Additive Manufacturing: High Performance Polymers including Poly Aryl Ether Ketones (PAEKs)

CALM is a leading centre of excellence for Additive Manufacturing working with High Performance Polymers including Poly Aryl Ether Ketones (PAEKs). The PAEK family of polymers, including PEEK, PEK and PEKK, are high performance polymers offering good mechanical performance combined with high resistance to corrosion and are biocompatible.

CALM is the only independent centre worldwide researching laser sintering of high temperature and high performance engineering polymers and composites using both the commercial high temperature laser sintering platform EOS P 800 and EOS P 810.

We have been researching PAEK materials for AM since 2011 and we are working with powder bed and extrusion deposition technologies tailoring existing materials and developing new ones. In 2018, the group signed a 5 year joint research collaboration with Victrex to exploit the full potential of high-performance PAEK polymers in Additive Manufacturing. 

Research projects include:

Combining nano-particles with PAEK polymers, this project is looking to develop new bespoke lightweight multifunctional materials that can be 3D printed using powder bed fusion technology and FFF. PAEK polymers are temperature resistant, tough, and corrosion resistant. They are increasingly being used for metal replacement within aviation and military application.

Boron nitride and graphene have been selected as the nano-materials most suited for the intended applications here. These new materials will offer multifunctional capabilities including lightweighting, thermal and electro-magnetic properties. Incorporation of nanomaterials with different particle sizes and shape which will significantly affect powder flow, polymer viscosity and subsequently sintering mechanisms are very important to the success of this project.

The project will study the surface chemistry of the nanoparticles for good interface bonding with PAEK; fabrication of the composite powder (encapsulation of the nanoparticles either on the surface or within the bulk of the PAEK particles) and laser sintering of these new powders. Powder properties (bulk density, compaction, shape - roundness and circularity, aspect ratio, viscosity, surface tension) are key parameters for a good sintering process,

Funded by: Innovate UK

Partners: Qioptiq Ltd, Thales UK Ltd, Victrex Manufacturing Ltd, Hosokawa Micron Ltd, Airbus Operations Ltd, 2-DTech Ltd, Haydale Ltd

SEM image of Graphene-PEEK structure

CALM in partnership with Bond 3D are co-funding a PhD studentship seeking to investigate polymer behaviour and performance of Poly Ether Ether Ketone (PEEK) polymers. Bond 3D is a fast growing, young and entrepreneurial company based in the Netherlands who are developing a novel, ultra-performance Free Form Fabrication (FFF) printer for printing high performance polymers such as PEEK. 

CALM is pleased to provide research support for the PhD programme which will focus on understanding the polymer behaviour from molecular scale to macro-scale performance throughout the new manufacturing process. Aspects such as crystal structure, size, amorphous and crystalline behaviour, layer-to-layer bonding, degradation effects, mechanical performance and design considerations will form part of the PhD study.

Funded by: University of Exeter and Bond High Performance 3D

 

 

The University of Exeter is part of a consortium of 8 organisations, led by Victrex, to develop PAEK for various 3D printing processes. This project was conceived and the team established following the conference held by the University of Exeter – European Strategy for Additive Manufacturing with High Temperature Polymers.

A key objective is the improvement of the recycle rate for powders used in laser sintering. This would significantly reduce polymer wastage in this type of additive manufacturing process and reduce costs. The project will also address unpredictability of inter-layer adhesion and parts surface finish in filament-based printing.

Funded by: Innovate UK (Aerospace Technology Institute)

Partners: Victrex Manufacturing Limited, E3D-Online Ltd, 3T RPD, South West Metal Finishing Limited, Airbus Group Limited, EOS, HiETA

The aim of this project is to develop novel high performance, nanocomposite feedstock powder materials and filament for two processes: Laser Sintering and Fused Deposition Modelling (FDM). It will examine the potential use of inorganic fullerene-like tungsten disulfide (WS2) as nanofillers for high value, PAEK (Poly Aryl Ether Ketone) based products.

The incorporation of these nanomaterials has been shown to improve thermal, mechanical and tribological properties of various thermoplastic polymers. It reduces wear and the coefficient of friction as well as offering processability benefits with dispersion characteristics that are superior to 1D and 2D nanoparticles. They are also the best shock absorbing cage structures known to mankind and importantly, they are non-toxic and thermally stable.

Funded by: EPSRC

Partners: University of Exeter and Ulster University. Supported by Victrex Polymer Solutions, Laser Prototype Europe, Bombardier Aerospace, Daido Metals Co. Ltd.

This project investigated the way the polymeric powders of different shapes and sizes flow, interact and sinter in the laser sintering (LS) process, through modelling and experimental validation. The spreading and compaction of the powder is an important part of the LS process. A non-uniform layer of powder leads to high porosity and weaker bonding between layers and therefore a structure with poor mechanical performance.

Similarly, the size and shape of particles can change the sintering process. Larger contact areas between particles lead to a good sintering profile and ultimately to a high density part and good mechnical properties. Surface area of particles, polymer viscosity and surface tension were characteristics which were investigated when modelling the flow and sintering process.

Findings

It was a highly innovative project and its findings have the potential to help unlock the materials limitations for polymeric laser sintering. This allows rapid expansion into a wider range of higher value applications due to lower powder costs, wider choices and better understanding of their behaviour within the manufacturing process.

Funded by: EPSRC

Partners: University of Exeter and University of Edinburgh. Supported by Victrex Manufacturing Ltd and 3T RPD

 

Discrete Element Method

Reference https://doi.org/10.1016/j.powtec.2016.11.002 ‌

Arkema and CALM are working together on optimising Poly Ether Ketone Ketones (PEKK) for the EOSINT P 800 powder bed process. The PhD aims to gain a deep understanding of the material at the microstructure level in order to optimise it for the manufacturing process.

Arkema is a European chemical company leader in the field of high performance polymer materials, one of which is PEKK, invented in the 1960s as part of the Apollo space program.

PEKK Kepstan®, one of Arkema’s PEKK materials, has a very high melting point (300°C to 360°C depending on the grade) and provides excellent resistance to chemicals and abrasion. Reinforced with carbon fibres, it is as rigid as some metals, but very much lighter and it is non-flammable without releasing any toxic fumes.

Funded by: University of Exeter and Arkema

Particle coalescence 

High temperature laser sintering is an additive manufacturing technique enabling the highest level of design freedom currently achievable. High customisation, multi-functional integration and design optimisation are the most outstanding characteristics of this process.

However, the small number of polymers currently available constitute a significant drawback for many engineering applications, especially in the automotive and aerospace industrial sectors, where only one grade, PolyEtherKetone PEK HP3, can meet the material performance required.

In an attempt to expand the choice of materials for laser sintering manufacturing, this research project has focused on the investigation and implementation into laser sintering of a new high temperature polymer, Poly Ether Ether Ketone (PEEK). This research work has examined some of the key requirements needed for the successful development of new materials in laser sintering at experimental and theoretical levels and led to the manufacture and testing of some medical applications using a medical grade of PEEK.

Supported by: Victrex, Invibio Biomaterial Solutions

This 6-month feasibility study is proposing to combine the unique properties of two materials - Carbon nano tubes (CNTs) and high temperature polymers (PEEK) - with the exceptional capabilities offered by laser sintering to achieve lightweight parts with complex geometries and enhanced mechanical performance such as strength and fracture toughness.

This research is a key enabler towards the development of highly complex multifunctional structures. The incorporation of the CNTs into polymeric powders for use in additive manufacturing is envisaged to provide good CNT dispersion across the manufactured part, and enhance part strength in all directions (X, Y and especially Z direction, generally known to give weak structures in SLS processes).

This study will allow for the first time the use of the bespoke high temperature laser sintering system P800 (EOS, 2013).

Supported by: Airbus Group Ltd

Funded by: Defence Science and Technology Laboratory [DSTL]

Carbon nanotubes (CNTs) are of great interest for the next generation of composite materials due to their exceptional mechanical and physical properties. They can be manufactured as vertically aligned "forests" at predetermined sites on a surface using a micro-patterned catalyst film to initiate growth by chemical vapour deposition. This allows them to be organised to form complex architectures, with the potential to act as aligned reinforcements in polymer composite films.

The project investigated the development of unique CNT polymer composite structures with a high potential for application in the aerospace industry.

Findings

It successfully demonstrated some of the key requirements for the realisation of the UTOPIUM concept, of embedding patterned aligned CNTs within layers, bridging the interlayer boundaries and providing continuously aligned reinforcement.

In particular, the work showed that due to the strong capillary forces which occur at the nanoscale, careful control of the resin viscosity and gel time is necessary for the required partial wetting, as well as monitoring of the presence of resin via chromium based marker dyes.

In addition, we were able to investigate and demonstrate rapid-patterning techniques which would be necessary to manufacture patterned nanotube forests during ALM. This was demonstrated by the use of inkjet-patterned nanoparticles as catalysts for nanotube growth, as part of a collaboration with the Kroto Research Institute at the University of Sheffield.

By demonstrating these two key requirements (partial wetting techniques and rapid patterning of carbon nanotubes) this project laid essential groundwork for the UTOPIUM concept. In future, the UTOPIUM idea could provide the reinforcement effectiveness of carbon nanotube composites in combination with the versatility of design offered by ALM.

Funded by: Airbus Group Innovations (formerly EADS Innovation Works)