Effect of Hydrothermal Treatment and Doping on the Microstructural Features of Sol-Gel Derived BaTiO3 Nanoparticles

Barium Titanate (BaTiO₃) is one of the most promising lead-free ferroelectric materials for the development of piezoelectric nanocomposites for nanogenerators and sensors. The miniaturization of electronic devices is pushing researchers to produce nanometric-sized particles to be embedded into flexible polymeric matrices. Here, we present the sol-gel preparation of crystalline BaTiO₃ nanoparticles (NPs) obtained by reacting barium acetate (Ba(CH₃COO)₂) and titanium (IV) isopropoxide (Ti(OⁱPr)₄). The reaction was performed both at ambient conditions and by a hydrothermal process carried on at 200 °C for times ranging from 2 to 8 h. Doped BaTiO₃ nanoparticles were also produced by addition of Na, Ca, and Bi cations. The powders were annealed at 900 °C in order to improve NPs crystallinity and promote the cubic-to-tetragonal (c⟶t) phase transformation. The microstructural features of nanoparticles were investigated in dependence of both the hydrothermal reaction time and the presence of dopants. It is found that short hydrothermal treatment (2 h) can produce BaTiO₃ spherical and more homogeneous nanoparticles with respect to longer hydrothermal treatments (4 h, 6 h, 8 h). These particles (2 h) are characterized by decreased dimension (approx. 120 nm), narrower size distribution and higher tetragonality (1.007) in comparison with particles prepared at ambient pressure (1.003). In addition, the short hydrothermal treatment (2 h) produces particles with tetragonality comparable to the one obtained after the longest process (8 h). Finally, dopants were found to affect to different extents both the c⟶t phase transformation and the crystallite sizes.     

Low-Temperature Hydrothermal Treatment Surface Functionalization of the Ultrafine-Grained TiMo Alloys for Medical Applications

Hydroxyapatite (HAp) is the most widely used material for bio coating. The functional layer can be produced by many methods, however, the most perspective by its utility, easy to scale up, and simplicity aspects remains a hydrothermal treatment approach. In this work, an HAp coating was produced by low-temperature hydrothermal treatment on the ultrafine-grain beta Ti-xMo (x = 23, 27, 35 wt.%) alloys. The proposed surface treatment procedure combines acid etching, alkaline treatment (AT), and finally hydrothermal treatment (HT). The uniqueness of the approach relies on the recognition of the influence of the molar concentration of NaOH (5 M, 7 M, 10 M, 12 M) during the alkaline treatment on the growth of hydroxyapatite crystals. Obtained and modified specimens were examined structurally and microstructurally at every stage of the process. The results show that the layer after AT consist of titanium oxide and phases based on sodium with various phase relations dependent on NaOH concentration and base composition. The AT in 7 M and 10 M enables to obtain the HAp layer, which can be characterized as the most developed in terms of thickness and porosity. Finally, selected coated samples were investigated in terms of surface wettability test managed in time relation, which for the results confirm high hydrophilicity of the surfaces. Conducted research shows that the low-temperature hydrothermal processing could be considered for a possible adaptation in the drug encapsulation and delivery systems.     

Preparation and Characterization of Lignocellulosic Oil Sorbent by Hydrothermal Treatment of Populus Fiber

This study is aimed at achieving the optimum conditions of hydrothermal treatment and acetylation of Populus fiber to improve its oil sorption capacity (OSC) in an oil-water mixture. The characteristics of the hydrolyzed and acetylated fibers were comparatively investigated by FT-IR, CP-MAS ¹³C-NMR, SEM and TGA. The optimum conditions of the hydrothermal treatment and acetylation were obtained at 170 °C for 1 h and 120 °C for 2 h, respectively. The maximum OSC of the hydrolyzed fiber (16.78 g/g) was slightly lower than that of the acetylated fiber (21.57 g/g), but they were both higher than the maximum OSC of the unmodified fiber (3.94 g/g). In addition, acetylation after hydrothermal treatment for the Populus fiber was unnecessary as the increment of the maximum OSC was only 3.53 g/g. The hydrolyzed and the acetylated Populus fibers both displayed a lumen orifice enabling a high oil entrapment. The thermal stability of the modified fibers was shown to be increased in comparison with that of the raw fiber. The hydrothermal treatment offers a new approach to prepare lignocellulosic oil sorbent.     

Improving the Properties of Composite Titanium Nitride Layers on the AZ91D Magnesium Alloy Using Hydrothermal Treatment

Coating magnesium alloys with nitride surface layers is a prospective way of improving their intrinsically poor surface properties; in particular, their tribological and corrosion resistance. These layers are usually produced using PVD methods using magnetron sputtering or arc evaporation. Even though the thus-produced layers significantly increase the wear resistance of the alloys, their effects on corrosion resistance are unsatisfactory because of the poor tightness, characteristic of PVD-produced products. Tightness acquires crucial significance when the substrate is a highly-active magnesium alloy, hence our idea to tighten the layers by subjecting them to a post-deposition chemical-hydrothermal-type treatment. This paper presents the results of our experiments with a new hybrid surface engineering method, using a final tightening pressure hydrothermal gas treatment in overheated steam of the composite titanium nitride layers PVD, produced on AZ91D magnesium alloy. The proposed method resulted in an outstanding improvement of the performance properties, in particular resistance to corrosion and wear, yielding values that exceed those exhibited by commercially anodized alloys and austenitic stainless 316L steel. The developed hybrid method produces new, high-performance corrosion and wear resistant, lightweight magnesium base materials, suitable for heavy duty applications.     

Crystallization Behavior and Mechanical Properties of Poly(ε-caprolactone) Reinforced with Barium Sulfate Submicron Particles

Poly(ε-caprolactone) (PCL) was mixed with submicron particles of barium sulfate to obtain biodegradable radiopaque composites. X-ray images comparing with aluminum samples show that 15 wt.% barium sulfate (BaSO₄) is sufficient to present radiopacity. Thermal studies by differential scanning calorimetry (DSC) show a statistically significant increase in PCL degree of crystallinity from 46% to 52% for 25 wt.% BaSO₄. Non-isothermal crystallization tests were performed at different cooling rates to evaluate crystallization kinetics. The nucleation effect of BaSO₄ was found to change the morphology and quantity of the primary crystals of PCL, which was also corroborated by the use of a polarized light optical microscope (PLOM). These results fit well with Avrami–Ozawa–Jeziorny model and show a secondary crystallization that contributes to an increase in crystal fraction with internal structure reorganization. The addition of barium sulfate particles in composite formulations with PCL improves stiffness but not strength for all compositions due to possible cavitation effects induced by debonding of reinforcement interphase.     

Effects of Solution Treatment on Damping Capacities of Binary Mg-X (X = Ga and Er) Alloys

Designing new materials for vibration and noise reduction that are lightweight is of great significance for industrial development. Magnesium (Mg) alloy is considered one of the best damping metal structural materials because of its low density, high specific strength, good energy storage characteristics and rich resources. Solution atoms have an important effect on the damping capacities of Mg alloys, but the relevant laws have not been completely clarified. In this work, two kinds of alloying elements (Ga and Er) with various atomic sizes were selected to study the metallographic structure and damping capacities of binary Mg-X (X = Ga and Er) alloys in the as-cast and solid solution states, respectively. Solution treatment can improve the damping capacities of binary Mg-X (X = Ga and Er) alloys, and the damping mechanisms of the two solid solution alloys are consistent with the G-L damping mechanism. The influence of alloy elements with different atomic sizes on damping capacities is also different. This influence is due to the various radii of solute atoms and Mg atoms which can result in different degrees of lattice distortion. This work provides a research basis for development and design of high-performance damping Mg alloy materials.     

High Dose of Tranexamic Acid for Treatment of Severe Menorrhagia in Patients with von Willebrand Disease

Menorrhagia is one of the most important and frequent complications in women with congenital von Willebrand disease (vWD). Three cases of menorrhagia with vWD (type 1; 1 case, type 2A; 2 cases) were successfully treated with tranexamic acid at dose of 3 grams daily in four divided doses for the first 5 days of the menstrual cycle. All patients had severe menorrhagia lasted for more than 10 days with iron deficiency anemia of hemoglobin levels of 6.5–8.4 g/dl. Common dosage of tranexamic acid of 1 gram daily in 4 divided doses on days 1–5 of their menstrual cycles did not correct their menorrhagia. The treatment was then changed to the daily dose of 3 grams in 4 divided doses on days 1–5 of their menstrual cycles. Thereafter, their menorrhagia became well-controlled with improvement of their anemia up to hemoglobin of 11.5–12.4 g/dl. High dose of tranexamic acid has been administered safely in all patients for 3–5 years without significant complications. Oral high-dose administration of tranexamic acid is very convenient and useful for treatment of menorrhagia in the patients with vWD.     

Treatment of primary sclerosing cholangitis with low-dose ursodeoxycholic acid: results of a retrospective Italian multicentre survey

BACKGROUND: Data concerning the usefulness and type of drugs employed to treat patients with primary sclerosing cholangitis are controversial. Ursodeoxycholic acid has been shown to be a useful agent, however the drug dosage and its effect on the clinical course are still under debate. AIM: To evaluate the efficacy of low-dose ursodeoxycholic acid in the treatment of primary sclerosing cholangitis. METHODS: We retrospectively analysed data from 86 patients with primary sclerosing cholangitis from eight centres in Italy between 1987 and 1997: 69 were treated with ursodeoxycholic acid (8-13 mg/kg/day), while 17 received symptomatic treatment and served as controls. The effect of therapy was evaluated by standard liver function tests and symptom analysis. RESULTS: Ursodeoxycholic acid treatment was associated with significant improvement in serum alkaline phosphatase (735+/-833 vs. 519+/-448 U/l, p<0.001), gamma-glutamyl transpeptidase (401+/-352 vs. 234+/-235 U/l, p<0.001), aspartate aminotransferase (87+/-70 vs. 56+/-42 U/l, p=0.001), alanine aminotransferase (146+/-139 vs. 76+/-73 U/l, p<0.001), and total bilirubin (1.88+/-2.44 vs. 1.76+/-4.12 U/l, p=0.01); there was also amelioration of fatigue (p=0.007), jaundice (p=0.002), and body weight loss (p=0.002). CONCLUSIONS: Ursodeoxycholic acid, at a dose of 8-13 mg/kg/day was beneficial for the general condition and liver biochemistry of patients with primary sclerosing cholangitis; high-dose ursodeoxycholic acid treatment requires further evaluation.     

Treatment of isolated fat cells with trypsin inhibits the effects of insulin on incorporation of leucine into protein

Summary Incorporation of 0.1 mM³H-leucine into protein by isolated fat cells, with pyruvate as the only extracellular carbohydrate, was stimulated by: a) insulin, 0.1–4 ng/ml, or b) a mixture of 19 amino acids, 0.05–5 mM. Treatment of fat cells with trypsin, under conditions known to reduce binding of insulin by their plasma membranes, abolished stimulation of incorporation by the hormone but not by the amino acid mixture. These results imply that the actions of insulin on incorporation of amino acids into protein are initiated by interaction with plasma membranes.A preliminary report of this work was presented on June 22, 1972, at the IVth International Congress of Endocrinology, Washington, D.C. (abstract No. 423).     

Removal of Fe2+ and Mn2+ from Polluted Groundwater by Insoluble Humic Acid/Tourmaline Composite Particles

Insoluble humic acid/tourmaline composite particles (IHA/TM) were prepared by combining inorganic tourmaline (TM) with the natural organic polymer humic acid (HA) and carbonizing them at 330 °C to study the removal characteristics and mechanism of Fe²⁺ and Mn²⁺. The results showed that the optimal ratio of TM to IHA is 2:3. When the temperature of the IHA/TM composite particles was 35 °C and the pH was 6, the adsorption of Fe²⁺ and Mn²⁺ by IHA/TM reached equilibrium at 240 min. The optimum dose of the adsorbent was 10 g/L, and the equilibrium adsorption capacities of Fe²⁺ and Mn²⁺ were 5.645 mg/g and 3.574 mg/g, respectively. The process of IHA/TM adsorption of Fe²⁺ and Mn²⁺ in water was spontaneous, endothermic and sustainable, and cooling was not conducive to adsorption. The pseudo-second order kinetic equation can well reflect the adsorption mechanism of IHA/TM on Fe²⁺ and Mn²⁺, and the Langmuir adsorption model better describes the isothermal adsorption behaviour. The material characterisation and adsorption experiments indicate that surface coordination and chemical precipitation are the main mechanisms of Fe²⁺ and Mn²⁺ removal by IHA/TM.     

Facile Synthesis of BiVO4@ZIF−8 Composite with Heterojunction Structure for Photocatalytic Wastewater Treatment

Water pollution has always been a serious problem across the world; therefore, facile pollutant degradation via light irradiation has been an attractive issue in the field of environmental protection. In this study, a type of Zn-based metal–organic framework (ZIF−8)-wrapped BiVO₄ nanorod (BiVO₄@ZIF−8) with high efficiency for photocatalytic wastewater treatment was synthesized through a two-step hydrothermal method. The heterojunction structure of BiVO₄@ZIF−8 was confirmed by morphology characterization. Due to the introduction of mesoporous ZIF−8, the specific surface area reached up to 304.5 m²/g, which was hundreds of times larger than that of pure BiVO₄ nanorods. Furthermore, the band gap of BiVO₄@ZIF−8 was narrowed down to 2.35 eV, which enabled its more efficient utilization of visible light. After irradiation under visible light for about 40 min, about 80% of rhodamine B (RhB) was degraded, which was much faster than using pure BiVO₄ or other BiVO₄-based photocatalysts. The synergistic photocatalysis mechanism of BiVO₄@ZIF−8 is also discussed. This study might offer new pathways for effective degradation of wastewater through facile design of novel photocatalysts.     

High-Selective Extraction of Scandium (Sc) from Bauxite Residue (Red Mud) by Acid Leaching with MgSO4

Bauxite residue, also known as red mud (RM), from alumina production is the most promising technogenic material for the production of scandium (Sc) and other rare earth elements (REEs). Conveniently, RM is processed by using a strong acid (pH < 2.5), which lead to co-dissolution of iron and other undesirable major components. In this work, for the first time, the possibility of selective extraction of scandium from red mud by using highly diluted acid (pH > 4) in the presence of MgSO₄ was shown. The effect of temperature (40–80 °C), time (0–60 min), pH (2–5), and the MgSO₄ concentration (12–36 g L⁻¹) on Sc extraction efficiency was evaluated. It was shown that Sc extraction was higher than 63% even at a pH of 4, at 80 °C, after 1 h, while more than 80% could be extracted at a pH of 2. Iron extraction reduced from 7.7 to 0.03% by increasing the pH from 2 to 4. The kinetics study using the shrinking core model (SCM) has shown that diffusion through a product layer is a rate-limiting stage of the process at high temperatures (>60 °C) and low pH (<3), whereas, at lower temperatures and higher pH values, the leaching rate is limited by diffusion through the liquid film.     

Development of Antifouling Polysulfone Membranes by Synergistic Modification with Two Different Additives in Casting Solution and Coagulation Bath: Synperonic F108 and Polyacrylic Acid

This study deals with the development of antifouling ultrafiltration membranes based on polysulfone (PSF) for wastewater treatment and the concentration and purification of hemicellulose and lignin in the pulp and paper industry. The efficient simple and reproducible technique of PSF membrane modification to increase antifouling performance by simultaneous addition of triblock copolymer polyethylene glycol-polypropylene glycol-polyethylene glycol (Synperonic F108, M_n =14 × 10³ g mol⁻¹) to the casting solution and addition of polyacrylic acid (PAA, M_n = 250 × 10³ g mol⁻¹) to the coagulation bath is proposed for the first time. The effect of the PAA concentration in the aqueous solution on the PSF/Synperonic F108 membrane structure, surface characteristics, performance, and antifouling stability was investigated. PAA concentrations were varied from 0.35 to 2.0 wt.%. Membrane composition, structure, and topology were investigated by Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The addition of PAA into the coagulation bath was revealed to cause the formation of a thicker and denser selective layer with decreasing its pore size and porosity; according to the structural characterization, an interpolymer complex of the two additives was formed on the surface of the PSF membrane. Hydrophilicity of the membrane selective layer surface was shown to increase significantly. The selective layer surface charge was found to become more negative in comparison to the reference membrane. It was shown that PSF/Synperonic F108/PAA membranes are characterized by better antifouling performance in ultrafiltration of humic acid solution and thermomechanical pulp mill (ThMP) process water. Membrane modification with PAA results in higher ThMP process water flux, fouling recovery ratio, and hemicellulose and total lignin rejection compared to the reference PSF/Synperonic F108 membrane. This suggests the possibility of applying the developed membranes for hemicellulose concentration and purification.