Identification of BR and NBR using a TGA-

FTIR Combination
Purpose
BR and NBR are difficult to distinguish from one another by thermal analysis alone. One possibility
of differentiating between these two polymers is to use a combined technique such as TGA-FTIR. 
Sample
Technical NBR and BR elastomers
Conditions
Measuring cell: TGA/SDTA851e connected to a Nicolet Nexus FTIR spectrometer by a heated
transfer line.
Pan: Alumina 70 µl
Sample preparation: Pieces of approx. 20 mg (NBR) and 30 mg (BR)
TGA measurement: Heating from 50 °C to 700 °C under nitrogen (50 ml/min) Heating rate 10
K/min
 Atmosphere: Nitrogen

The diagram displays the TGA and DTG curves of the NBR and BR samples.  
Evaluation
The pyrolysis of NBR and BR takes place in practically the same temperature range. On the basis of
the pyrolysis alone, it is not possible to identify the polymer concerned. 
NBR differs from BR in that it has a nitrile group. In the infrared (IR) spectrum, the nitrile group
absorbs in the range 2260-2180 cm-1 . The absorption band cannot always be identified with
certainty in the IR spectrum under typical TGA-FTIR measurement conditions because it is
sometimes of low intensity and is in any case close to the CO2 absorption bands. In such cases, it is
advantageous to evaluate the chemigram recorded with data from the wavenumber range of interest.
In simple terms, the IR absorption in this wavenumber range is continuously integrated and plotted
as a function of temperature (or time). 

The diagram displays the DTG curve and the chemigram for the wavenumber range 2260-2180 cm-
1 . In the BR measurement, no peak was observed in the chemigram during pyrolysis. It follows that
none of the volatile compounds evolved contained a nitrile group. With NBR, the pyrolysis peak in
der DTG curve corresponds to the peak observed in the chemigram. This nitrile absorption indicates
that the material pyrolyzed contained a nitrile group. This confirms that is was NBR.
Evaluation
An analysis of of the evolved gases with an online TGA-FTIR combination is a useful technique to
identify the type of elastomer measured. If the IR absorption intensity is low, as in the above case of
NBR, sensitivity can be increased by evaluating the chemigram of the wavenumber range of the
characteristic absorption bands of interest. 

Identification of BR and NBR using a TGA-FTIR Combination | Thermal Analysis Application No. HB601 |
Application published in METTLER TOLEDO TA Application Handbook Elastomers, Volume 2.
TGA of Styrene-Butadiene Rubber (SBR)
Purpose
To perform thermogravimetric measurements on SBR that had been produced under different
conditions
Sample
Two types of unvulcanized SBR:  
• Krylene 1500 made by emulsion polymerization, with a wide molecular weight distribution
• VSL5025-0 polymerized from solution, with a narrow molecular weight distribution 
Conditions
Measuring cell: TGA/SDTA851e 
Pan: Alumina 30 µl 
Sample preparation: Pieces of rubber of approx. 15 mg 
TGA measurement: Heating from 50 °C to 625 °C under nitrogen (50 ml/min), and then from 625
°C to 860 °C under air (50 ml/min) Heating rate 30 K/min  
Atmoshpere: Nitrogen then air, automatically switched

Interpretation
The measurement curves show that the thermal degradation of SBR depends on the polymerization
conditions. Emulsion polymerized SBR contains more volatile components than SBR polymerized
in solution. In the Krylene1500 DTG curve, a peak appears just before the actual pyrolysis at about
400 °C. SBR polymerized in solution does not show this step. With both materials, the main step of
the pyrolysis causes a peak in the DTG curve with a maximum at about 470 °C. The pyrolysis of
SBR produces only a small amount of carbon black (approx. 0.3%). The ash content is also low
(approx. 0.2%). 
Evaluation
The evaluation of the individual steps is summarized in the following table:

Conclusions
SBR pyrolyzes at about 470 °C. The amount of carbon black formed during pyroplysis and the
residual ash are negligible. With emulsion polymerized SBR, the loss of mass due to vaporization of
the emulsifying agent before pyrolysis can be measured.
TGA of Styrene-Butadiene Rubber | Thermal Analysis Handbook No.HB428| Application published in METTLER
TOLEDO TA Application Handbook Elastomers, Volume 2