“High Performance Thermoplastics

– Finally a dawn for truly specialty thermoplastics products?”

APIC 2016, Singapore

Dr Nurallah (Noor) Jivraj

Director and Principal Consultant, AGNI Energy & Synergy Ltd,

Worcester Park, UK

Presentation Agenda Plastics Pyramid – a select band of “top-notch” niche

market High Performance Thermoplastics (HPTPs)

Attributes of and a Semi-Quantitative Comparative of Selected High Performance Thermoplastics

Performance Requirements for HPTPs in Aerospace, Medical and Dental, Semi-Conductors, and Renewables

PEEK and PPS – Discussion on demand drivers, key players, demand and capacity growth

Outlook for High Performance Thermoplastics

Plastics Pyramid - Qualitative Segmentation The Pyramid Apex has been

to date a small market

Many invented between 1960s and 1980s, some like PTFE much earlier

1990s: High synthesis costs, developmental costs, limited applications kept these a niche zone – generally well less than 10-15 kta – some as low as 2-5 kta

High Time for HPTPs? HPTs have suddenly seen immense demand growth and capacity

investments, and new players emerged

Customers pay $15 - $25/kg for the “low end” materials like PPS, through $40 - $60 for mid-specialties to even $100/kg for top end materials like PEEK in certain medical applications

Some of the HPTPs have seen double digit growth in some years, with 8 – 10 % CAGR over a decade

So what has changed so much in an age where previous performance plastics like PC and PA-6/66 have become commoditized ?

Families & Chemical Structures of Key HPTs …1

PEI – PolyEther Imide

Families & Chemical Structures of Key HPTs …1

PA 6-10

High Temperature Performance of Key HPTPs

Continuous high temperature performance with low creep is just one of a series of very stringent requirements for HPTPs

Qualitative Ranking of Key HPTs PEEK generally has the best

all round performance

PPS’s popularity partly due to simpler synthesis route leading to a lower cost but suffers from relative brittleness

Fluoro-polymers have excellent low temperature properties but tensile strength and processibility is a major challenge, especially with PTFE

Aerospace and Carbon Fibre Composites Cycling Low and High Service Temperatures under load

Low Creep across full service temperature range

Good chemical resistance

Inherent flame-resistance: UL94 Fire behaviour with regard to smoke gas density, smoke gas toxicity, heat release

High specific strength due to fibre-reinforced plastics

Convincing gliding properties

ASTME 595 outgassing requirements - Low outgassing in vacuum

Good radiation resistance

Aerospace and Carbon Fibre Composites Huge strides made in new

aircraft design – lightweighting by use of composites

Kevlar Fibre, Glass Fibre, Carbon Fibre and Nano-Fillers combined with thermoplastics like PEEK and thermosetting ones like Polybenzimidazoles (PBI) and Polyimides like PEI

Carbon Fibre Thermoplastic composites can offer up to 70% weight reduction against steel equivalents

Medical and Dental Medical/Dental Plastics have the most rigorous qualification

processes and standards, and apart from usual properties such impact strength, creep strength, and dimensional stability, other performance requirements can be:

Resistant to cleaning agents and disinfectants, hydrolysis and hot steam Excellent sterilization resistance Excellent chemical resistance Extremely abrasion and wear resistant Excellent dimensional stability Physiological harmlessness (ISO 10993) – GRAS status Biocompatibility (FDA-compliant, meet ISO 10993 for Cytotoxicity, ISO

13485 Certified Plastic Materials) Good radiation resistance

Medical and Dental

Increasingly HPTs such as PPSU and PEEK are replacing metal implants and surgical instruments in dentistry

Automotive – under the hood, lighting, battery power For structural components within the battery

module and the battery pack housing, polyphthalamide (PPA) is material of choice

High voltage rechargeable batteries for electric vehicles need high-temperature stability, chemical resistance to electrolytes, dimensional stability and flame retardancy – PPO is popular as casing material

Aerospace materials filter down to performance cars – novel lighting, confined interiors, displays – higher power demands means batteries with higher voltage and in more confined interiors

PES, PPSU and PSU, being transparent are popular in automotive lighting

Oil and Gas Industry As more and more gas and oil is ultra

deep water (>1500m water depth). There has been a boom in flexible yet robust and high strength materials carrying corrosive liquids (riser systems)

The largest markets for HPTPs in the oil and gas industry are in the cords, wires, cables and flexible and reinforced pipes and liners applications. PA 11 and PA 12 are particularly well suited

Electronics and Semi-Conductors High purity materials are vital during processing of e.g. wafer

production. Almost zero outgassing properties under high vacuum is critical – PEEK, PEI etc have very low outgassing

Examples of HPTs applications include:

Cleaning tanks made of PEEK, PVDF and other fluoropolymers Vacuum grippers from PPS or PEEK: low outgassing in vacuum and

high mechanical strength Wafer containers and Front Opening Unified Pods (FOUP) made of PPS

or PEEK: high mechanical stability Wafer handling systems made of nanoparticle filled PEEK for high

temperature stability, and electrostatic dissipative behaviour

Power Generation – Coal & Renewables

Hot particulate collection filter bags for coal power plants Traditional glass fibre epoxy/vinyl ester wind turbine

blades deemed to heavy and inefficient for next generation – research centres on HPTPs and carbon fibres

Wind power applications demand low creep, excellent abrasion resistance, flame resistance, electrical isolation

Wind turbine applications such as bearing separators, connectors, braking systems, and pitches and yaw drive components

Applications include sliding friction stressed mechanical components (sliding bearings, rollers, pressure discs, piston rings, seals)

PPS (Polyphenylene Sulphide) Commercial process for polymerizing was

successfully developed and manufactured by Phillips Petroleum (USA) in 1973

PPS had always been popular for automotive plastics applications requiring high temperature light weight durable, non-wearing components

PPS demand shot up when LUMENA (formerly Deyang Plastics) acquired PPS technology and commercialised high temperature particulate collection bags for coal fired power plants

PPS, compared to other HPTPs, is a relatively simple molecule - synthesis is much less complex (reflected in its modest pricing) - thus typically the first stop point in high temperature thermoplastics design

PPS Demand/Capacity 1990-2017

PPS demand now approaches 100 kta having been just 11 kta in 1990

PEEK (Polyether Ether Ketone) PEEK is an injection mouldable material and can be reinforced with

glass, mineral, and graphite fibres.

PEEK has one of the lightest strength to weight ratios and exhibits outstanding resistance to aggressive chemicals, especially hydraulic fluids

PEEK operates at extremely high temperatures, 260° C long term and 315 ° C short term.

PEEK meets ASTME 595 outgassing requirements and UL 94 flammability tests as well as zero halogen requirements.

Why can PEEK command the high price ? Excellent strength, stiffness, long-term

creep and fatigue properties Low Smoke and Toxic Gas Emission Exceptionally low outgassing and

extractables Low moisture absorption, resistant to

steam, water and sea water with low permeability

High abrasion and cut through resistance combined with a low coefficient of friction

Electrical properties maintained over a wide frequency and temperature range

PEEK Demand/Capacity 1990 - 2017

Victrex is a management buy out of ICI’s PEEK technology and business Victrex still dominates the PEEK production and is particularly optimistic

about prospects and may be trying to squeeze other players by increasing capacity substantially

Key players with portfolio of HPTPs

Solvay – PAI, PAEK, PEEK, PPSU, PPA, PPS, PTFE, PVDC, PVA , PA 6-10 etc

DuPont – Kevlar PA LCP, PI, PTFE, ETFE, PFA, FEP, PBT BASF – PPSU, PES, PSU, PBT Arkema – PEKK, PVDF, PA 1-1, PA 1-2 Kureha – PPS, PVDF Toray – PI, PPS, PBT, PA 1-2 SABIC – PEI, PBT

DSM – PA 4-6, PBT

In Summary … Innovation in thermoplastics, thermosets and associated composite

materials has propelled demand growth for HPTPs

Aerospace, power generation, medical and dental, electronics and semiconductor industries driving new generation of applications

Margins for the top end HPTPs remain high despite capacity additions

Application development time and certifications protect the competitive advantage

Processing know-how is critical and a major competitive advantage

A select few companies have a long term strategy to develop a strong portfolio of HPTPs