Environmental resistance of composites John Summerscales Outline of lecture • • • • • • • • glass transition temperature moisture osmosis and blistering cavitation erosion galvanic corrosion marine coatings antifouling paints flame, smoke and toxicity (FST) Glass transition temperature (Tg) • Tg is a function of: molecular structure o ratio of chain ends to backbone polymer o loading rate o moisture content can reduce Tg o • A key design parameter in aerospace applications is “hot wet Tg” Moisture (Fickian diffusion) Moisture content equilibrium/saturation √(time) Osmosis ... • Osmosis can be defined (Clegg, 1996) as “the equalisation of solution strength by passage of a liquid (usually water) through a semi-permeable membrane membrane Weak solution Strong solution Osmosis ... • normally the fluid will pass through the material without affecting it • but, there may be soluble materials, e.g. residual glycol from UP resin o soluble binder on CSM o PVA release agents, etc o see pp 231-233 of Searle and Summerscales for a more complete list! • these materials will dissolve in the solvent Osmosis and blistering • a little solvent and a lot of solute -> a strong solution • strong driving force for osmotic cell • high pressures generated cause/expand void containing strong solution • swelling leads to blisters with associated surface undulation • Image from: http://www.wessex-resins.com/ westsystem/wsosmosis.html http://www.insightmarinesurveyors.co.uk/osmois%20ringed.jpg Osmosis and blistering • For marine applications, consider changing from orthophthalic to isophthalic polyester resin o and to improve “iso” resin further, use NPG (neo pentyl glygol): o HO-CH2-C(CH3)2-CH2-OH 2,2-dimethyl-1, 3-propanediol • Durability: o ortho < iso < NPG Chemical structure from: http://chemicalland21.com/specialtychem/perchem/NEOPENTYL%20GLYCOL.htm Osmosis and blistering • To avoid osmosis leading to blistering: o o o o o o o o no soluble components in resin system avoid moisture on mould and reinforcement completely wet-out the fibres consolidate to minimise voids gel coat of lower permeability than laminate use a light glass scrim in the gelcoat use primer (tie-coat) between gel coat and structural laminate control gelcoat thickness and quality Cavitation erosion • Collapsing bubble: Solid surface model from Lauterborn and Bolle (1975) Cavitation erosion • Collapsing bubble: Solid surface model from Lauterborn and Bolle (1975) Cavitation erosion • Collapsing bubble: Solid surface model from Lauterborn and Bolle (1975) Cavitation erosion • Collapsing bubble: Solid surface model from Lauterborn and Bolle (1975) Cavitation erosion • Collapsing bubble creates jet towards a hard surface which loosens material structure and removes material: Solid surface model from Lauterborn and Bolle (1975) Cavitation erosion • Very limited data in public domain • composites may perform better than metals because fibre > grain size student projects* suggested CFRP proportional loss in weight only 40% of that for Al under identical conditions o but difficult experiment o CFRP absorbs some water may have low initial - but accelerating - loss rate * Handley ..and.. Ladds (1995) Galvanic corrosion 1 • corrosion involves flow of an electric current • most constituents of fibre-composites are insulators and hence electrochemical corrosion is not an issue • However, carbon (graphite) acts as a noble metal, lying between platinum and titanium in the galvanic series. Galvanic corrosion 2 • Carbon fibres should not come into contact with structural metals (especially Al or Mg) in the presence of a conducting fluid (eg sea-water). • A thin glass fibre surface layer may be sufficient to prevent the formation of such a galvanic corrosion cell. Marine coatings • Surface coatings may be for provide aesthetic finish o improve resistance to corrosion o protect against fouling o especially for marine or process plant applications • gel-coat is normally applied to the mould before the laminate is laid-up/injected • a major issue in the marine industry is “print-through” o surface echoes topology of reinforcement Antifouling paints • Toxic compositions cuprous oxide – increasing concern o tri-butyl tin – now banned worldwide o • Exfoliating/self-polishing surfaces – increasing concern • Non-toxic low surface energy compositions • Bio-inspired approach (biomimetics) Liedert and Kesel: shark skin as the analogue o surface microstructure, Rz = 76 μm o soft silicone material (shore A = 28) o low surface energy (25 mN/m) Flame, Smoke and Toxicity (FST) • especially important for submarines, o underground railways, and o underground mines o • F = low spread of Flame • S = minimal emission of Smoke • T = no Toxic products of combustion o phenolic resins burn to just H2O and CO2 in the presence of a good supply of air Balmoral offshore lifeboat • glass reinforced plastic fire-retardant resins carries 21-66 people • certification required to withstand 30 m high kerosene flames and temperatures of 1150°C • throughout the fire test, the temperature inside never exceeded 27°C. Image from the front cover of International Reinforced Plastics Industry May/June 1983, 2(5), 1