Study of the kinetics and mechanism of rapid self-assembly in block copolymer thin films during solvo-microwave annealing

Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high- lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during "solvo-microwave" annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 degrees C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during "solvo-microwave" annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O-2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.

Analysis of the failure of cracked biscuits

Cracks or checks in biscuits weaken the material and cause the product to break at low load levels that are perceived as injurious to product quality. In this work, the structural response of circular digestive biscuits, with diameter 72 mm and thickness 7.2 mm, simply supported around the circumference and loaded by a central concentrated force was investigated by experiment and theory. Tests were conducted to quantify the distribution in breakage strength for structurally sound biscuits, biscuits with natural checks and biscuits with a single known part-through crack. For sound biscuits the breakage force is Normally distributed with a mean of 12.5 N and standard deviation of 1.2 N. For biscuits with checks, the corresponding statistics are 9.6 N ± 2.62 N respectively. The presence of a crack weakens the biscuit and strength, as measured by breakage force falls almost linearly with crack length and crack depth. The orientation of the crack, whether radial or tangential, and its location (i.e. position of the crack mid-point on the biscuit surface) are also important. Deep, radial, cracks located close to the biscuit centre can reduce the strength by up to 50%. Two separate failure criteria were examined for sound and cracked biscuits respectively. The results from these tests were in good accord with theory. For a biscuit without defects, breakage occurred when maximum biscuit stress reached or exceeded the failure stress of 420 kPa. For a biscuit with cracks, breakage occurred as above or alternatively when its critical stress intensity factor of 18 kPam0.5 was reached.