In the world of engineering polymers, plastics capable of withstanding temperatures above 150°C come at a price. While Polyamides, POM (Delrin®), and PVDF (Kynar®) are all well suited to temperatures within this barrier, when we look beyond we find the options become rather expensive.
Polymers that can accommodate higher temperatures, such as PTFE, PEEK and Polyimides tend to be in the range of 3x-20x the price of lesser plastics. As a result, the cost implications of designing a system using high-temperature polymers are significant.
What do we mean by high-temperature polymer?
While the phrase seems fairly self-explanatory, high-temperature polymers need to be further evaluated to understand exactly how they behave. Usually, an OEM or product designer will look for the continuous service temperature to assure themselves that a part made using the polymer can withstand the conditions it will be subjected to.
| Polymer | Common Brand Name | Glass Transition Temperature (°C) | Continuous Service Temperature (°C) | Melting Point (°C) |
| PTFE | Teflon® | -20 | 260 | 375 |
| PEEK | Victrex®/Ketaspire® | 150 | 250 | 340 |
| Polyimide (PI) | Kapton® | 400 | 450 | NA |
| Polyetherimide (PEI) | Ultem® | 220 | 185 | 250 |
| Polysulfone (PSU) | Udel® | 190 | 170 | 350 |
| Polyphenylsulfone (PPSU) | Radel® | 220 | 180 | 370 |
However, for the component manufacturer, the service temperature is less relevant than the melting point and the glass transition temperature of the material. This is because these are the temperatures that directly impact the production of the component – both in molding as well as machining. We will be focusing here on glass transition temperatures and trying to understand how this metric needs to be used in component design and manufacture.
What is glass transition?
Put simply, a material moves from crystalline to amorphous states beyond its glass transition temperature. All polymers, when in a crystalline state, have internal stresses that keep it dimensionally stable. These stresses are a culmination of the inherent molecular arrangement of the molded shape and further stresses lent to it during the machining stage. Heating the part above the glass transition point causes the molecules to realign, thereby relieving the stresses and causing dimensional changes to the part. As stress due to machining can be significant, most polymers are subjected to an annealing cycle prior to machining, to ensure that the stress build up does not cause the part to crack during the process. Polymers such as PEEK will crack under so little as a simple turning operation of not annealed beforehand.
The stresses are very relevant for machined components, as it ensures that machined parts subjected to temperatures within their glass transition point will not deviate dimensionally. However, it is equally true that in the event of higher temperatures, the deviation may result in part failure. This is typically the case for highly machined components.
Consideration for Dimensional Stability
Our experience with dimensional stability rests around the use of PTFE and PEEK. Both polymers behave very differently both during machining and after. We shall look at them one by one.
PTFE
Among high temperature polymers, PTFE is unique in that it has a glass transition temperature under 0°C. The implication of this is that PTFE is generally amorphous even at room temperature and therefore does not suffer the internal stresses that other polymers do. As a result, PTFE typically does not require annealing, although it is still done as a means to improve the hardness of the material. No internal stresses mean that the material undergoes minimal duress during machining and any cracking of the machined part is avoided.
The flip side of this property is that PTFE has a very weak dimensional stability when subject to applications where a high range in temperatures may be present. While PTFE can easily withstand high temperatures, close tolerances would need to be abandoned when subjecting it to these conditions as the material itself experiences an up to 3% deviation in linear dimensions between 0 and 100°C.
So although PTFE is capable of surviving the harshest of environments, a PTFE part machined with close tolerances is usually employed only in areas where the temperature, while high, must remain range bound within +/-15°C.
PEEK
In contrast to PTFE, achieving close dimensional tolerances in PEEK and difficult due to the constant build up of stress during machining. In our own experience, PEEK parts may sometimes need to be annealed multiple times to ensure that after each stage of machining, the internal stresses are adequately relieved so that the part does not crack/deform after the next stage.
Unlike PTFE, which constantly gives off heat as it is applied to it, PEEK needs external help in cooling it down. As a result, the use of a coolant is common in PEEK machining and helps reduce the extent of stress induced in the part.
Finally, while close tolerances of up to +/-0.01mm have been achieved on PEEK parts, there is no guarantee these tolerances will be retained should the part be subjected to a temperature above its glass transition point during application. In such an event, stresses induced during the final operation of machining will relieve themselves and cause the molecules within the PEEK material to realign slightly, causing dimensional deviations in the part.
So given the above hazards, why are PTFE and PEEK still so widely used? One reason is that there exist very few applications where strict dimensional stability in temperatures above 200°C are a co-requisite. Hence, we have applications of high temperature where the dimensional tolerances tend to be very lax and we have applications with tight machining tolerances, where the part may experience a maximum temperature of only 150-160°C.
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