The Effect of Binder Loading on the Pore Size of 3D Printed PMMA.

Binder jetting is known to produce porous objects by depositing the binder selectively layer by layer on a powder bed. In this study, the pore size of printed parts and the correlating mechanical properties are investigated on a commercially available PMMA powder binder system. Pore sizes are measured via capillary flow porometry and mechanical properties via tensile tests. Porometry indicates that the pore size stays at a constant level of 22 µm at 5 to 10 wt% binder loading before decreasing to 6 µm at loadings of 30 wt% or higher. The results were compared with the mechanical testing and related to the agglomerate strength model of Rumpf. The highlights of the article are the application of a binder jetted part as a filter and the identification of a close relationship between porosity and mechanical strength, similar to phenomena in agglomeration science.

Unusually selective synthesis of chlorohydrooligosilanes.

New pathways towards molecular chlorohydrooligosilanes enable their one-pot synthesis in preparative amounts either by the selective chlorination of the corresponding perhydrosilanes with HCl/AlCl3 or by the partial hydrogenation of perchlorooligosilanes with substoichiometric amounts of iBu2AlH. The unexpected selective formation of Cl3Si-substituted species in the partial hydrogenation reactions could be related to mechanistic aspects.

Synthesis and Properties of Branched Hydrogenated Nonasilanes and Decasilanes.

Branched higher silicon hydrides Si nH2 n+2 with n > 6 were recently found to be excellent precursors for the liquid phase deposition of silicon films. Herein we report the gram-scale synthesis of the novel nona- and decasilanes (H3Si)3Si(SiH2) nSi(SiH3)3 (2: n = 1, 5: n = 2) from (H3Si)3SiLi and Cl(SiPh2) nCl by a combined salt elimination/dephenylation/hydrogenation approach. Structure elucidation of the target molecules was performed by NMR spectroscopy and X-ray crystallography. 2 and 5 are nonpyrophoric and exhibit a bathochromically shifted UV absorption compared to neopentasilane and the structurally related octasilane (H3Si)3SiSi(SiH3)3. TG-MS analysis elucidated increased decomposition temperatures and decreased ceramic yields for branched hydrosilanes relative to cyclopentasilane. Otherwise, very similar thermal properties were observed for hydrosilane oligomers with linear and branched structures.

Branched Hydrosilane Oligomers as Ideal Precursors for Liquid-Based Silicon-Film Deposition.

Herein a convenient synthetic method to obtain 2,2,3,3-tetrasilyltetrasilane 3 and 2,2,3,3,4,4-hexasilylpentasilane 4 on a multigram scale is presented. Proton-coupled 29 Si NMR spectroscopy and single-crystal X-ray crystallography enabled unequivocal structural assignment. Owing to their unique properties, which are reflected in their nonpyrophoric character on contact with air and their enhanced light absorption above 250 nm, 3 and 4 are valuable precursors for liquid-phase deposition (LPD) and the processing of thin silicon films. Amorphous silicon (a-Si:H) films of excellent quality were deposited starting from 3 and characterized by conductivity measurements, ellipsometry, optical microscopy, and Raman spectroscopy.

Selective Synthesis and Derivatization of Germasilicon Hydrides.

Mixed Si/Ge hydrides SixGeyHz are valuable precursors for the deposition of binary Si-Ge alloys. This work describes the synthesis and full characterization of the previously unknown germaisotetrasilane Ph3GeSi(SiH3)3 (2) on a multigram scale from the reaction of the lithium silanide LiSi(SiH3)3 with Ph3GeCl. The stability of the Si-Ge bond in 2 versus electrophiles and nucleophiles has been investigated with the primary aim of developing new approaches to mixed sila-H-germanes (H3Ge)xSi(SiH3)4-x. With 1 equiv of MeLi, 2 reacted cleanly under cleavage of one Si-Si bond to give Ph3GeSi(SiH3)2Li, which is a valuable synthon for further derivatization. In contrast, the dephenylation reaction of 2 with 1 or 2 equiv of CF3SO3H/iBu2AlH proceeded much less selectively and afforded the desired Ph/H-germasilanes Ph2HGeSi(SiH3)3 and PhH2GeSi(SiH3)3 along with considerable amounts of Si-Ge scission products.