Unravelling Polymers

The Definitive Blog on Polymers by Poly Fluoro Ltd.

Exploring the Polymer Cousins of PTFE: ETFE, PCTFE, and ECTFE

When PTFE was developed back in the sixties, it quickly became one of the most versatile polymers. Thermal resistance, chemical resistance, electrical resistance, and a coefficient of friction that made it virtually irreplaceable in applications requiring wear resistance or sliding movements. However, as the industry has evolved, specialised applications have called for polymers with ever more specific properties.

High-performance fluoropolymers like ETFE (Ethylene Tetrafluoroethylene), PCTFE (Polychlorotrifluoroethylene), and ECTFE (Ethylene Chlorotrifluoroethylene) have become indispensable in industries that demand chemical resistance, thermal stability, and excellent electrical insulation. While they share a fluorinated backbone, each has unique properties that tailor them to specific applications. Although similar to PTFE, they have each carved a niche for themselves in the polymer space.


1. ETFE (Ethylene Tetrafluoroethylene)

Properties

ETFE is a copolymer of ethylene and tetrafluoroethylene, boasting impressive mechanical toughness and chemical resistance. Compared to PTFE, it has slightly lower chemical resistance but significantly better impact strength and radiation resistance.

  • Melting point: ~270°C

  • Tensile strength: ~40 MPa

  • Elongation at break: >300%

  • Dielectric strength: Excellent

  • Transparency: High light transmission (up to 95%)

  • Weatherability: Exceptional UV and radiation resistance

  • Friction coefficient: Low

These properties make ETFE ideal for outdoor and high-impact applications.

Processing

Unlike PTFE, ETFE is melt-processable, allowing for standard thermoplastic processing techniques such as:

  • Extrusion

  • Injection molding

  • Blow molding

  • Rotational molding

It is often extruded into films or sheets and can be thermoformed or welded. Adhesion to other materials can be challenging and often requires surface treatments like plasma or chemical etching.

Applications

ETFE is well known for its use in architectural applications—particularly as a lightweight, translucent cladding material. Other uses include:

  • Architectural membranes (e.g., Allianz Arena, Eden Project)

  • Wire and cable insulation for aerospace and electronics

  • Tubing and liners in chemical processing

  • Greenhouse films due to its UV permeability and strength

  • Automotive fuel line coatings


2. PCTFE (Polychlorotrifluoroethylene)

Properties

PCTFE is a homopolymer of chlorotrifluoroethylene (CTFE) and is characterized by its low moisture absorption and excellent dimensional stability. The presence of chlorine gives it unique performance characteristics compared to other fluoropolymers.

  • Melting point: ~210–215°C

  • Tensile strength: 34–45 MPa

  • Water vapor transmission rate (WVTR): Extremely low

  • Gas permeability: Very low

  • Transparency: Good optical clarity

  • Flame resistance: Non-flammable

  • Chemical resistance: Excellent, but less so than PTFE

Its low permeability to gases and moisture makes it a favored choice in vacuum systems and cryogenics.

Processing

PCTFE is melt-processable and can be shaped using:

  • Injection molding

  • Compression molding

  • Extrusion

However, it has a narrower processing window than ETFE or ECTFE and requires careful control of temperature to avoid degradation.

Applications

Thanks to its barrier properties, PCTFE is ideal in critical packaging and sealing environments:

  • Pharmaceutical blister packaging where moisture resistance is crucial

  • Cryogenic seals and gaskets (used down to -200°C)

  • Semiconductor equipment for low-outgassing properties

  • Aerospace: seals and insulators

  • Optical lenses and coatings


3. ECTFE (Ethylene Chlorotrifluoroethylene)

Properties

ECTFE is a copolymer of ethylene and chlorotrifluoroethylene. It sits between ETFE and PCTFE in terms of chemical resistance and mechanical strength. ECTFE offers a balanced combination of thermal stability, electrical insulation, and outstanding chemical resistance, especially to strong acids and alkalis.

  • Melting point: ~240°C

  • Tensile strength: ~50 MPa

  • Elongation at break: ~300%

  • UV and weather resistance: Good

  • Chemical resistance: Excellent, especially to chlorinated and oxidizing agents

  • Flame resistance: V-0 rating (UL94)

  • Permeability: Low for gases and liquids

ECTFE maintains its properties over a wide temperature range (-76°C to +150°C), making it suitable for harsh environments.

Processing

ECTFE is melt-processable and works well with standard thermoplastic forming methods:

  • Extrusion: for pipes, tubes, and films

  • Injection molding: for fittings and components

  • Rotational lining: for corrosion-resistant linings in tanks and reactors

  • Welding: high-quality weld joints are possible

Like ETFE, ECTFE may require surface pre-treatment for adhesive bonding.

Applications

ECTFE is preferred where both high chemical resistance and structural integrity are required:

  • Chemical processing equipment linings

  • Scrubber linings for flue gas desulfurization systems

  • Wire insulation in corrosive environments

  • Semiconductor wet benches

  • Battery separators and components in energy storage

  • Protective films for photovoltaic panels and electronics


Comparative Summary of Key Fluoropolymers

Property

ETFE

PCTFE

ECTFE

PTFE

Tensile Strength (MPa)

40–50

34–45

45–55

20–30

Elongation at Break (%)

300–400

100–200

200–300

200–500

Specific Gravity

1.70

2.10–2.15

1.67

2.13–2.20

Young’s Modulus (MPa)

1000–1400

1400–1800

1000–1300

400–800

Temperature Range (°C)

-185 to +150

-240 to +150

-76 to +150

-200 to +260

UV Resistance

Excellent

Moderate

Good

Excellent

Moisture Barrier

Moderate

Excellent

High

Excellent

Chemical Resistance

Very Good

Excellent

Excellent

Outstanding

Flame Resistance

Good

Excellent

Excellent (UL94 V-0)

Excellent (non-flammable)

Processability

Melt-processable

Melt-processable

Melt-processable

Non-melt-processable


Conclusion

ETFE, PCTFE, and ECTFE each serve critical roles in specialized industries. Whether it's ETFE’s light transmission and durability in modern architecture, PCTFE’s moisture resistance in cryogenic and pharmaceutical packaging, or ECTFE’s chemical inertness in corrosive chemical processing environments, these materials provide reliable performance under extreme conditions.

As industries continue pushing for lighter, more durable, and chemically resilient materials, these fluoropolymers are likely to see expanded use—especially in emerging fields like hydrogen energy, medical devices, and next-generation electronics.


1. Multi Layered Ptfe Bellows - A True Feat in Both Precision Moulding and Machining

2. Understanding Polyamide: A Versatile Engineering Polymer

3. Crystalline vs. Amorphous Polymers: Structural Overview

Multi Layered Ptfe Bellows - A True Feat in Both Precision Moulding and Machining

Introduction

Machining PTFE bellows has always been as much an art as a science. Because of the nature of PTFE as a non-injection mouldable polymer, the only option is to mould a rod or bush and have a tool that creates alternate grooves on the inside and outside, giving the bellow shape needed. Even a small offset in the movement of the tool will result in a bellow where the wall thickness becomes increasingly uneven as the tool makes subsequent cuts.  

The development of PTFE bellows with three distinct layers - PTFE+15% Polyimide at both ends and virgin modified PTFE in the middle—presents a unique challenge in both compression molding and machining. 

This case study explores the intricate process of creating these specialized bellows, detailing the difficulties encountered and the innovative solutions that enabled us to achieve the required specifications with a tolerance of within 1mm.

Challenges in Compression Molding

Molding PTFE with three different layers is an intricate task that demands extreme precision. Unlike homogeneous PTFE components, the layering process necessitates meticulous control to ensure clear demarcation between the materials. The polyimide-filled PTFE at both ends provides enhanced wear resistance and mechanical strength, while the virgin modified PTFE in the middle section offers superior flexibility for the bellow function.

One of the primary difficulties is achieving a distinct joint between each layer. During compression molding, the pressure must be carefully regulated to prevent blending of the materials. If the pressure is too high, the interface between layers can become indistinct, leading to inconsistent performance. Conversely, if the pressure is too low, the adhesion between layers may be insufficient, compromising structural integrity. Similarly, any play in the alignment between the compression moulding dies will result in a slant, meaning a part that is visually uneven and therefore cannot be used.

Another critical challenge is maintaining the correct thickness of each section. The distance between the two PTFE+15% Polyimide layers is strictly defined, requiring exact placement of each material during molding. Achieving this tolerance within 1mm has been particularly difficult, as slight variations in powder distribution, compaction, or sintering can lead to non-conforming parts. However, through continuous optimization of the molding process—including precise measurement of powder distribution and controlled sintering cycles—we have successfully maintained the required tolerances while minimizing rejections.

Complicating this further is the fact that Polyimide is prohibitively expensive. PTFE+15% PI costs nearly 5 times as much as regular modified PTFE. Considering that any bush we mould needs an additional 10-15mm of holding space (which will eventually be disposed of as scrap), making this holding area with PTFE+15% PI is commercially wasteful. Hence, the bellow requires a 4th layer – one with regular PTFE, that is considerably cheaper.

Each layer needs to be of a specific thickness, with only some leeway on the last holding layer. 

Machining Complexities

Once the multi-layered PTFE billet is molded and sintered, machining the final bellow shape presents a new set of challenges. The machining process requires precise positioning of the tool to ensure that both ends (PTFE+15% PI) are threaded while the middle section, made of virgin modified PTFE, forms the bellow’s main functional body.

The difference in material grades complicates the machining process. PTFE+15% Polyimide is harder and more abrasive than virgin modified PTFE, leading to variations in tool wear and cutting behavior. A standard cutting tool would struggle to accommodate these differences, resulting in uneven machining or excessive wear. To overcome this, we developed a specialized high-speed steel (HSS) tool designed specifically for this application. This tool provides superior durability while ensuring smooth transitions between the different material layers.

Positioning and securing the part during machining is another significant challenge. The part must be clamped firmly to prevent any movement that could distort the fine details of the bellow structure. At the same time, excessive clamping force could deform the relatively soft PTFE material. To address this, we developed a customized fixture that securely holds the part without introducing unwanted stress or distortion.

Precision and Efficiency

Each PTFE bellow takes close to an hour to complete, given the precision required in both molding and machining. The time-consuming nature of the process is necessary to ensure high-quality results and compliance with stringent specifications. Despite the extended production time, our refined methodology has allowed us to improve yield rates and maintain consistency across batches.

By optimizing both the compression molding and machining stages, we have successfully produced PTFE bellows that meet all functional and dimensional requirements. The ability to maintain a tolerance within 1mm ensures that the final product performs reliably in its intended application, whether in chemical processing, semiconductor manufacturing, or other demanding industries.

Conclusion

Developing a three-layer PTFE bellow requires expertise in both material science, manual moulding, and precision engineering. The challenges of achieving distinct layer separation during compression molding and accommodating different material behaviors during machining were significant, but through careful process refinement, we have successfully overcome these hurdles. Our ability to manufacture these complex components with high precision reinforces our expertise in high-performance polymer solutions, ensuring that our clients receive products of the highest quality and reliability.


Read More

1. Understanding Polyamide: A Versatile Engineering Polymer

2. Crystalline vs. Amorphous Polymers: Structural Overview

3. Exploring Polyetherimide (PEI) - The No Fuss Polymer

Case Study: PEEK Gears - Evolution in High-precision Machining Capabilities

Introduction

In the realm of high-performance engineering plastics, PEEK (Polyether Ether Ketone) stands out for its exceptional mechanical properties, chemical resistance, and high thermal stability. However, machining PEEK – or indeed any polymer - to extremely tight tolerances presents significant challenges. The nature of the polymer, combined with external factors such as the use of coolants, the material of the tools, and even the post-machining environment, causes the material to misbehave. As a result, expecting tolerances within 50 microns becomes challenging.

We were approached by a client to manufacture specialized PEEK gears with a required tolerance of 0.01mm (10 microns). Given that polymers typically struggle to maintain such tight tolerances, this was a formidable challenge that required innovation in tooling, machining strategies, and metrology.

The Challenge

The primary challenge was achieving and consistently maintaining the required 0.01mm tolerance. The key hurdles we encountered were:

  1. Material Limitations: PEEK, despite its excellent mechanical properties, exhibits thermal expansion and elasticity, making it difficult to achieve stable machining tolerances.

  2. Erratic Machining Results: Initial CNC machining trials produced inconsistent results. Some gears met the required tolerances, while others deviated beyond acceptable limits.

  3. Metrology Complexity: Standard measurement tools were inadequate for accurately gauging the fine tolerances and runout required for the gears.

  4. Tooling and Setup: Conventional machining tools and methods were not providing the repeatability and accuracy required for this project.

The Solution

To overcome these challenges, we took a multi-faceted approach:

1. Developing Special Gauges for Measurement

Measuring tolerances at the micron level required specialized metrology. Standard callipers and micrometers were insufficient due to their limitations in precision and the difficulty of measuring polymer components without deformation. Our VMS equipment – which has a least count of 3 microns – was able to measure the part, but the process was time consuming. We developed custom gauges and used high-precision coordinate measuring machines (CMM) to accurately assess dimensions and runout. This ensured that we could reliably validate the tolerances achieved during machining.

2. Optimizing the CNC Machining Process

To address the erratic results from our initial trials, we experimented with various machining strategies and tools. We identified several key improvements:

  • Using Special Tooling: We sourced and developed special cutting tools with optimized geometries to reduce tool deflection and wear. Carbide and diamond-coated tools were used to ensure minimal wear and improved cutting precision.

  • Controlling Machining Parameters: We fine-tuned cutting speeds, feed rates, and toolpath strategies to minimize thermal expansion effects. Slow, precise cuts with controlled cooling helped maintain dimensional stability.

  • Using Our 5-Axis CNC Machine: A critical breakthrough came from leveraging our advanced 5-axis CNC machine. This allowed for better control over the machining angles, reduced setup errors, and enabled us to achieve highly precise and repeatable results.

3. Process Validation and Iterative Improvement

Once we identified the optimal machining strategy, we performed multiple validation runs to ensure process stability. Each gear was carefully measured using our custom gauges and CMM, allowing us to refine the process further. Over time, we were able to achieve consistent results, meeting the stringent 10-micron tolerance requirement.

The Outcome

Through our systematic approach to overcoming machining and metrology challenges, we successfully manufactured PEEK gears with the required 0.01mm tolerance. This achievement positions us as a leader in precision polymer machining. While the industry norm for polymer machining tolerances is typically around 50 microns, we have demonstrated the ability to achieve and maintain 10-micron tolerances consistently.

Conclusion

This project provided us with deeper insights into the machinability of PEEK and the factors influencing dimensional stability. By investing in specialized tooling, high-precision metrology, and leveraging our 5-axis CNC capabilities, we have set a new benchmark for precision polymer machining. The knowledge gained through this project will not only benefit future PEEK machining applications but also enhance our overall capabilities in high-precision polymer components for demanding industries such as aerospace, medical, and semiconductor manufacturing.


Read More

1. Case Study - PVDF Compression Moulding

2. Case Study - PEEK in Coffee Machines

3. Short Neutral Section Development for Railway Applications : Case Study