Arcelor Research Industry Gent - OCAS

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Service sheet n°:

MC.CH.7

Polymer characterization tests (DSC,

TGA, GPC)

Category: Material characterization

Subcategory: Chemical analysis

Written by: N. Van den Bossche

Approved by:
Version n°: 2
Last update: 05/05/2006

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Polymer characterization tests (DSC, TGA, GPC) MC.CH.7
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DSC (Differential Scanning Calorimetry), TGA (Thermogravimetric analysis) and GPC (Gel
Permeation Chromatography) are widely used techniques to characterize polymers. DSC
measures temperature and heat flow of physical and chemical changes that involve endothermic
or exothermic processes, or changes in heat capacity. TGA provides information about the
temperature-dependent weight loss, while GPC provides the molecular weight of the polymers in
solution.

DSC (Differential Scanning Calorimetry)

DSC measures the temperature and heat flow associated with phase transitions in
materials. With this technique a sample and an inert reference are heated and cooled in a
controlled environment. The reference pan is subjected to a chosen heating/cooling
program, e.g. 20°C/min. The heat flow to the sample is adjusted in such a way that, at all
time the temperature of the sample is equal to that of the reference. If a heat-related change
takes place in the sample (glass transition, melting, crystallisation), the sample either
absorbs or emits heat. In order to keep the temperature of sample and reference the same,
more or less heating power is needed. The heating power difference between sample and
reference from such a heat change is directly related to the heat flow, which is shown on the
DSC-curves. DSC measurements provide thus quantitative and qualitative information
about physical and chemical changes that involve endothermic or exothermic processes, or
changes in heat capacity.

Instrument specifications:
TA instruments DSC 2920 with modulated DSC option
RCS cooling system temperature range: - 70°C to 350°C
Gas switching accessory ability to change between gases (N2, O2) during analysis

Operating parameters:
Temperature range -70 °C to 350°C
Heating/cooling rate Max. 50 °C/min (depends also on the
temperature range of your experiment)
Atmospheres N2, O2, He

TGA (Thermogravimetric Analysis)

TGA is a thermal analysis technique for measuring the mass variation in a sample as a
function of temperature under a controlled atmosphere. This variation of mass can be
positive (mass gain) when the sample has been subjected to oxidation or corrosion, or else
negative (mass loss) when part of the sample has been transformed into vapour. Thermal
stability behaviour can be investigated in both conditions
(1) dynamic, in which the temperature is increased at a linear rate
(2) isothermal, in which the temperature is kept constant.

Instrument specifications
TA instrument TGA 2950 with Hi-Res option
Gas switching accessory ability to change between gases (N2, O2) during analysis
Heat exchanger to dissipate heat from the furnace

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Operating parameters

Temperature range 25°C to 1000°C

Heating rate (standard furnace) 0,1 to 100°C/min
Weighing capacity 1,0 g
Atmospheres N2, O2, He

Applications of DSC and TGA

DSC (T, H) TGA ( ∆ m)

PHYSICAL PROPERTIES
Glass transition ++
Melting ++
Evaporation ++ +
Phase transition ++
Crystallization/Crystallinity rate ++
Pyrolysis + ++
THERMODYNAMICS
Heat Capacity (Cp) +
CHEMICAL PROPERTIES
Adsorption/desorption + ++
Loss of weight ++
Loss of solvent ++
Hydration/dehydration + ++
decomposition + ++
(T) : Termperature measurement
(H) : Enthalpy measurement
(∆ m) : Mass variation measurement
+ : the technique permits measuring this property
++ : the technique is especially well adapted for measuring this property

GPC (Gel Permeation Chromatography)

GPC is a column chromatography technique that enables polymer molecules of different

sizes in solution to be separated from one another, such that the large molecules elute first
and small molecules elute last. As they emerge from the bottom of the column, they are
detected by a differential refractometer. Since the molecular size in solution (hydrodynamic
volume) is related to Mw (molecular weight), a picture of the entire Mw distribution is
obtained quickly and simply.

Instrument specifications
Waters 515 HPLC pump
Waters Column Heater Module
Waters 2410 RI detector

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The background and context of the demand, the expected deliverables of the test.

DSC

sample weight : 0,5 mg – 100 mg

sample volume : 10 mm3
the sample pan has a diameter of 6 mm.

TGA

Sample weight : maximum 1 g

Sample volume : 100 µ-liter and 250 µ-liter
The sample pans have a diameter of 10 mm

GPC

The samples need to be soluble in THF (tetrahydrofuran). The injection volume is about
20µL.
Molecular weight range of the polymers : 0 – 20.000 Da

DSC

The research report contains the DSC-curve, showing heat flow against temperature. For every
phase transition, the temperature is annotated including peak integration, which yields the
experimental heat in joules per gram.

Tg : glass transition temperature

Tc : cristallization temperature
Tm : melt temperature

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TGA

The research report contains the TGA-curve, showing weight change against temperature. For
every mass variation, the temperature and weight change will be given.
Below you find the thermogram of Ca-oxalate.

GPC

The research report contains a GPC-chromatogram in which concentration is plotted against

retention time. In a table you can find Mn, Mw and the polydispersity of all the peaks.
Mn : numerical average molecular weight
Mw : weight average molecular weight

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Feasibility

All the equipment and instruments necessary to execute these tests described, is available at
Arcelor Research Industry Gent.

The temperature range for the DSC lies between -70°C and 350°C.
The temperature range for the TGA lies between room temperature and 1000°C.

Maturity

Good experience with these tests, so good maturity.

Success stories

Different success stories have been executed:

Study of degradation behaviour of coatings

Determination of % water in coatings, paints
Determination of the reversibility of phase-transition in materials
Study of precipitates in alloys

Determination of the percentage phase change particles in a coating

In order to determine the percentage Phase Change Materials (PCMs) in a coating, the coating
was characterized with TGA and DSC.

→ In a first stage, the PCM solution was characterized with TGA and DSC. The PCMs store
latent heat, which can be measured with DSC. Figure 1 gives the DSC-thermogram of the PCM
solution in the second heating.

Figure 1: DSC thermogram of the PCM solution in the second heating.

When the temperature increases, the PCMs are melting and give an endothermic peak on the
DSC thermogram. In this case two endothermic peaks are visible due to the solid-solid and solid-
liquid transitions. The area under the peaks is defined as the latent heat which is 47.52 J/g.

In order to determine the latent heat of the pure PCM particles, a TGA measurement was done to
determine the percentage of PCM particles in the PCM solution. Figure 2 gives the TGA
thermogram of the PCM solution.

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Figure 2: TGA thermogram of the PCM solution.

TGA measures the weight change as function of temperature. As the temperature increases,
water evaporates leading to decrease in weight of the sample. From figure 2 it can be concluded
that the PCM solution contained 40% PCM particles.

From the DSC and TGA measurements, the latent heat of the pure PCM particles is 118.81 J/g.

→ In a second stage, a known amount of coating was analyzed with the DSC (figure 3).

Figure 3: DSC thermogram of the PCM coating.

Because no other component of the coating absorbs energy in the temperature range 0°C to 40
°C, the percentage of PCM particles in the coating could be calculated from the determination of
the latent heat of the coating. In this case the latent heat of the coating was 0.35 J/g and thus
0.30% PCM particles were present in the coating.

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