Regulated phase separation in nanopatterned protein-polysaccharide thin films by spin coating.

Patterned films are essential to the commonplace technologies of modern life. However, they come at high cost to the planet, being produced from non-renewable, petrochemical-derived polymers and utilising substrates that require harsh, top-down etching techniques. Biopolymers offer a cheap, sustainable and viable alternative easily integrated into existing production techniques. We describe a simple method for the production of patterned biopolymer surfaces and the assignment of each biopolymer domain, which allows for selective metal incorporation used in many patterning applications. Protein and polysaccharide domains were identified by selective etching and metal incorporation; a first for biopolymer blends. Morphologies akin to those observed with synthetic polymer blends and block-copolymers were realised across a large range of feature diameter (200 nm to - 20 µm) and types (salami structure, continuous, porous and droplet-matrix). The morphologies of the films were tuneable with simple recipe changes, highlighting that these biopolymer blends are a feasible alternative to traditional polymers when patterning surfaces. The protein to polysaccharide ratio, viscosity, casting method and spin speed were found to influence the final film morphology. High protein concentrations generally resulted in porous structures whereas higher polysaccharide concentrations resulted in spherical discontinuous domains. Low spin speed conditions resulted in growth of protuberances ranging from 200 nm to 22 µm in diameter, while higher spin speeds resulted in more monodisperse features, with smaller maximal diameter structures ranging from 300 nm to 12.5 µm.

Nanopatterned protein-polysaccharide thin films by humidity regulated phase separation.

Greater sustainability in mass manufacturing is essential to alleviating anthropogenic climate change. High surface-area, micro- and nano-patterned films have become a fundamental tool in materials science, however these technologies are subject to a dwindling petrochemical supply, increasing costs and disposability concerns. This paper describes the production of patterned biopolymer films utilizing controlled phase separation of biopolymeric thin films into nanopatterns using easily transferable variables and methods. Similar morphologies to those commonly observed with synthetic block-copolymers (BCPs) were achieved across a large range of feature sizes, from 160 nm to >5 µm: Bicontinuous, porous, droplet-matrix, particulated and dimpled. Protein and polysaccharide type, protein to polysaccharide ratio, casting method and ambient humidity were primary conditions found to influence the pore morphology of the films. High protein concentrations (4:1 and 2:1 blends) generally resulted in porous structures whereas high polysaccharide concentrations (1:2 and 1:4 blends) resulted in spherical structures. High humidity conditions (60% + relative humidity) resulted in the growth of large protuberances up to 10 µm in diameter while lower humidity (10-30%) resulted in discrete features smaller than 200 nm.