PPB structure elimination,DRX nucleation mechanisms and grain growth behavior of the3rd-generation PM superalloy for manufacturing aviation components

Previous Particle Boundary(PPB),as the detrimental structure in Powder Metallurgy(PM)components,should be eliminated by subsequent hot process to improve the mechanical properties.The objective is to investigate the Dynamic Recrystallization(DRX)nucleation mechanisms and grain growth behavior of the 3rd-generation PM superalloy with PPB structure.Microstructure observation reveals that PPB decorated with(Ti,Ta,Nb)C carbides belongs to the discontinuous chain-like structure.The elimination of PPB networks can be achieved effectively via hot deformation due to the occurrence of DRX.Four different DRX nucleation mechanisms were proposed and discussed in detail according to the special microstructure characteristics of the PM superalloy.Firstly,local lattice rotations can be detected in the vicinity of(Ti,Ta,Nb)C carbides during hot deformation and thus PPB structure serves as the preferential nucleation sites for DRX grains via Particle-Stimulated Nucleation(PSN).Then,Discontinuous-DRX(DDRX)characterized by grain boundary bulging dominates the microstructure refinement and Continuous-DRX(CDRX)operated by subgrain rotation can be regarded as an important assistant mechanism.At last,the initial Σ3 boundaries would lose their twin characteristics owing to the crystal rotation and then transform into the general High Angle Grain Boundaries(HAGBs).The distorted twins provide additional DRX nucleation sites,viz.,twin-assisted nucleation.Particular attention was focused on the grain growth behavior of the PM superalloy in subsequent annealing process.The recrystallization temperature was determined to be about 1110.C and 1140.C can be considered as the critical temperature for grain growth.The findings would provide theoretical support for microstructure refinement of the 3rd-generation PM superalloy,which is of pivotal significance for improving the mechanical properties of aviation components.

[4+1]Annulation of in situ generated azoalkenes with amines:A powerful approach to access 1-substituted 1,2,3-triazoles

1-Substituted 1,2,3-triazoles represents‘privileged’structural scaffolds of many clinical pharmaceuticals.However,the traditional methods for their preparation mainly rely on thermal[3+2]cycloaddition of potentially dangerous acetylene and azides.Here we report a base-mediated[4+1]annulation of azoalkenes generated in situ from readily available difluoroacetaldehyde N-tosylhydrazones(DFHZ-Ts)with amines under relatively mild conditions.This azide-and acetylene-free strategy provides facile access to diverse 1-substituted 1,2,3-triazole derivatives in high yield in a regiospecific manner.This transformation has great functional group tolerance and can suit a broad substrate scope.Furthermore,the application of this novel methodology in the gram-scale synthesis of an antibiotic drug PH-027 and in the late-stage derivatization of several bioactive small molecules and clinical drugs demonstrated its generality,practicability and applicability.

Neighbouring carbonyl group-assisted sequential 1,2-azide and1,4-oxygen migrations of vinyl azides leading to α-azido ketones

The development of azide migration reactions is a formidable challenge due to potential competition from side processes driven by the release of molecular nitrogen. Here, we show a novel neighbouring carbonyl group-assisted sequential 1,2-azide and 1,4-oxygen migration reaction of α-vinyl azides for the efficient preparation of a range of α-azido ketones. This represents the first transformation of α-vinyl azides into α-azido ketones. Notable features of this method are its high efficiency, broad substrate scope, excellent functional group compatibility, and high yields. The computational studies gave a key insights into the regioselective 1,2-azide and 1,4-oxygen migrations assisted by the neighbouring carbonyl group. Further conversions into a variety of nitrogen-containing compounds demonstrated the synthetic utility of the α-azido ketone products. Preliminary mechanistic studies disclosed a novel reaction mechanism involving neighbouring carbonyl group-assisted sequential 1,2-azide and1,4-oxygen migrations.