How polymers burn
...they react to heat strangely

The large molecules of polymers do not follow the classical physical states and phase transitions observed by small molecules. For example you know that water has the three physical states of solid, liquid, and gas. And you are likely familiar with the state changes such as melting, freezing, boiling (vaporization), and condensation.

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You may have experienced cases where a plastic or rubber material was affected by temperature changes. The video clips below show how the properties of a rubber racquet ball change as it warms from a "frozen" glass state to a "rubber" state.

This is a racquet ball at room temperatureThis is a racquet ball near its glass transition temperature

Below is an overview of how polymers change as heat is applied.

Soften: as heat is added, polymers change from a stiff solid at low temperatures to a soft pliable material at the glass transition temperature, Tg.

Melt: similar to the wax of a candle, crystalline polymers can melt when heated but usually at relatively high temperatures. Some polymers are amorphous and do not show a clear melt transition, Tm.

Decompose: polymers do not vaporize (become a gas) after melting, they breakdown or depolymerize into smaller molecules (fragments) at high temperatures.

Burn: for many commodity polymers the fragment vapors will burn in the presence of oxygen and heat (ignition source)

Soot: some polymers produce large amounts of soot when they burn

How can we change the polymers so they don't burn or burn poorly?