Bentonite is an abundant natural resource in the Maghnia region of Algeria that may have potential value in catalysis, but heretofore has been considered of low value for this purpose due to its low acidity and low catalytic activity. Low cost is one of the main criteria for choosing a suitable material for catalysis. Because bentonite is abundant and low-cost, its use as a starting material for the preparation of catalysts deserves reconsideration. The present study was undertaken, therefore, to optimize the performance of bentonite as a catalyst in one of the most promising reactions in organic synthesis, namely, cyclohexene epoxidation. The bentonite was subjected to adjustment of its structure by means of a number of laboratory treatments based on its large cation exchange capacity. These modifications aimed to achieve an environmentally friendly catalytic process by incorporating transition metals, specifically titanium and vanadium, into the modified bentonite structure through acid activation. Redox properties were enhanced and Lewis and Brønsted acidities were introduced. The vanadium oxide, supported on titania-pillared, acid-activated bentonite (5V/Ti-AAC), was characterized comprehensively using various techniques, including diffuse-reflectance UV-visible spectroscopy (DR UV-Vis), Fourier-transform infrared spectroscopy (FTIR) for surface acidity analysis, X-ray diffraction (XRD), nitrogen adsorption-desorption isotherms, and scanning electron microscopy (SEM) coupled with energy-dispersive X-ray elemental analysis (EDX). The catalytic activity was investigated in response to certain variables, such as catalyst mass, nature of the solvent, amount of oxidant, and reaction temperature. A kinetic study was conducted to understand the reaction behavior. The experimental results demonstrated intriguing catalytic activity, achieving a 42% conversion rate with ~68% selectivity toward the epoxide product when employing tert-butyl hydroperoxide (TBHP) as the oxidant and heptane as the solvent. This study highlights the potential of 5V/Ti-AAC as an environmentally friendly catalyst applied in the epoxidation of cyclohexene.

A unique vanadium-titanium-bearing mixed-layered clay is currently being mined as an ore of vanadium at Potash Sulphur Springs, AR. The clay contains 80% expandable portion and has both a 14.22 and 18.24 Å hydration state in addition to the 9.49 Å dehydrated state; ethylene glycol expands this material to 16.69 Å. The 060 reflection for all hydration states is between 1.50 and 1.51 Å indicating the material is dioctahedral. The “mean chemical formula” calculates as(Ca0.08 K0.02 Na0.03)0.13 (Al0.11 V0.90 Ti0.19 Fe0.64 Mg0.14)1.98 (Si3.79 Al0.21)4 O10 (OH)2·nH2O.

A series of mixed iron and titanium oxide coprecipitates ranging in composition between 0 < Ti/Ti + Fe < 1 was synthesized and aged under varying conditions of pH, temperature and time in order to establish a working model for pedogenic titanium and titano-ferric oxides. X-ray powder diffraction (XRD), selective chemical dissolution, magnetic susceptibility, charge distribution and electron optical data indicate that the freshly prepared Fe-Ti oxides consist of an Fe-rich (Ti-ferrihydrite) phase (Ti/Ti + Fe ⩽ 0.70) having pH-dependent positive charge and a Ti-rich phase (Ti/Ti + Fe ⩾ 0.7) with permanent and pH dependent negative charge.

Synthetic Ti-ferrihydrite and amorphous TiO2 were completely soluble in acid ammonium oxalate (2 hr extraction in the dark) whereas poorly crystalline anatase (width at half height, WHH > 2.0°2θ) was partly oxalate soluble. NH4-oxalate soluble Ti was particularly high in soils developed under a cool montane climate (afro-alpine) and lower in soils of warmer subtropical climate, which contain anatase and rutile.

Several mixed Fe-Ti crystalline phases were identified after aging NH3 coprecipitates of Fe and Ti nitrate at 70°C and pH 5.5 for 70 days:

1. (1) goethite and hematite in the composition range 0 < Ti/Ti + Fe ⩽ 0.20; at low Ti concentrations (<5 mole %) goethite was favored and/or hematite inhibited

2. (2) microcrystalline pseudorutile in the composition range 0.20 ⩽ Ti/Ti + Fe ⩽ 0.70

3. (3) anatase and ferriferous anatase in the range 0.70 ⩽ Ti/Ti + Fe < 1.0; with decreasing proportion of Ti the crystal-Unity of anatase decreased.

The results suggest that secondary or pedogenic Ti-Fe oxides can form by coprecipitation and crystallization in the weathering solution, and emphasize the essential role of water (as opposed to dry oxidation) in the alteration of primary titaniferous minerals.

Six kaolin samples from the Lower Tertiary Huber Formation near Wrens, Georgia were analyzed using transmission electron microscopy (TEM), electron diffraction (ED), powder X-ray diffraction (XRD), chemical analysis, and magnetic susceptibility to characterize the Ti-bearing phases. Selected samples were treated with 5 M NaOH to remove kaolinite and concentrate the Ti-bearing phases for additional analysis. TiO2 content in the bulk fraction ranges from 1.2 to 5.4 wt. %. There are at least three Ti-bearing phases, including anatase, rutile, and a poorly defined nanocrystalline form. Anatase is most abundant and is commonly found with {010} faces in association with kaolinite edge and basal faces. The nanocrystalline form occurs at 0–1 wt. %, and rutile occurs in trace amounts. Bulk XRD analysis correlates well with the bulk TiO2 chemical measurements. Average anatase unit-cell parameters are a = 0.37908 ± 0.0002 nm and c = 0.951 ± 0.001 nm. These parameters indicate an approximate chemical formula of Fe3+0.05Ti4+0.95O1.95(OH)0.05.

The distribution of TiO2 content as a function of depth may be useful to obtain original grain-size variations associated with relative sea-level changes responsible for the deposition of the Huber Formation. Evidence for original depositional sediment properties can be seen in the occurrence of pseudomorphic replacement of micas and fecal pellets by kaolinite. Additional evidence for post-depositional changes includes the sub-micrometer euhedral character and low Fe content of the anatase (relative to soil-derived anatase). These observations for the Huber Formation are consistent with a previously published theory for kaolin genesis that includes biomineralization of originally coarser-grained aluminosilicates into a kaolinite-rich ore body.

The modification of montmorillonite with metallic species affects directly its crystalline structure, texture, porosity, and surface. The interaction of the metallic molecules with the clay matrix, derived from the modification pathway and the characteristics of the adsorbate, modifies the physicochemical properties of montmorillonite, enabling the creation of materials with varied characteristics to be used both as catalysts and adsorbents. Small amounts of metallic species can confer various structural and physicochemical characteristics on the same montmorillonite matrix, depending on the metal incorporated. The objective of the present study was to create an acid-base catalyst based on montmorillonite K10 (K10 Mnt), modified with Ti, Ce, and Ni, for the catalytic esterification of acetic acid and penta-1-ol. K10-Mnt was modified using particles of Ti and of Ti modified with Ce and Ni. The effect of the inclusion of Ti and modified Ti species on the transformation of the physicochemical properties of the K10 Mnt and their contributions to the catalytic esterification syntheses were investigated. Samples were characterized by scanning electron microscopy coupled to an energy-dispersive X-ray spectroscopy system (SEM-EDS), powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), physisorption of N2 at 77 K (BET and BJH), and thermogravimetric analysis (TGA-DTGA). Finally, the original and modified K10 Mnt samples were tested for their catalytic esterification of acetic acid and penta-1-ol in the liquid phase.

This review is concerned with the synthesis and physical-chemical characteristics of a specific type of modified clay material: Ti-PILCs. The two general synthetic procedures and the main problems associated with the scale-up synthesis of these pillared materials are discussed in detail. The general characteristics of Ti-PILCs in terms of basal spacing, pillar homogeneity, surface area, microporosity, mesoporosity, pore size and distribution, thermal resistance and acidity are discussed in depth. Likewise, the most important synthesis parameters that have a clear and marked influence on the final characteristics of the materials are summarized.

In-home pet food testing has the benefit of yielding data which is directly applicable to the pet population. Validated and standardised in-home test protocols need to be available, and here we investigated key protocol requirements for an in-home canine food digestibility protocol. Participants were recruited via an online survey. After meeting specific inclusion criteria, sixty dogs of various breeds and ages received, during 14 consecutive days, a relatively low and high digestible complete dry extruded food containing titanium (Ti) dioxide. Both foods were given for 7 d in a cross-over design. Owners collected faeces daily allowing daily faecal Ti concentrations and digestibility of nitrogen (N), dry matter (DM), crude ash, organic matter (OM), crude fat (Cfat), starch and gross energy (GE) to be determined. Faecal Ti and digestibility values for all nutrients were not different (P > 0·05) from the second day onwards after first consumption for both foods. One day of faecal collection yielded reliable digestibility values with additional collection days not reducing the confidence interval around the mean. Depending on the accepted margin of error, the food and the nutrient of interest, the minimal required sample size was between 9 and 43 dogs. Variation in digestibility values could in part be explained by a dog’s neuter status (N, crude ash) and age (crude ash, Cfat) but not sex and body size. Future studies should focus on further identifying and controlling sources of variation to improve the in-home digestibility protocol and reduce the number of dogs required.

This paper presents the comparison of the microstructure of the interface zone formed between titanium (Ti Gr. 1) and steel (P265GH+N) in various processing stages—directly after explosive welding versus the annealing state. Transmission electron microscopy technique served as an excellent tool for studies of the sharp interface in-between the waves. Directly after the welding process in this area, a thin layer of the metastable β-Ti (Fe) solid solution was observed. In the next step, two variants of annealing have been employed: ex situ and in situ in TEM, which revealed the complete information on the interface zone transformation. The results have shown that during the annealing at 600°C for 1.5 h, the diffusion of carbon towards titanium caused the formation of titanium carbides with a layered arrangement. Compared to our previous studies, the carbides found here have a hexagonal structure. Furthermore, changes in the dislocation structure were observed, indicating the occurrence of recovery processes. Possible reasons for differences observed in the microstructure of the interface formed due to ex situ and in situ annealing are also discussed. The microstructure observations are accompanied by the microhardness measurements, which showed that the annealing caused a significant reduction in the microhardness values.

The new mineral bianchiniite, Ba2(Ti4+V3+)(As2O5)2OF, has been discovered in the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. It occurs as brown {001} tabular crystals, up to 1 mm across, with a vitreous lustre. It is brittle, with a perfect {001} cleavage. Streak is brownish. In reflected light, bianchiniite is grey, with orange–yellow internal reflections. It is weakly bireflectant, with a very weak anisotropy in shades of grey. Minimum and maximum reflectance data for COM wavelengths [Rmin/Rmax (%), (λ, nm)] are: 5.0/5.8 (470), 5.7/6.5 (546), 5.7/7.0 (589) and 5.2/6.3 (650). Electron microprobe analyses gave (wt.% – average of 10 spot analyses): TiO2 10.34, V2O3 3.77, Fe2O3 3.76, As2O3 44.36, Sb2O3 0.22, SrO 0.45, BaO 34.79, PbO 0.28, F 1.77, sum 99.74, –O = F –0.75, total 98.99. On the basis of 12 anions per formula unit, the empirical formula of bianchiniite is (Ba2.00Sr0.04Pb0.02)Σ2.06(Ti4+1.14V3+0.44Fe3+0.42)Σ2.00[(As3.96Sb0.02)Σ3.98O10](O1.18F0.82)Σ2.00. Bianchiniite is tetragonal, space group I4/mcm, with unit-cell parameters a = 8.7266(4), c = 15.6777(7) Å, V = 1193.91(12) Å3 and Z = 8. Its crystal structure was refined from single-crystal X-ray diffraction data to R1 = 0.0134 on the basis of 555 unique reflections with Fo > 4σ(Fo) and 34 refined parameters. The crystal structure shows columns of corner-sharing [Ti/(V,Fe)]-centred octahedra running along c, connected along a and b through (As2O5) dimers. A {001} layer of Ba-centred [10+2]-coordinated polyhedra is intercalated between (As2O5) dimers. Bianchiniite has structural relations with fresnoite- and melilite-group minerals. The name honours the two mineral collectors Andrea Bianchini (b. 1959) and Mario Bianchini (b. 1962) for their contribution to the knowledge of the mineralogy of pyrite ± baryte ± iron-oxide ore deposits from the Apuan Alps.

Potential secondary influences on titanium distribution should be evaluated when using ash beds as volcanic source indicators and for correlation purposes. In this study, well-correlated altered ash beds in Permian–Triassic boundary (PTB) successions of various facies in South China were investigated to better understand their use in source discrimination and stratigraphic correlation. The ash beds deposited in lacustrine and paludal facies contain significantly more Ti relative to deposits in marine facies. Neoformed anatase grains nanometres to micrometres in size are associated closely with clay minerals, whereas detrital anatase was observed in the remnants of altered ash beds of terrestrial facies. Extraction of the clay fraction of altered ash beds may exclude significantly detrital accessory minerals such as anatase and rutile added during sediment reworking, and the concentrations of immobile elements in the clay fraction may therefore be used to interpret more effectively their source igneous rocks.

New occurrences of derbylite, Fex2+Fe3+4–2xTi4+3+xSb3+O13(OH), and graeserite, Fex2+Fe3+4–2xTi4+3+xAs3+O13(OH), have been identified in the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy. Derbylite occurs as prismatic to acicular black crystals in carbonate veins. Iron and Ti are replaced by V (up to 0.29 atoms per formula unit, apfu) and minor Cr (up to 0.04 apfu). Mössbauer spectroscopy confirmed the occurrence of Fe2+ (up to 0.73 apfu), along with Fe3+. The Sb/(As+Sb) atomic ratio ranges between 0.73 and 0.82. Minor Ba and Pb (up to 0.04 apfu) substitute. Derbylite is monoclinic, space group P21/m, with unit-cell parameters a = 7.1690(3), b = 14.3515(7), c = 4.9867(2) Å, β = 104.820(3)° and V = 495.99(4) Å3. The crystal structure was refined to R1 = 0.0352 for 1955 reflections with Fo > 4σ(Fo). Graeserite occurs as prismatic to tabular black crystals, usually twinned, in carbonate veins or as porphyroblasts in schist. Graeserite in the first kind of assemblage is V rich (up to 0.66 apfu), and V poor in the second kind (0.03 apfu). Along with minor Cr (up to 0.06 apfu), this element replaces Fe and Ti. The occurrence of Fe2+ (up to 0.68 apfu) is confirmed by Mössbauer spectroscopy. Arsenic is dominant over Sb and detectable amounts of Ba and Pb have been measured (up to 0.27 apfu). Graeserite is monoclinic, space group C2/m, with unit-cell parameters for two samples: a = 5.0225(7), b = 14.3114(18), c = 7.1743(9) Å, β = 104.878(3)°, V = 498.39(11) Å3; and a = 5.0275(4), b = 14.2668(11), c = 7.1663(5) Å, β = 105.123(4)° and V = 496.21(7) Å3. The crystal structures were refined to R1 = 0.0399 and 0.0237 for 428 and 1081 reflections with Fo > 4σ(Fo), respectively. Derbylite and graeserite are homeotypic. They share the same tunnel structure, characterised by an octahedral framework and cuboctahedral cavities, hosting (As/Sb)O3 groups and (Ba/Pb) atoms.

Novel three-dimensional (3D) hierarchical macro- to nano-porous titanium (Ti) and TiMo alloys with sufficient compressive strength (CS) were prepared using NaCl spacer and dealloying methods. The dealloying process was implemented by the heat treatment of TiCu and TiMoCu master alloys in Mg powders. The 3D-hierarchical porous structures were composed of large pores having a mean size of 400 μm with interconnected micro-pores in the size of 10–30 μm, where the pore walls possessed numerous nano-pores with a size range of 10–50 nm. The CS and elastic modulus values were 72.4 MPa and 2.67 GPa as well as 92.62 MPa and 3.36 GPa for Ti and TiMo, respectively. The hierarchical porous structure is beneficial for the fast nucleation of bone-like apatite after immersion in simulated body fluid (SBF). In addition, TiMo samples after NaOH and heat treatments provide better apatite formation after soaking in SBF for a week, in comparison with the samples without treatment.

In this paper, we report the recent progress on the $1~\text{PW}/0.1~\text{Hz}$ laser beamline of Shanghai Superintense Ultrafast Laser Facility (SULF). The SULF-1 PW laser beamline is based on the double chirped pulse amplification (CPA) scheme, which can generate laser pulses of 50.8 J at 0.1 Hz after the final amplifier; the shot-to-shot energy fluctuation of the amplified pulse is as low as 1.2% (std). After compression, the pulse duration of 29.6 fs is achieved, which can support a maximal peak power of 1 PW. The contrast ratio at $-80~\text{ps}$ before main pulse is measured to be $2.5\times 10^{-11}$. The focused peak intensity is improved by optimizing the angular dispersion in the grating compressor. The maximal focused peak intensity can reach $2.7\times 10^{19}~\text{W}/\text{cm}^{2}$ even with an $f/26.5$ off-axis parabolic mirror. The horizontal and vertical angular pointing fluctuations in 1 h are measured to be 1.89 and $2.45~\unicode[STIX]{x03BC}\text{rad}$, respectively. The moderate repetition rate and the good stability are desirable characteristics for laser–matter interactions. The SULF-1 PW laser beamline is now in the phase of commissioning, and preliminary experiments of particle acceleration and secondary radiation under 300–400 TW/0.1 Hz laser condition have been implemented. The progress on the experiments and the daily stable operation of the laser demonstrate the availability of the SULF-1 PW beamline.

Influence of boron nitride (BN) addition in commercially pure titanium (Cp-Ti) was characterized for their microstructural variation, hardness, and oxidation kinetics. Feedstock powders, Cp-Ti with 3 wt% BN (3BN) and 6 wt% BN (6BN), were prepared by roller mill followed by additive manufacturing using laser engineered net shaping (LENS™). Rate of oxidation was measured from thermogravimetric analysis (TGA) at 1000 °C for 50 h. Average instantaneous parabolic constants (kp) for Cp-Ti, 3BN, and 6BN were 41.2 ± 12.0, 28.6 ± 2.8, and 18.2 ± 9.2 mg2/(cm4 h), respectively. Cp-Ti displayed acicular α-Ti microstructure. After TGA, large equiaxed grains along with TiO2 formation at the grain boundaries were observed, which increased the hardness. With BN addition, plate-like TiN and needle-like TiB secondary phases were also observed. Hardness for Cp-Ti, 3BN, and 6BN were 256.9 ± 7.7, 424.0 ± 33.6, and 548.3 ± 49.7 HV0.2, respectively. Overall, a small addition of BN was effective in improving the oxidation resistance of Cp-Ti.

The design and the processing of a new class of titanium boride (TiB)-based bulk cermets containing a metallic phase (β-Ti phase) for toughening is presented. The general approach is rapid reaction and densification, using starting powders of Ti, TiB2, Fe, and Mo, by electric-field-activated sintering. The cermets consist of two-phase microstructures in which the boride phase formed as a networked structure of TiB whiskers that were created in situ upon the reaction between the powders. Hardness, flexural strength, and fracture toughness measurements of these materials revealed that they possess an interesting set of properties up to: hardness values of 1090 kg/mm2, flexural strength values of 953 MPa, and fracture toughness values of 18 MPa m1/2. A remarkable finding is that although the metallic phase fractured by microscopic cleavage, the cermets showed good fracture toughness values. The present study not only illustrates the process details and microstructure leading to these properties but also provides a broad powder metallurgical approach to design and synthesize cermets that may yield further improved properties.

A commercially pure titanium (CP-Ti) of grade 1 as a hard-to-deform material was processed successfully by ECAP processing up to four passes at room temperature via the core–sheath method using a die with an internal channel angle of 90°. The simulation and analytical calculations demonstrated that imposed back pressure on the core was increased at each pass due to strain hardening of sheath metal (AISI 1015 steel) during deformation which prevented damage accumulation and crack initiation at a high number of passes. The scanning electron microscopy and transmission electron microscopy observations of ECAP-processed Ti revealed a severely deformed microstructure which consisted of a high dislocation density and an average grain size of ∼250 nm. Mechanical properties of four-pass ECAP-processed CP-Ti showed a substantial enhancement of ultimate tensile strength up to 890 MPa associated with a reasonable elongation to failure of 15.3%.

Contamination by bacterial biofilms has a strong negative impact, especially on the surface of prostheses, implants, pins, and other medical-surgical devices. To prevent their formation, one of the alternatives is the modification of the metal surface incorporating silver by low-energy ion implantation, thus avoiding initial bacteria adhesion to the modified surface and further development of the biofilm. The bactericidal properties of silver atoms incorporated on commercially pure titanium surfaces by low-energy ion implantation (4 keV) were evaluated. The surface modifications were analyzed by Rutherford backscattering spectrometry, glow discharge-optical emission spectroscopy, contact angle measure, optical profilometry, and X-ray photoelectron spectroscopy. The microbiological assays were conducted by using Escherichia coli (E. coli). The results demonstrated a reduction on bacterial counting. No toxic effect of silver was detected on human MG-63 cells. The choice of parameters to obtain a bactericidal and nontoxic biomaterial for human cells should consider the ideal combination “energy + silver concentration”. Therefore, it can be considered for industrial application.

The absorption spectrum of Ti3+ in quartz is typical for that element in an octahedral site, except for the high oscillator strength of the band which indicates intensive charge transfer, most likely between a substitutional Ti4+ and an interstitial Ti3+. The biaxial anisotropy of the band is similar to that of octahedral Fe2+ in the same crystal, suggesting the same site for the Ti3+, an interstitial site at the intersection of the threefold axis with two twofold axes. The dynamic nature of the Ti and Fe ions is indicated when the crystal is subjected to X-irradiation and then to bleaching treatment with UV-light or heat. Ti(IV) ions are acceptors of electrons donated by Fe2+ during X-irradiation. This is indicated by increase of the 2.4 eV band intensity with decrease in the Fe2+ band intensities and appearance of Fe3+ charge transfer bands in the UV-region. Heat and UV-light treatment decrease the Fe3+ CT bands and increase the Fe2+ crystal-field bands along with decrease in the 2.4 eV band related to titanium.