Influence of periodic pressure on dendritic morphology and sidebranching

The influence of periodic pressure with low and high frequencies on microstructure and dendritic sidebranching was studied by using 3-D phase field method. In both low and high frequency cases, the variation trend of SDAS (secondary dendritic arm spacing) with increasing pressure frequency is opposite to that of sidebranching frequency, while the variation trend of the average length of secondary arms is consistent with that of sidebranching frequency. The high sidebranching frequency indicates that more secondary arms share the whole driving force of dendrite growth, resulting in lower driving force for each one and leading to less developed secondary arms. The smallest SDAS is obtained when perturbed by the periodic pressure with the frequency of 0.157/τ0 (τ0 is the physical unit of time in the dimensionless phase field model) and 2.200/τ0 in low and high frequency cases, respectively. Comparisons of dendritic morphology and secondary arms are made between the low and high frequency cases. Firstly, in the low frequency case, secondary arms are luxuriant especially when pressure frequency is low, with many high-order side branches stretching out. Secondly, the average length of secondary arms in primary dendrite is longer in the low frequency case than that without pressure, and much longer than that in the high frequency case. Thirdly, the dendrite tip without side branches in the high frequency case is much longer than that in the low frequency case. All of the differences in dendritic morphology and sidebranching in the two cases can be attributed to the different modulation mechanism. In the low frequency case, periodic pressure determines tip velocity and then modulates sidebranching directly. While in the high frequency case, periodic pressure cannot determine sidebranching directly, but via modulating tiny protuberances in dendrite tip, part of which evolves into side branch. In this case, the tiny protuberances take part of the whole driving force, leading to less developed secondary arms.

Distinctions of dendritic behavior influenced by constant pressure and periodic pressure

The distinctions of dendritic morphology and sidebranching behavior when solidified under atmosphere pressure,constant pressure which is higher than atmosphere pressure (hereinafter referred to as constant pressure) and periodic pressure were investigated using 3-D phase field method.When growing at atmosphere pressure,side branches (secondary dendritic arms) are irregular.When solidified under constant pressure with a relatively high value,side branches are much more luxuriant,with more developed high-order side branches.When applied with periodic pressure,resonant sidebranching happens,leading to many more regular side branches and the smallest secondary dendritic arm spacing (SDAS) in the three cases.The significant difference in dendritic morphology is associated with tip velocity modulated by total undercooling including pressure and temperature undercooling.In the case of constant pressure,tip velocity increases linearly with total undercooling,and it varies periodically in periodic pressure case.The different variation trend in tip velocity is the reason for the distinct dendrite growth behavior in different cases.Unlike the phenomenon in constant pressure case where the dendrite grows faster with higher pressure,the dendrite grows slower under periodic pressure with higher amplitude,resulting in less developed primary dendrite and side branches.This is influenced by tip remelting due to low undercooling or even negative undercooling.It is revealed that the accelerated velocity of tip remelting increases with the decline of undercooling.The greater the amplitude of periodic pressure,the faster the tip remelting velocity during one period.This is the reason why the average tip velocity decreases with the rise of amplitude of periodic pressure.

Aerobic Alcohol Ammoxidation Catalyzed by Copper（I）/Amino Acid： a Scalable Protocol to Nitriles

A facile, practical and scalable catalyst system for alcohols ammoxidation into nitriles was developed using amino acid as ligand, oxygen as terminal oxidant and copper iodide（CuI） as catalyst. The catalyst system shows excellent functional groups compatibility for a wide range of testing substrates, even the substrates bearing oxidationsensitive groups such as MeS-, alkenyl and --NH2 can also work well. In addition, the protocol is readily scaled up to more than 20 g and the product can be obtained just through filtration or distillation without conventional column chromatography.