Natural structural materials are built at ambient temperature from a fairly limited selection of components. They usually comprise hard and soft phases arranged in complex hierarchical architectures, with characteristic dimensions spanning from the nanoscale to the macroscale. The resulting materials are lightweight and often display unique combinations of strength and toughness, but have proven difficult to mimic synthetically. Here, we review the common design motifs of a range of natural structural materials, and discuss the difficulties associated with the design and fabrication of synthetic structures that mimic the structural and mechanical characteristics of their natural counterparts.

Bioinspired structural materials

This paper reviews the past, present, and future of the hydroxyapatite (HAp)-based biomaterials from the point of view of preparation of hard tissue replacement implants. Properties of the hard tissues are also described. The mechanical reliability of the pure HAp ceramics is low, therefore it cannot be used as artificial teeth or bones. For these reasons, various HAp-based composites have been fabricated, but only the HAp-coated titanium alloys have found wide application. Among the others, the microstructurally controlled HAp ceramics such as fibers/whiskers-reinforced HAp, fibrous HAp-reinforced polymers, or biomimetically fabricated HAp/collagen composites seem to be the most suitable ceramic materials for the future hard tissue replacement implants.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0884291400042527

Processing and properties of hydroxyapatite-based biomaterials for use as hard tissue replacement implants

Composition of reactive powder concretes

This paper reviews the crystal chemistry, synthesis, densification, microstructure, mechanical properties, and oxidation behavior of zirconium diboride (ZrB2) and hafnium diboride (HfB2) ceramics. The refractory diborides exhibit partial or complete solid solution with other transition metal diborides, which allows compositional tailoring of properties such as thermal expansion coefficient and hardness. Carbothermal reduction is the typical synthesis route, but reactive processes, solution methods, and pre-ceramic polymers can also be used. Typically, diborides are densified by hot pressing, but recently solid state and liquid phase sintering routes have been developed. Fine-grained ZrB2 and HfB2 have strengths of a few hundred MPa, which can increase to over 1 GPa with the addition of SiC. Pure diborides exhibit parabolic oxidation kinetics at temperatures below 1100°C, but B2O3 volatility leads to rapid, linear oxidation kinetics above that temperature. The addition of silica scale formers such as SiC or MoSi2 improves the oxidation behavior above 1100°C. Based on their unique combination of properties, ZrB2 and HfB2 ceramics are candidates for use in the extreme environments associated with hypersonic flight, atmospheric re-entry, and rocket propulsion.

Refractory Diborides of Zirconium and Hafnium

The influence of cobalt particle size in the range of 2.6-27 nm on the performance in Fischer-Tropsch synthesis has been investigated for the first time using well-defined catalysts based on an inert carbon nanofibers support material. X-ray absorption spectroscopy revealed that cobalt was metallic, even for small particle sizes, after the in situ reduction treatment, which is a prerequisite for catalytic operation and is difficult to achieve using traditional oxidic supports. The turnover frequency (TOF) for CO hydrogenation was independent of cobalt particle size for catalysts with sizes larger than 6 nm (1 bar) or 8 nm (35 bar), while both the selectivity and the activity changed for catalysts with smaller particles. At 35 bar, the TOF decreased from 23 x 10(-3) to 1.4 x 10(-3) s(-1), while the C5+ selectivity decreased from 85 to 51 wt % when the cobalt particle size was reduced from 16 to 2.6 nm. This demonstrates that the minimal required cobalt particle size for Fischer-Tropsch catalysis is larger (6-8 nm) than can be explained by classical structure sensitivity. Other explanations raised in the literature, such as formation of CoO or Co carbide species on small particles during catalytic testing, were not substantiated by experimental evidence from X-ray absorption spectroscopy. Interestingly, we found with EXAFS a decrease of the cobalt coordination number under reaction conditions, which points to reconstruction of the cobalt particles. It is argued that the cobalt particle size effects can be attributed to nonclassical structure sensitivity in combination with CO-induced surface reconstruction. The profound influences of particle size may be important for the design of new Fischer-Tropsch catalysts.

/pdf/cobalt-particle-size-effects-in-the-fischer-tropsch-reaction-nvtmg7gy4b.pdf

Cobalt particle size effects in the fischer- : Tropsch reaction studied with carbon nanofiber supported catalysts

Physical properties of high strength cement pastes

The porosity of hardened cement paste was analysed using fluid displacement methods, optical, scanning and transmission electron microscopy and mercury intrusion porosimetry. Attention has been drawn to the problems of mercury porosimetry and in particular to the extent of the pore volume which is missed by mercury. Previous workers have assigned the “lost porosity” to pore sizes too fine to be seen by mercury but this paper considers the contribution of closed pores. Nitrogen and water adsorption studies have been carried out on the pastes to determine qualitatively the magnitude of the pore volume beyond the range of mercury porosimetry. This volume was found to be very small. Emphasis has been placed upon the importance of large spherical pores, which may be missed by mercury porosimetry and adsorption studies, in determining the strength of cement pastes.

An assesment of porosity and pore sizes in hardened cement pastes

A theoretical argument for the existence of high strength cement pastes

The columbite niobate ceramics ZnNb2O6, MgNb2O6, CaNb2O6 and CoNb2O6 have low dielectric losses at microwave (1–10 GHz) frequencies, resulting in Qf values between 40 000 and 90 000 GHz, making them suitable materials for use in dielectric resonator applications. However, their temperature coefficient of resonant frequency (τf) values were high, at between −50 and −90 ppm, and the optimum sintering temperatures were found to be between 1150°C and 1350°C. This paper details the doping of these ceramics with 1 wt%V2O5, 1 wt% CeO2, 2 wt% WO3 and 0.5 wt% CuO, in an attempt to reduce the sintering temperature. It was found that in many cases the dopants also had an extremely beneficial effect upon microwave properties, increasing er, and decreasing τf considerably. Although the dopants often had a deleterious effect upon the quality factor (Q), in some cases they caused an increase in Q. Qf values of over 20 000 GHz were often obtained at lower temperatures, even in poorly sintered niobates, and CuO-doped CaNb2O6 yielded Qf values in excess of 65 000 GHz. CoNb2O6+V2O5 or CuO gave 90% sintered and poorly sintered materials with Qf over 10 000 GHz and 25 000 GHz, respectively, at temperatures within low temperature Co-fired ceramic limits.

N. McN. Alford

Papers

Physical properties of high strength cement pastes

An assesment of porosity and pore sizes in hardened cement pastes

A theoretical argument for the existence of high strength cement pastes

The effects of sintering aids upon dielectric microwave properties of columbite niobates, M2+Nb2O6

The effect of lead nitrate on the physical properties of cement pastes