Ceramics, Volume 4, Issue 4 (December 2021) – 10 articles

Porous functional graded ceramics (porous FGCs) offer immense potential to overcome the low mechanical strengths of homogeneously porous bioceramics used as bone grafts. The tailored manipulation of the graded pore structure including the interfaces in these materials is of particular interest to locally control the microstructural and mechanical properties, as well as the biological response of the potential implant. In this work, porous FGCs with integrated interface textures were fabricated by a novel two-step transfer micro-molding technique using alumina and hydroxyapatite feedstocks with varied amounts of spherical pore formers (0–40 Vol%) to generate well-defined porosities. Defect-free interfaces could be realized for various porosity pairings, leading to porous FGCs with continuous and discontinuous transition of porosity. The microstructure of three different periodic interface patterns (planar, 2D-linear waves and 3D-Gaussian hills) was investigated by SEM and µCT and showed a shape accurate replication of the CAD-designed model in the ceramic sample. The Young’s modulus and flexural strength of bi-layered bending bars with 0 and 30 Vol% of pore formers were determined and compared to homogeneous porous alumina and hydroxyapaite containing 0–40 Vol% of pore formers. A significant reduction of the Young’s modulus was observed for the porous FGCs, attributed to damping effects at the interface. Flexural 4-point-testing revealed that the failure did not occur at the interface, but rather in the porous 30 Vol% layer, proving that the interface does not represent a source of weakness in the microstructure. Full article

Al₂O₃-TiO₂ systems with Ti:Al 0.1, 0.5 and 1.0 molar ratio obtained by the sol–gel method have been used as a platinum support. As a precursor of alumina gel, aluminum isopropoxide has been chosen. Titanium tert-butoxylate was applied to obtain titania gel and hexachloroplatinic acid was applied as a source of platinum. The systems have been characterized by the following methods: thermogravimetric analysis (TGA), Fourier transformation infrared spectroscopy (FTIR), X-ray powder diffraction (XRPD), low-temperature nitrogen adsorption–desorption isotherms (BET, BJH), temperature-programmed reduction with hydrogen (TPR-H₂) and hydrogen chemisorption. Reactions of toluene to methylcyclohexane and selective o-chloronitrobenzene (o-CNB) to o-chloroaniline (o-CAN) hydrogenation were used as the tests of systems’ catalytic activity. The application of Al₂O₃-TiO₂ as a support has enabled the obtaining of platinum catalysts showing high activities for hydrogenation of toluene and selective hydrogenation of o-chloronitrobenzene to o-chloroaniline in the liquid phase. The highest activity in both reactions has been found for Pt/Al₂O₃-0.5TiO₂ catalyst and the highest selectivity for Pt/Al₂O₃-. The activity of Pt/Al₂O₃-TiO₂ catalysts was higher than that of alumina-supported ones. Full article

It is well known that doloma bricks present better coating adherence than magnesia–spinel bricks when applied in cement rotary kilns, which is related to the different coating formation mechanism. The coating has an essential role in prolonged operation by protecting the refractory lining; thus, it is important to improve its adherence on magnesia–spinel refractories. The objective of this investigation is to study different compositions of magnesia–spinel bricks, achieved by varying additives used (calcined alumina, limestone, hematite and zirconia) and firing temperature (1500 °C and 1700 °C), to enhance the coating adherence measured by the sandwich test. The results have pointed out that the use of higher firing temperature contributes positively to physical adherence due to well-sintered refractory structure and elevated permeability, attaining coating strength superior to 2 MPa. For the chemical adherence, the addition of 2 wt.% of limestone increased the coating strength to 3 MPa, but resulted in a drop in hot properties. In this context, the most suitable approach to improve adherence of clinker coating and maintain hot properties in suitable levels is to increase the firing temperature. Full article

Glass-ceramic nanopowder with a composition of 55SiO₂-35CaO-10MgO (mol %) was synthesized by the sol–gel method and was heat treated at three temperatures (T1 = 835 °C, T2 = 1000 °C, T3 = 1100 °C) in order to obtain different materials (C1, C2, C3, respectively) varying in crystal structure. Bioactivity and oxidative stress were evaluated in simulated body fluid (SBF) for various time periods (up to 10 days). The structure of the synthesized materials and their apatite-forming ability were investigated by X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning Electron Microscopy and Energy Dispersive Spectroscopy (SEM/EDS). The antibacterial properties of the synthesized materials were evaluated against three Gram-positive and four Gram-negative bacterial strains and their biocompatibility was verified on a primary cell line of human gingival fibroblasts (HGFs) by the MTT (3-[4, 5-dimethylthiazol-2-yl]-2, 5 diphenyl tetrazolium bromide) assay. The crystallization of the materials was increased by sintering temperature. Heat treatment did not inhibit the bioactive behavior of the materials as apatite formation started after 3 days in SBF. C2, C3 showed some indications of apatite forming even from the first day. Regarding cell viability, a variety of biological behaviors, concerning both dose and time points, was observed between the positive control and the tested materials by both the MTT assay and oxidative stress analysis. In conclusion, the nanobioceramic materials of this study possess a multitude of attractive physicochemical and biological properties that make them suitable candidates for bone regeneration applications, fillers in nanocomposite scaffolds, or as grafts in bone cavities and periodontal lesions. Full article

Spark Assisted Chemical Engraving (SACE) is a micro-machining technology for non-conductive materials, mainly glass, based on thermal assisted etching. Generally, during SACE, drilling proceeds at a fast rate reaching 100 µm/s for the first 100 µm and then it slows down for depths higher than 300 µm. While several techniques have been proposed to establish faster drilling, they mainly rely on tuning the machining parameters to enhance the machining performance. However, with this approach machining parameters need to be constantly tuned to achieve certain machining performance depending on the size of the tool and the features needed. Therefore, this necessitates further work to enhance understanding regarding the SACE machining process fundamentals in order to enhance machining speed and quality. Since SACE is a thermal assisted etching process, both local heating and flushing of electrolyte in the machining zone are required. However, to the authors’ knowledge there is not any study that attempts to analyze the effect of each of these machining limiting factors on the machining performance. This work attempts to clarify the effect of each flushing and heating on the drilling progress for hole depths higher than 100 microns. It therefore provides a deeper understanding of the fundamentals of the SACE machining process. Full article

In this study, the compressive strength and the permeation properties of fly ash-based Geopolymer were experimentally investigated. Type 2 Portland cement (T2PC) was partially or entirely replaced with 0, 10, 20, 30, 50, 70, and 100% of fly ash (FA). The laboratory tests were conducted for compressive strength at 7, 28, and 90 days, and permeation properties such as water absorption at 7 and 28 days. The main goal was to produce eco-friendly concrete with high strength and low permeability through blending cementitious materials including low Calcium (Ca) (T2PC and FA) for protecting concrete against sulphate attacks and other chemically destructive compounds in the environment. This study focused on the effectiveness of the curing period, combinations of chemical activators by varying the molarity of alkaline solutions between 4.16 and 12.96 M and keeping the sodium silicate (SS) to sodium hydroxide (SH) by the weight ratio of 2.5. Lab observations from this study demonstrated that the compressive strength was enhanced with the increment in fly ash content at all ages, with optimum being at 20% as the replacement of T2PC. Full article

Metal–ceramic composites are obtained via ex-situ or in-situ routes. The in-situ route implies the synthesis of reinforcement in the presence of a matrix and is often regarded as providing more flexibility to the microstructure design of composites than the ex-situ route. Spark plasma sintering (SPS) is an advanced sintering method that allows fast consolidation of various powder materials up to full or nearly full density. In reactive SPS, the synthesis and consolidation are combined in a single processing step, which corresponds to the in-situ route. In this article, we discuss the peculiarities of synthesis of ceramic reinforcements in metallic matrices during SPS with a particular consideration of reactant/matrix mutual chemistry. The formation of carbide reinforcements in Cu, Al, and Ni matrices is given attention with examples elaborated in the authors’ own research. Factors determining the suitability of reactive SPS for manufacturing of composites from a matrix/reactants system and features of the structural evolution of the reaction mixture during sintering are discussed. Full article

In this work, Zn²⁺-doped TiO₂:WO₃ nanostructured films, with different doping levels, were produced by electrospinning followed by sintering, and tested as potential materials for relative humidity (RH) detection. The materials microstructure was investigated by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, and X-ray diffraction (XRD). The electrical characterization was performed by electrical impedance spectroscopy in the range of 400 HZ–40 MHZ, at 20 °C. The sensors’ sensitivity to moisture was evaluated from the impedance variations in response to changes in RH (10–100%). The analyses confirmed the interaction of water molecules with the oxides surface, and showed that zinc atoms were incorporated into the titanium vacancies in the crystal lattice. All the studied sensors showed a p- to n-type conduction transition taking place at around 40% RH. The nanocomposite with 2 wt% of dopant presented the best sensitivity to moisture, with an impedance variation of about 1 order of magnitude. The results are discussed in relation to the microstructure and fabrication route. Full article

In this paper, the thermal decomposition of crystalline Al(OH)₃ was studied over the temperature range of 260–400 °C for particles with a size between 10 and 150 µm. The weight losses and thermal effects occurring in each of the dehydration process were assessed using thermogravimetry (TG) and differential scanning calorimetry (DSC) thermal analysis. X-ray diffraction (XRD) patterns, refined by the Rietveld method, were used for mineral phase identification, phase composition analysis, and crystallinity degree determination. Moreover, the particle size distributions and their corresponding D10, D50, and D90 numeric values were determined with a laser analyzer. We observed a strong relationship between the calcination temperature, the initial gibbsite grade particle size, and the crystallinity of the resulting powders. Hence, for all endothermic effects identified by DSC, the associated temperature values significantly decreased insofar as the particle dimensions decreased. When the gibbsite was calcined at a low temperature, we identified small amounts of boehmite phase along with amorphous new phases and unconverted gibbsite, while the powders calcined at 400 °C gradually yielded a mixture of boehmite and crystalized γ-Al₂O₃. The crystallinity % of all phase transition products declined with the increase in particle size or temperature for all the samples. Full article

Calcium phosphates (CaPs) are biocompatible and biodegradable materials showing a great promise in bone regeneration as good alternative to the use of auto- and allografts to guide and support tissue regeneration in critically-sized bone defects. This can be certainly attributed to their similarity to the mineral phase of natural bone. Among CaPs, hydroxyapatite (HA) deserves a special attention as it, actually is the main inorganic component of bone tissue. This review offers a comprehensive overview of past and current trends in the use of HA as grafting material, with a focus on manufacturing strategies and their effect on the mechanical properties of the final products. Recent advances in materials processing allowed the production of HA-based grafts in different forms, thus meeting the requirements for a range of clinical applications and achieving enthusiastic results both in vitro and in vivo. Furthermore, the growing interest in the optimization of three-dimensional (3D) porous grafts, mimicking the trabecular architecture of human bone, has opened up new challenges in the development of bone-like scaffolds showing suitable mechanical performances for potential use in load bearing anatomical sites. Full article