Development of scalable plasma polymerisation processes Jason Whittle

Development of scalable plasma polymerisation processes Jason Whittle School of Engineering, University of South Australia Future Industries Institute, University of South Australia Cell Therapy Manufacturing CRC

Applications Mechanisms Plasma Polymers Properties Translation

Plasma Polymerisation Plasma Chamber (under vacuum) Monomer Vapour Flows into Chamber Radiofrequency Power Applied to System Plasma Substrate

Plasma Polymerisation • • • Uniform Reproducible Substrate Independent Stable Pinhole Free Scalable Yasuda Parameter W FM

Uniform? Shirazi et al. Colloids and Surfaces B: Biointerfaces 161, 261 -268 (2018)

Uniform?

Reproducible? Small Scale • Mean N/C 0. 23 (n=10) • SD = 0. 045 Medium Scale • Mean N/C 0. 22 (n=11) • SD = 0. 01

Reproducible?

Substrate Independent Vasilev et al. Chem. Comm. p 3600 -02 (2009)

Stable? Whittle et al. Chemistry of Materials 12 (9), 2664 -2671 (2000)

Translatable? Steel Barrel (2) • non-coaxial geometry • Internal Electrodes Steel Cylinder (3) • Axial Symmetry • Internal Electrodes Glass Cylinder (2) • Substrates perpendicular to flow • Insulating walls, Internal Electrodes Glass Barrel (7) • Substrates parallel to flow • External Electrodes • Band (5) or Coil (2) Electrodes Glass Cross-piece (2) • Substrates parallel to flow • External Coil electrodes Whittle et al. Plasma Processes and Polymers, Vol. 10, p 767 (2013)

Translatable? Whittle et al. Plasma Processes and Polymers, Vol. 10, p 767 (2013)

Translatable? Whittle et al. Plasma Processes and Polymers, Vol. 10, p 767 (2013)

Unfractionated Heparin (4 th Int. Std) Low Molecular Weight Heparin Chondroitin-4 -Sulfate Hyaluronan Dermatan Sulfate

Power Plasma Processes and Polymers Vol. 11. p 833 -41 (2014).

0 W 2 W 4 W 8 W 16 W 32 W

2 sccm 4 W 8 W 16 W 32 W 4 sccm 6 sccm 8 sccm

AVS Tampa 2012 Ps. Th. A 8 Principal Component Analysis (PCA) Goals: • Reveal Underlying structure • Reduce Complexity Take m spectra (around 140) each with n peaks (150 -300) Once we have a PCA model, we can project new data points into it.

EI Mass spectra of neutral species 2 sccm 4 sccm 6 sccm 8 sccm

EI Mass spectra of neutral species

Positive Ions

Ion Energy Ion energy distributions (M+H)+ at 1. 3 Pa

Ion Flux Michelmore et al. , ACS Appl. Mater. Interf. Vol. 5. 5387 -91 (2013)

Black Box Power (W) Pressure (p) Temperature (T) Flow Rate (mols-1) Duration (s) Geometry Substrate Plasma External Parameters Film Chemistry Crosslink Density Deposition Rate Optical Properties Morphology Surface Properties Internal Parameters Electron Temperature (Te) Ion Temperature (Ti) Ion Density (ni) Electron Density (ne) Plasma Potential (Vp) Sheath Potential (Vs) Mass Spectrum Optical Emission

Large-scale 650 mm

Acknowledgements • Uni. SA • • • Sameer Al-Bataineh Nick Rogers Solmaz Saboohi Giles Kirby Hanieh Safizadeh Shirazi Andrew Michelmore Louise Smith David Robinson Tara Fernandez Rob Short • Elsewhere • Claire Homan, Josef Gecz (Uni. Adelaide) • Tony Day, Andy Marson, David Mahoney (Oxford/Manchester) • John Gallagher (Iduron Ltd. ) • Morgan Alexander, Cathy Merry (Manchester/Nottingham)