PEEK filled PTFE – A Useful Blend

The blending of polymers with additives is a common practice. There are very few materials that are used purely in their virgin form and PTFE is no exception here. Adding materials such a bronze, carbon and glass (to name but a few) have allowed us to augment the properties of PTFE to suit specific applications. In each case, we sacrifice some element of the original property of the PTFE, but enhance another. To take the case of bronze – the addition significantly increases the coefficient of friction of the PTFE and eliminates all electrical insulation properties. However, this is offset by a large and highly sought after increase in wear and hardness. Hence bronze filled PTFE is a preferred compound for a number of automotive and industrial applications.

In exploring what different additives do to the final properties of PTFE, we have found literature relating to materials such as those above, as well as less used additives such as molybdenum-di-sulphide, ekonol, stainless steel and graphite.

With the addition of PEEK, however, we find few sources with which to refer to on properties. While we do receive many requests for PEEK filled PTFE, the actual test data to support the compound is not easily obtained.

A 2006 paper titled: “A low friction and ultra-low wear rate PEEK/PTFE composite”, by David L. Burris, W. Gregory Sawyer, is all we have to refer to in this respect, but we will see that there are sufficient insights to help any OEM designer to assess the exact composition needed.

PTFE with PEEK fillers

We have come across a few applications where PEEK filled PTFE is the requested material. In most cases, what we receive is only a sample from the client. The light brown colour combined with the fact that the material “feels like”PTFE, is usually all we have to go with. Usually, the compound is used in sealing applications where high RPMs are involved.

Blending PEEK and PTFE

Unlike most other additives, PEEK blends with PTFE quite effortlessly. The lower particle size of PEEK (about 5microns against 25microns for PTFE) means that the grains of loose PEEK powder flow easily in between the PTFE grains and allow for a reasonably good blend. Further mixing is needed to ensure that the blend is uniform, but in our experience, it was less of a challenge to blend PEEK with PTFE than to blend pigments with PTFE.

Processing the material requires some minor fine tuning in the sintering cycle. However, when done properly, the resulting product is a very light brown that machines easily and offers some interesting properties.

Properties of PEEK filled PTFE

The paper by David L. Burris, W. Gregory Sawyer only looks into the wear and coefficient of friction of the blends of PEEK with PTFE. The paper looks at ratios (by weight) of 5%, 10%, 20%, 30%, 40%, 50% and 70%. The results obtained can be seen on the graphs below.

Coefficient of friction

Coefficient of Friction – PEEK filled PTFE

PTFE has a lower coefficient of friction than PEEK, so it would be reasonable to assume that the value keeps increasing with the addition of more PEEK. However, it is surprising to note that the coefficient is lowest at 50% of PEEK – at about 0.12.

It is important to mention than even at its lowest, the coefficient of friction is still much higher than for pure virgin PTFE(between 0.03-0.05). However, from a design standpoint, it is useful to know that adding a very small amount of PEEK is not the key to keeping the overall coefficient of friction as low as possible.

Wear resistance

Wear Resistance – PEEK filled PTFE

Again, given that virgin PEEK has better wear resistance when compared with virgin PTFE, we would assume that adding more PEEK keep improving this property. However, we again see that the best performing blend is PTFE+32% PEEK.

Conclusion

The above findings are useful from the point of view of grade selection. If an OEM wishes to design a seal using a combination that minimises the coefficient of friction and wear rates, they would be better off using a filler percentage close to 40%.

Charting the standards used in defining PTFE properties

It was recently brought to our notice by an astute client that the data quoted in many of the generic online sources did not give a complete picture of the values and correct test methods needed in checking the properties of PTFE.

A quick online search of a given property of PTFE churns out a number of data sheets from various supplier websites. And although the values and standards more or less match across these sources, our own study has revealed the following:

1. Some of the standards quoted are incorrect
2. The values quoted do not have any reference as many of the standards only specify the test method and not the value reference

As a result, with an obscure polymer like PTFE, we find that information has been carried forward from older data sheets and passed on until no one is very sure what the “correct” value is anymore. We ourselves have reached a dead-end on a number of metrics, but we have done our best to fill the gaps using verifiable data.

Let’s look at point (1) above. The most commonly quoted standard for PTFE is ASTM D 1457. We see this standard in a number of places and only after trying to buy a copy online were we informed that ASTM D 4894 had replaced the ASTM D 1457 in 2001.

Clients who – due to the effect of legacy – still refer to the ASTM D 1457 sometimes get upset when we send them test reports quoting ASTM D 4894 and it requires some discussion with their QA team before the new standard is accepted.

However, even the ASTM D 4894 only applies to virgin PTFE. For filled grades of PTFE, we refer to the ASTM D 4745. This again requires a discussion with the client as is especially problematic when the client orders a very specialized grade. Since the ASTM D 4745 only covers the more general filled grades of PTFE, clients who order an irregular grade feel frustrated that there is no standard pertaining to their requirement.

Both the standards, however, do provide some basic values of tensile strength, elongation and specific gravity, which help in checking whether the properties attained after testing are in line with the requirements.

However, as the table below shows, very few of the standards actually give any values. For a whole list of properties, the standards only tell you how to check the value, but do not make any recommendations on what those values should be. Furthermore, due to PTFEbeing a niche polymer, some of the standards – such as ASTM D 2240 – actually pertain to other materials and the test method is simply employed for PTFE.

	Virgin		Filled grades
	Standard	Value in standard	Standard	Value in standard
Density	ASTM D 4894	Yes	ASTM D 4745	Yes
Avg. Particle Size	ASTM D 4894	Yes	ASTM D 4894	Yes
Tensile Strength	ASTM D 4894	Yes	ASTM D 4745	Yes
Elongation at break	ASTM D 4894	Yes	ASTM D 4745	Yes
Shore D Hardness	ASTM D 2240	No	ASTM D 2240	No
Linear Expansion Coefficient (-50°C to +15°C)	ASTM E 831 / ASTM D 696	Yes (696)	ASTM E 831 / ASTM D 696	No
E-modulus (tensile)	ISO R 527	No	ISO R 527	No
Wear resistance (with Taber abraser method)	ASTM G 195-08	No	ASTM G 195-08	No
Deformation Under Load – Total deformation after 24H	ASTM D 621 A	No	ASTM D 621 A	No
Static Coefficient of friction	ASTM D 1894	No	ASTM D 1894	No
Dielectric Strength	ASTM D 149	No	ASTM D 149	No
Dieelectric Constant	ASTM D 150	No	ASTM D 150	No

As mentioned earlier, my client was curious to know what benchmarks were being followed when we quoted the values expected for each metric. However, we were unable to find any organisation that actively published data on PTFE and its filled grades.

In trying to trace back the values seen across so many data sheets (they are all in the same range, so we assumed they have some common source), we were able to find references old manuals released by DuPont, Dyneon and Daikin from where these values were obtained. Obviously, once we referenced DuPont, the client was satisfied and we were able to neatly define both the correct standard and the value with the proper reference.

It is however interesting to note that as widely used and accepted as PTFE is, there still does not exist any up-to-date properties standard that can be used by manufacturers as reference. The DuPont website does have values of virgin PTFE – but they reference the ASTM D 1457 – which suggests that maybe the information is dated. Not to say that the values would have changed significantly, but QA is a continuous process and something published within the last decade might offer a lot of support to both manufacturers and OEMs alike.

PEEK in India – A Growing Market with Many Challenges

At Poly Fluoro Ltd. we started our journey with PTFE and gradually expanded into other polymers. Initially, this was at the behest of existing customers, but over time our expertise in machining plastics meant that we were comfortable offering a variety of options to our clients, rather than try and force fit PTFE into their application.
We discovered the benefits of PEEK in one such exercise. Although we have already blogged extensively on the benefits and properties of PEEK, our own experience in dealing with this material serves to explain much of the commercial and technical queries surrounding this material.

PEEK in India is a small market in terms of volumes. The total consumption is only about 35 Tonnes. Of this, most of the material is imported as semi-finished rods and sheet, with only 12-15 Tonnes being processed from resin indigenously. Small as these numbers are, keep in mind that semi-finished PEEK sells at anywhere between US$275-US$400 per Kg – so in value terms, the market is not as small as the volumes suggest. Nonetheless, it is very much a niche market – even among speciality polymers.

Being present in the PEEK market as a processor poses many challenges. Some of these are technical in nature, while others relate to the commercial issue (PEEK is very expensive) and how clients respond to PEEK. Again, we have touched on some of these points in our earlier article – but as we have delved deeper into PEEK processing, many new findings have arisen.

Compression moulding PEEK not a simple affair

There are many challenges in compression moulding PEEK and most of these do not get explicitly highlighted in manuals and guidebooks. In most manuals, the process is outlined in 5-6 basic steps, which at first glance make PEEK appear a very friendly material to deal with.

In reality, the process is time-consuming, highly sensitive to the exact process needed and very specific in the type of tooling required.

The benefit of compression moulding PEEK over, say extrusion is that we are able to make customized dimensions based on the customer drawings. The stock piece for a part measuring 70mm in diameter can be moulded as 72mm, rather than using a 75mm rod. Over a 50mm length, this saves almost 25 Grams per part – which is significant when we consider the cost per Kg. Furthermore, if the part has an internal diameter the saving is even more, as the same cannot be attained in extrusion for large diameters.

However, against this saving, the time consumed to make a 50mm part would be many times what extrusion would take. Compression moulding is known for low productivity and even a large processor is only able to consume 20-25 Kgs per day of production. In India, however, where labour is inexpensive, this is not a huge cost factor – it only limits volumes. And since PEEK is still a low volume polymer – even processing 4-5 Kgs a day can be significant.

The actual process of compression moulding PEEK is also not straightforward. The 5-6 steps mentioned in the manuals each contain nuances that need to be fine tuned until you reach a process that most suits the equipment available. In our own experience, we have found that over 25-30 trials had to be taken, each using up between 250-800 Grams of resin. After each trial, some parameters were changed before taking another trial. Parameters such as pressure, peak temperature and soak time all need to be varied to control issue such as porosity, cracking, black spots and cold spots.

In addition to this, the selection of dies is critical. PEEK, in its molten form can be a very aggressive material and we have had many steel dies get corroded during moulding. Again – finding a balance between a strong die metal and the correct process is critical in obtaining a final process that is both economical and productive and which yields a high quality final product.

Variants and substitutes do exist for the price conscious

We have had some success in blending PTFE with PEEK ratios of 5%, 10% and 15% by weight (ie: PTFE+5/10/15% PEEK). Again – the process of blending is not straightforward and the PTFE itself needs to be processed slightly differently owing to the fact that PEEK melts at a higher temperature than PTFE. However, the final blend has proven to be useful in applications involving sealing and needing high wear resistance, with a low coefficient of friction.

Another alternative to PEEK is PEK. PEK is very similar to PEEK and is processed in much the same way. As far as properties go, some have even suggested it is slightly superior on some parameters. Commercially, it is roughly half the price of PEEK – which makes it a very tempting alternative. However, PEK is still being proven in OEM applications, whereas PEEK has been around long enough to give any OEM designer confidence in its properties.

Marketing PEEK is a challenge

In a market like India – which is highly price sensitive – PEEK is a difficult product to win customers over with.

PEEK is usually the last choice of any OEM due to its price, and if someone has not come across the material before, it takes some educating before they are convinced that any polymer exists at such a price. And while PEEK is well established in the West – in India, it is still very nascent in comparison and clients do not always see the long-term benefits of using it.

Furthermore, the relatively recent introduction of PEK into India is threatening to take some of the long-term market share from PEEK, as in a price sensitive market, people may be willing to make the gamble on a cheaper substitute.

Applications and Considerations for PTFE Seals

As a sealing element, PTFE has proven itself many times over. PTFE is used in seals because it encompasses all the properties essential for a good sealing element, mainly:

• High wear resistance
• Low coefficient of friction
• Moderate hardness (allowing for better overall mating with metal parts)
• Durability – both with temperature as well as corrosion

While these properties are not new to us, every material has a limit to how much it can withstand. Furthermore, every grade of PTFE offers something different to the sealing application. Understanding these limits and differences gives us a better understanding into choosing and applying PTFE seals to best suit the requirement.

Sealing is vital to almost any mechanical assembly. It serves to both retain fluid within the assembly and allows the assembly to function freely. A good sealing material – such as PTFE, needs to be elastic enough to close gaps and assist with the fluid retention while strong enough to take the wear load applied on in by (usually) metal mating parts. Still, within any assembly, there is likely to be some trade off between fluid retention and durability, and this is where the choice of grade becomes important. Typically, the following metrics needs to be studied:

Surface Finish

PTFE wears off in layers, and will usually deposit a coating on the mating surface. In general, it is easy to attain a surface finish of as high as Ra < 0.4 on a virgin PTFE part. However, once we introduce other materials such as glass, carbon, graphite or bronze into the mix, there is a huge drop in the finish. We have successfully attained a finish of Ra < 1.2 on PTFE+15% Glass seals – but going below this is always a challenge.

For the mating part, the surface finish is somewhat more important – as it is usually a metal can wear the PTFE out significantly faster if not properly finished. When the metal surface is rough, more wear occurs until the crevices and valleys within the metal are filled with PTFE. PTFE will wear in direct proportion to the surface finish. Testing shows that the life of the seal is doubled when the finish is improved from 16rms to 8rms.

Surface finish also affects the sealing ability of PTFE. A rough finish creates a microscopic “line of sight” channels allowing a flow path through mating parts. Hence, when sealing gases with small molecules, such as, hydrogen, helium, or oxygen, a 2-4 RMS is highly recommended.

Hardness

When the mating part is hardened (via heat treatment or plating), there is a significant improvement in the life of the seal. Typically, when a hard and soft surface are in contact, there is an exchange of ions, which can lead to adhesion. This reduces the effectiveness of the seal. Improving the surface hardness of the metal part can control the adhesion.

PV Value

PV is an often-quoted metric for all PTFE grades. It offers a trade-off between the pressure that the PTFE can take, against the speed at which the mating part is sliding against the PTFE.  Understanding PV is key to understating whether the PTFE grade being considered at would be able to withstand the combination of load and RPM involved.

Disregarding PV values would almost certainly lead to a failure in the seal to perform. We have received many requests to look into the replacement of standard phosphor-bronze bushings, bearings and seal with PTFE grades. In most cases, PTFE looks to be a perfect substitute along most metrics. However, when we look at the pressure it can withstand under high RPMs, PTFE is not always suitable.

Types of seals

Given the diversity in automotive and mechanical applications, a number of different PTFE seal dimensions have been developed – each with it’s own unique property. When we cross these dimensions with the different PTFE grades, we end up with potentially hundreds of seals. Thus, choosing the right seal is important and a lot of thought needs to go into the same, before a decision is made.

The spring-energised seal is a sealing device consisting of a PTFE ‘energized’ by a corrosion resistant metal spring.  Put simply – as PTFE is a soft material, it can be easily deformed by the metal parts surrounding it. The spring acts as a strengthening medium – allowing the PTFE to take loads while also applying force on the sealing surfaces to create a tighter fit and ensure no leakages. The spring also provides resiliency to compensate for seal wear, gland misalignment or eccentricity.

Types of such spring energised seals include:

Finger Spring:

This is mainly used in dynamic applications, has good sealing and a low coefficient of friction. It is recommended for surface speeds up to 250ft/min.

Coil Spring:

This is designed for more static or slow dynamic applications. It is not as flexible as the finger design – owing to the fact that the spring is coiled and more rigid as a result. However, it is significantly better than the finger design in sealing – due to the uniform pressure applied on all sides by the coil spring.

Double Coil Spring:

A more augmented version of the single coil – this is designed for purely static applications, such as cryogenics. The increased load applied by the double coil significantly improves sealing ability.

O-ring Energised:

This can be used in both static and dynamic applications and offers a good balance between the seal-ability of the coil energised seal and the flexibility of the finger spring. It is typically incorporated in areas where metallic springs cannot be used due to compatibility issues.

Rotary Lip Seals

Lip seals are used primarily to seal rotary elements such as shafts and bores. They provide a self-lubricating medium between (usually) two metal elements – allowing for both smooth rotation and good sealing. Common examples include strut seals, hydraulic pump seals, axle seals, power steering seals, and valve stem seals.

Lip seals may be designed with or without springs – depending on the application.

The examples shown above are merely indicative of the basic designs available in PTFE seals. In truth, each of the above types of seals may be expanded into many variants, depending on the exact requirements of the mating elements involved in the OEM designs. Furthermore, each may be provided in any of a number of grades of PTFE compounds available.

Choosing a PTFE compound for your PTFE seals

The grade of PTFE is a critical choice in the design of the seal. We have touched elsewhere on the variants and properties offered by the commonly used fillers in PTFE. In a nutshell – glass offers stiffness and creep resistance; bronze and molybdenum di sulphide offer wear resistance, but increase the coefficient of friction; carbon and graphite offer wear resistance and dimensional stability.

In our experience, a mixture of glass and molybdenum di sulphide offers the ideal sealing properties for most applications. However – the exact grade is usually a choice made by the OEM, based on what information we are able to provide.

PTFE Compounds and their effects

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We have spent a significant amount of time looking at PTFE as a material, comparing it to other materials and analyzing its uses based on the various properties it exhibits.

However, our focus has been purely on “virgin” PTFE – namely, PTFE in its pure form. In this form, PTFE takes on an opaque-white hue, is best describes as a soft-waxy material and is smooth to the touch.

Compounding PTFE refers to the mixture of PTFE with additives, which would both add and remove certain characteristics from virgin PTFE. It is essentially a mixture of PTFE with other substances – done for the purpose of enhancing one or more of the characteristics of PTFE, so that the compounded material would be a better overall fit to a given application.

Compounding Process

Before we delve into the various compounds, let’s look briefly at the process behind PTFE compounds.

In truth – most of the large resin manufacturers (DuPont, Daikin, Solvay etc.) have focused on manufacturing virgin resins and left the compounding to smaller companies – who buy the virgin resin and use it in making their compounds. Although the compounder is very much the owner of the product’s quality – it must be mentioned that the input resin does have a huge impact on the final quality of the compounded grade.

For example – we had procured a large quantity of PTFE+Bronze resin from a Chinese company, only to find that when we moulded large pieces from the resin (in excess of 15-20 Kgs per piece) – the pieces would crack during sintering. When we took it up with the supplier, it became apparent that the base resin was of a poor quality, and unsuitable for large pieces.

The compounding process is usually a proprietary technology of the compounder. However, technical literature will point to one of two ways to compound resin:

1. - Physical blending – a physical process, done in an industrial blender where PTFE and the additives are added in the required proportion. The blended powder is then sifted through a mesh to separate the mixture from ‘lumps’ of PTFE that tend to form during blending. The process is repeated until all lumps are suitable removed.

Blending like this is a tedious process, and requires much iteration. Even when care has been taken, small lumps may still remain which will result in patches of white (assuming the blend is pigmented) on the final product.

- Chemical blending – this is more expensive, but also ensures fewer iterations and more uniformity in the blend. A range of chemicals is available for this process – but the basic principal is to have a liquid aid with a lower surface energy than PTFE. This will allow the pigment to flow in between the PTFE molecules so that even the lumps are suitably coated with the pigment.

However, the finer aspects of compounding are usually learnt only through experience and remain a technology that compounders would not part with easily (understandably!).

Properties of PTFE

We have looked at these before from a theoretical standpoint. Some of the properties remain unaffected (or hindered) by the addition of fillers, while others are impacted positively.

Temperature Resistance

It would be sufficient to say that compounded grades have to have at least, if not higher temperature resistance than PTFE – as else they would not survive the sintering process – which happens at 350-400 °C

Dielectric Strength

In most cases, this is only reduced by the addition of fillers – as PTFE in its virgin form shows exceptional electrical resistance. We have yet to come across an application where a filled grade of PTFE is used for purely insulation purposes

Hardness

Being a soft material, the addition of fillers can greatly increase the hardness. This is especially sought after in PTFE components – where the softness of the material can lead to deformation in the long run, affecting the overall assembly within which the component is used.

Coefficient of Friction

Like with dielectric strength, the dynamic coefficient is usually hindered with the addition of fillers. However, because virgin PTFE exhibits significant creep – there is a case for filled grades in applications with minimum movement where a low static coefficient of friction is required.

PV Value

The PV value of a compound is the product of the unit load P (MPa) on the projected area and the surface velocity V. The PV of PTFE is usually enhanced by the addition of fillers.

Wear

In general, the addition of fillers to PTFE resins improves wear resistance but reduces abrasive resistance by providing discontinuities in the PTFE resin which can be entered by sharp practices that may tear the material.

Moisture Absorption

Unfilled PTFE does not absorb water. Filled PTFE compounds absorb small amounts of moisture. Since PTFE resin and fillers are not hygroscopic, any moisture picked up simply fills the voids. Extent of pickup is so small that the dimensional stability is essentially unaltered.

Chemical Resistance

Again – given PTFE is unmatched amongst other materials in its ability to remain intern to chemicals, adding fillers can only reduce this property. However, it does depend ultimately on the application and whether there is a requirement for such a high level of inertness. Typically however, for applications needing this property (medical, labwares etc.) – virgin PTFE remains the preferred choice.

Standard Compounds

Now that we have looked at each of the properties, let’s look at some of the standard compounds and see how each compound alters the characteristics.

Glass Fiber

This is the most universally used PTFE filler and is normally mixed in either 15% or 25% ratios. Glass is itself highly resistant to chemicals and also exhibits very good dielectric properties; add to this the added mechanical properties and creep resistance that it provides and it’s not difficult to see why it is so sought after.

Glass fiber also offers improved wear resistance, but reduces the coefficient of friction. Furthermore, it imposes a higher wear rate on the tools while machining– making it a slightly more expensive material to machine. For the same reason, it is very difficult to ‘skive’ glass filled PTFE tapes to thicknesses of under 0.25mm – as the wear induced on the skiving blade renders the blade dull before a significant length can be skived.

Carbon-Graphite

Graphite is generally used in compounds destined for chemical and mechanical service. Graphite reduces initial wear and provides general strengthening characteristics to the composition. Also, graphite compounds generally display high load carrying capabilities in high-speed rubbing contact applications and exhibits the highest hardness of any of the compounds.

Of all the compounds, we have found Carbon-Graphite to wear out tools the fastest. The same tool that might give 200-300 components if done in virgin PTFE, will only give 15-20 components in Carbon-Graphite.

Bronze

Bronze is usually mixed in a 40% or 60% ratio. Bronze compounds have higher hardness, lower wear, higher comprehensive strength, better dimensional stability, higher thermal conductivity, lower creep and cold flow than most other compounds.

However, test data shows that bronze compounds are not suited to many electrical applications or to those that involve corrosive service environments.

Molybdenum Disulfide

MoS2 adds substantially to the hardness, stiffness and wear resistance of PTFE resins. It reduces starting friction and has little effect on PTFE 's electrical and chemical properties. Generally, only small amounts of molybdenum disulfide are used, most often in conjunction with complementary fillers (usually bronze or glass).

In addition to the above fillers, we have used fillers of ceramic, stainless steel and ekonol. Many branded compounds of PTFE continue to exist (eg: Rulon, Turcite etc) – but a comparison of properties shows that there is little difference between the branded compounds and one of the regular grades.

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Ultimately, choosing a compounded grade is a question of application – asking which property needs to be enhanced and which can be foregone (or compromised on). In most mechanical applications, it becomes a trade-off between higher mechanical properties (hardness, wear resistance, creep) and lower coefficient of friction.

It should be noted than very rarely does cost play a huge decider in choosing a compounded grade. While historically, bronze has been most expensive, followed by glass and then carbon-graphite (virgin PTFE has usually been priced around the same level as carbon-graphite) – their properties are so different that the end user rarely sees them as substitutes.

To know more, please view our site: www.polyfluoroltd.com; or view our PTFE (Teflon) Manual