for by a blank run

B) TEMPERATURE Temperature calibration difficult to carry out accurately.

Many methods exist, but none totally satisfactory.

Best accuracy from simultaneous TG-DTA or TG-DSC instrument.

calibration
MASS - Use standard weights. Use standard samples to check operation, but unwise to use them as weight standards. TEMPERATURE Four approaches: Observe deflection on Temperature/time curve Curie-point standards Drop-weight methods In simultaneous-type units, use melting standards DO NOT use decomposition events to define temperature.

calibration using sample thermocouple

calibration using drop weight

calibration using curie point

weight change/ mg

0.2

Nickel metal 0.0 3C/min. in nitrogen

350

370 temperature /C

calibration using TG-DTA

10mg Gold (99.999%), 10C/min, alumina pan, air.

polymer stability studies

a = PVC, b= nylon-6, c = LDPE, d= PTFE

compositional analysis of filled rubber

composition of PVAc

LDPE/nylon film

sample controlled TG

comparison of temperature programmes

modulated temperature thermogravimetry

thermogravimetry-EGA by mass spectroscopy

simultaneous DSC/DTA-thermogravimetry
T

TR

simultaneous DSC-thermogravimetry

TGA-MS of PVC

thermogravimetry-EGA by FTIR

summary
PROCESS Ad- or absorption Desorption, drying Dehydration, desolvation Sublimation Vaporisation Decomposition WEIGHT GAIN WEIGHT LOSS

Solid-solid reactions (some)

Solid-gas reactions Magnetic transitions

recommended reading

D. M. Price, D. J. Hourston & F. Dumont, Thermogravimetry of Polymers, R. A. Meyers (Ed.), Encyclopedia of Analytical Chemistry, John Wiley & Sons Ltd., Chichester (2000) pp. 8094-8105. G. R. Heal,Thermogravimetry & Derivative Thermogravimetry, in P.J. Haines (ed.) Principles of Thermal Analysis & Calorimetry, ch. 4, Royal Society of Chemistry, Cambridge (2002) pp. 10-54. C. M. Earnest (Ed.), Compostional Analysis by Thermogravimetry, ASTM STP 97, American Society for Testing and Materials (1988).