Chemical heterogeneities reveal early rapid cooling of Apollo Troctolite 76535

The evolution of the lunar interior is constrained by samples of the magnesian suite of rocks returned by the Apollo missions. Reconciling the paradoxical geochemical features of this suite constitutes a feasibility test of lunar differentiation models. Here we present the results of a microanalytical examination of the archetypal specimen, troctolite 76535, previously thought to have cooled slowly from a large magma body. We report a degree of intra-crystalline compositional heterogeneity (phosphorus in olivine and sodium in plagioclase) fundamentally inconsistent with prolonged residence at high temperature. Diffusion chronometry shows these heterogeneities could not have survived magmatic temperatures for >~20 My, i.e., far less than the previous estimated cooling duration of >100 My. Quantitative modeling provides a constraint on the thermal history of the lower lunar crust, and the textural evidence of dissolution and reprecipitation in olivine grains supports reactive melt infiltration as the mechanism by which the magnesian suite formed.

Fabrication of C/C–SiC–ZrB2 Ultra-High Temperature Composites through Liquid–Solid Chemical Reaction

In this paper, we aimed to improve the oxidation and ablation resistance of carbon fiber-reinforced carbon (CFC) composites at temperatures above 2000 °C. C/C–SiC–ZrB2 ultra-high temperature ceramic composites were fabricated through a complicated liquid–solid reactive process combining slurry infiltration (SI) and reactive melt infiltration (RMI). A liquid Si–Zr10 eutectic alloy was introduced, at 1600 °C, into porous CFC composites containing two kinds of boride particles (B4C and ZrB2, respectively) to form a SiC–ZrB2 matrix. The effects and mechanism of the introduced B4C and ZrB2 particles on the formation reaction and microstructure of the final C/C–SiC–ZrB2 composites were investigated in detail. It was found that the composite obtained from a C/C–B4C preform displayed a porous and loose structure, and the formed SiC–ZrB2 matrix distributed heterogeneously in the composite due to the asynchronous generation of the SiC and ZrB2 ceramics. However, the C/C–SiC–ZrB2 composite, prepared from a C/C–ZrB2 preform, showed a very dense matrix between the fiber bundles, and elongated plate-like ZrB2 ceramics appeared in the matrix, which were derived from the dissolution–diffusion–precipitation mechanism of the ZrB2 clusters. The latter composite exhibited a relatively higher ZrB2 content (9.51%) and bulk density (2.82 g/cm3), along with lower open porosity (3.43%), which endowed this novel composite with good mechanical properties, including pseudo-plastic fracture behavior.

Vitrimerization of Poly(butylene succinate) By Reactive Melt Mixing Using Zn(II) Epoxy-Vitrimer Chemistry

Vitrimers constitute a new class of covalent adaptable networks (CANs), in which thermally stimulated associative exchange reactions allow the topological rearrangement of the dynamic network while keeping the number of bonds and the crosslink density constant. The current study proposed a solvent-free method to synthesize vitrimers by reactive melt mixing using a commercial biobased/biodegradable polyester, poly(butylene succinate), PBS. More specifically, a two-step process was followed; the first step involved reactive mixing of PBS with the crosslinker (diglycidyl ether of bisphenol A, DGEBA) and the transesterification catalyst (Zinc(II) acetylacetonate hydrate, Zn(acac)2) in a twin-screw mini-compounder, in order to incorporate the epoxy groups in the polymer backbone. The second step (vitrimerization) comprised a crosslinking process of the homogenous mixtures in a vacuum oven at 170 °C, resulting in the formation of a dynamic crosslinked network with epoxy moieties serving as the crosslinkers. By tuning the crosslinker content (0–10% mol with respect to PBS repeating unit) and the Zinc(II) catalyst to crosslinker ratio (0 to 1), tailor-made vitrimers were prepared with high insolubility and improved melt strength. Moreover, PBS vitrimers could still be reprocessed by compression molding after the crosslinking, which enables the recycling process. This work was made possible by the “Basic Research Programme, NTUA, PEVE 2020 NTUA” [PEVE0050] of the National Technical University of Athens and is gratefully acknowledged.

Peroxide-Induced Synthesis of Maleic Anhydride-Grafted Poly(butylene succinate) and Its Compatibilizing Effect on Poly(butylene succinate)/Pistachio Shell Flour Composites

Framing the Circular Bioeconomy, the use of reactive compatibilizers was applied in order to increase the interfacial adhesion and, hence, the physical properties and applications of green composites based on biopolymers and food waste derived lignocellulosic fillers. In this study, poly(butylene succinate) grafted with maleic anhydride (PBS-g-MAH) was successfully synthetized by a reactive melt-mixing process using poly(butylene succinate) (PBS) and maleic anhydride (MAH) that was induced with dicumyl peroxide (DCP) as a radical initiator and based on the formation of macroradicals derived from the hydrogen abstraction of the biopolymer backbone. Then, PBS-g-MAH was used as reactive compatibilizer for PBS filled with different contents of pistachio shell flour (PSF) during melt extrusion. As confirmed by Fourier transform infrared (FTIR), PBS-g-MAH acted as a bridge between the two composite phases since it was readily soluble in PBS and could successfully form new esters by reaction of its multiple MAH groups with the hydroxyl (–OH) groups present in cellulose or lignin of PSF and the end ones in PBS. The resultant compatibilized green composites were, thereafter, shaped by injection molding into 4-mm thick pieces with a wood-like color. Results showed significant increases in the mechanical and thermomechanical rigidity and hardness, meanwhile variations on the thermal stability were negligible. The enhancement observed was related to the good dispersion and the improved filler-matrix interfacial interactions achieved by PBS-g-MAH and also to the PSF nucleating effect that increased the PBS’s crystallinity. Furthermore, water uptake of the pieces progressively increased as a function of the filler content, whereas the disintegration in controlled compost soil was limited due to their large thickness.

Fabrication and microstructure evolution of Csf/ZrB2-SiC composites via direct ink writing and reactive melt infiltration

Fiber damage and uniform interphase preparation are the main challenges in conventional short fiber reinforced ceramic matrix composites. In this work, we develop a novel processing route in fabrication of short carbon fiber reinforced ZrB2-SiC composites (Csf/ZrB2-SiC) overcoming the above two issues. At first, Csf preforms with oriented designation and uniform PyC/SiC interphase are fabricated via direct ink writing (DIW) of short carbon fiber paste followed by chemical vapor infiltration. After that, ZrB2 and SiC are introduced into the preforms by slurry impregnation and reactive melt infiltration, respectively. Microstructure evolution and optimization of the composites during fabrication are investigated in detail. The as-fabricated Csf/ZrB2-SiC composites have a bulk density of 2.47 g/cm3, with uniform weak interphase and without serious fiber damage. Consequently, non-brittle fracture occurs in the Csf/ZrB2-SiC composites with widespread toughening mechanisms such as crack deflection and bridging, interphase debonding, and fiber pull-out. This work provides a new opportunity to the material design and selection of short fiber reinforced composites.

Hybrid processing of TiC/TiCu/C composites with tailored hardness

This work reports the effect of TiC volume fractions on hardness of TiC/TiCu/C composites synthesized through in situ reactive infiltration of Ti-Cu alloy into porous carbon preforms prepared by 3 D-printing. Reactive melt infiltration of the alloy at 1100 °C under argon into C-preforms with different porosities resulted in materials composed of TiC, Cu-rich intermetallic matrix (Ti3Cu4) and residual carbon. The microstructure consists of TiC grains distributed along the Cu-Ti/C boundary. The hardness of TiC/Ti3Cu4/C composites could be tailored by the TiC volume fraction and the distribution in the composites, which are determined by the processing parameters and the initial porosity of the carbon templates in 3 D-printing stage. The hardness of the produced composites ranges from 350 HV to 570 HV and could be tailored by the TiC volume fraction and distribution in the composites, which are determined by the processing parameters and the initial porosity of the carbon-preforms.