Alkaline Oxides Research Articles

GENESIS OF EXTREMELY MAGNESIAN DAUGHTER OLIVINE OF SECONDARY MELT INCLUSIONS FROM OLIVINE MACROCRYSTS IN KIMBERLITE FROM THE UDACHNAYA-EAST PIPE (SIBERIAN CRATON)

The paper presents the results of studies of daughter olivine within secondary melt inclusions marking healed cracks in olivine macrocrysts from unserpentinized kimberlite from the Udachnaya-East pipe. Macrocrysts compose four olivine generations: core olivine (Ol1); olivine marking healed cracks (Ol2); daughter olivine of melt inclusions (Ol3); thin outer rims of olivine (Olr) around macrocryst cores. The relationship between different olivine generations and variations in its chemical composition indicate that macrocrystal cores (Ol1) are grains or grain fragments of disintegrated mantle rocks; melt inclusions and Ol2 were formed due to infiltration of kimberlite melts into the grain cracks. Crystallization of a hybrid melt of inclusions and formation of an extremely magnesian daughter olivine (Ol3) occurred later, at lower PT conditions. Among the daughter minerals in the melt inclusions, in addition to Ol3 there were identified alkaline carbonates, sulfates, chlorides, oxides, and sulfides. It has been shown that the daughter olivine of melt inclusions (Ol3) has high Mg# (97–98) content, high MnO (0.18–0.41 wt. %) and CaO (0.12–0.25 wt. %) concentrations, and low NiO (0.02–0.04 wt. %) contents. The ratios between the daughter minerals of the melt inclusions indicate that the hybrid melt from which extremely magnesian olivine was formed was alkaline carbonate or silicate-carbonate liquid with a low water content. Our study directly showed for the first time that almost pure forsterite is able to be crystallized from evolved kimberlite melts of carbonate or silicate-carbonate composition, which confirms the previously proposed model for the formation of extremely magnesian outer rims of olivine crystals from worldwide kimberlites during crystallization of evolved kimberlite melts of carbonate composition.

An Overview of Different Water Electrolyzer Types for Hydrogen Production

While fossil fuels continue to be used and to increase air pollution across the world, hydrogen gas has been proposed as an alternative energy source and a carrier for the future by scientists. Water electrolysis is a renewable and sustainable chemical energy production method among other hydrogen production methods. Hydrogen production via water electrolysis is a popular and expensive method that meets the high energy requirements of most industrial electrolyzers. Scientists are investigating how to reduce the price of water electrolytes with different methods and materials. The electrolysis structure, equations and thermodynamics are first explored in this paper. Water electrolysis systems are mainly classified as high- and low-temperature electrolysis systems. Alkaline, PEM-type and solid oxide electrolyzers are well known today. These electrolyzer materials for electrode types, electrolyte solutions and membrane systems are investigated in this research. This research aims to shed light on the water electrolysis process and materials developments.

Leaching Thermodynamics of Low-Grade Copper Oxide Ore from [(NH4)2SO4]-NH3-H2O Solution.

This paper describes a highly alkaline low-grade copper oxide ore. Copper can be selectively leached out while other metals are retained. A thermodynamic model of the CuO-(NH4)2SO4-NH3-H2O system was established for the leaching of tenorite (CuO) under conditions of mass and charge conservation. MATLAB's fitting functions, along with the diff and solve functions, were used to calculate the optimal ammonia concentration and total copper ion concentration of tenorite under different ammonium sulfate concentrations. The effects of various ammonia-ammonium salt solutions (ammonium sulfate, ammonium carbonate, ammonium chloride) on the copper leaching rate were investigated. Results show that under the conditions of an ammonia concentration of 1.2 mol/L, an ammonia-ammonium ratio of 2:1, a liquid-solid ratio of 3:1, a temperature of 25 °C, and a leaching time of 4 h, the copper leaching rate from the ammonium sulfate and ammonium chloride solutions reaches 70%, which is slightly higher than that of ammonium carbonate. Therefore, an ammonia-ammonium sulfate system is selected for leaching low-grade copper oxide due to its lower corrosion to equipment compared to the chlorination system. The impact of this study on industrial applications includes the potential to find more sustainable and cost-effective methods for resource recovery. The industry can reduce its dependence on resources and mitigate its environmental impact. Readers engaged in low-grade oxidized copper research will benefit from this study.

Substantial CO2 uptake by biomass ashes under natural condition in China

A considerable amount of biomass ashes, resulting from agricultural waste field burning, wildfire, and solid biofuel incineration, is typically discarded in field or stored in dumps, where the alkaline oxides (CaO, MgO) they contain undergo carbonation and weathering-erosion processes over extended periods, continuously absorbing CO2 from the atmosphere and soil. However, their CO2 absorption behavior under natural conditions remains insufficiently explored in China. Using life cycle assessment (LCA) and material flow analysis (MFA) methods, this study developed a CO2 absorption analysis model for biomass ashes under natural conditions. We estimated the CO2 absorption of 9 different types of biomass ash from 1950 to 2022 through Monte Carlo uncertainty simulation. The results show that biomass ashes in China absorbed approximately 24.17Mt/year (95 % CI, 11.10–43.56) of CO2 under nature conditions, with the annual average CO2 uptake showing a steady increase from 1950 to 2022. The total CO2 uptake reached 856.85Mt (95 % CI, 368.73–1526.01) over these decades, mainly due to the significant contribution of biomass ash produced by domestic straw burning and fuelwood combustion, which accounted for 51.97 % and 22.08 %, respectively. Our findings highlight the substantial carbon sink benefits of biomass ash, providing valuable insights for further studies on carbon cycles in natural ecosystems and the potential integration of biomass ash in Carbon Capture, Utilization, and Storage (CCUS) technologies.

Reactive Condensation of Cr Vapor on Aluminosilicates Containing Alkaline Oxides

This study is part of a series with the objective of improving fundamental understanding of reactive condensation of Chromium (Cr) vapors, which are generated from Cr containing alloys used in many high-temperature (>500 °C) process environments and can form potentially problematic condensed hexavalent (Cr(VI)) species downstream. This study specifically focuses on the effects of alkaline oxide additives in aluminosilicate fibers on Cr condensation and speciation. Cr vapors were generated by flowing high-temperature (800 °C) air containing 3% water vapor over chromia (Cr2O3) powder, with aluminosilicate fiber samples positioned downstream where the temperature decreases (<500 °C). Total condensed Cr and ratios of oxidation states were measured using inductively coupled plasma optical emission spectroscopy (ICP-OES) and diphenyl carbazide (DPC) colorimetric/direct UV–vis spectrophotometric analyses. Results indicate presence of hexavalent Cr (Cr(VI)) species condensed on all samples investigated. The ratio of Cr(VI) to total Cr detected was consistently higher on aluminosilicate fiber samples containing alkaline oxide (CaO and MgO) additions. Computational thermodynamic equilibrium modelling corroborated experimental results showing stabilities of Ca and Mg chromate (Cr(VI)) compounds. Comparative results and analyses are presented and discussed to help inform mechanistic understanding and future related research and engineering efforts.

(Digital Presentation) Reactive Evaporation of Cr Vapors from Chromia-Alkaline Oxide Mixtures Generated in 800℃ Air and Subsequent Condensation Onto Aluminosilicate Fibers

This research aims to improve fundamental understanding of the reactive evaporation and condensation of Chromium (Cr) vapors, which are generated from Cr containing alloys used in many high-temperature (>500℃) process environments and can form potentially problematic condensed hexavalent (Cr(VI)) species downstream. This study focuses on the effects of alkaline oxides present in the Cr source on the resultant Cr evaporation and condensation. Vapor species were generated by flowing high-temperature (800℃) air containing 3% water vapor over chromia (Cr2O3) and mixtures of chromia with calcium oxide (CaO) or magnesium oxide (MgO) powders. Lab-grade quartz and alumina fiber samples were positioned downstream from the Cr-alkaline oxide source where the temperature decreases (<500℃) to collect condensed vapor species. Total condensed Cr and ratios of oxidation states were measured using inductively coupled plasma optical emission spectroscopy (ICP-OES) and diphenyl carbazide (DPC) colorimetric/direct UV-VIS spectrophotometric analyses. Preliminary results indicate a decrease in partial pressures of generated Cr vapor species as well as a decrease in condensed Cr species on the aluminosilicate fibers when alkaline oxides are present in the Cr source compared to a pure Cr source. These results also indicate presence of hexavalent Cr (Cr(VI)) species condensed on all samples investigated. Computational thermodynamic equilibrium modelling corroborated the experimental results showing partial pressures of produced vapor species in the presence of alkaline oxides as well as stabilities of condensed Cr compounds on the fiber samples. Comparative results and analyses are presented and discussed to help inform mechanistic understanding and future related research and engineering efforts. Figure 1

Development of multicomponent glasses for application as a glazing layer on dental zirconia

AbstractThis study presents the development of multicomponent glasses for glaze layers for dental yttria‐stabilized tetragonal zirconia (Y‐TZP). The samples were melted in the temperature range of 1 250–1 400°C and were cast in water to obtain a frit. The frits were grounded to a powder with a particle size of less than 40 µm. To study the crystallization tendency of melted glasses, they were thermally treated at 800°C and X‐ray diffraction analyses were performed for both types of samples. The structure of the glasses was investigated by the Fourier‐transform infrared spectroscopy. The thermal expansion coefficient, CTE, the glass‐transition temperature, Tg, and the softening temperature, Ts, were defined. To test the glaze layer on zirconia ceramic, glass powders with different compositions were mixed with modeling fluid and applied on zirconia specimens and then fired at 800°C in a vacuum dental furnace. Scanning electron microscopy, SEM, was used to observe a cross‐section of the glass–ceramic contact on a glazed zirconia ceramic specimen. Glass with the highest content of alkaline oxides is characterized by the closest CTE to zirconium ceramics (10.10−6 K−1), the greatest transparency and good fluidity, and shows good adhesion to the zirconia. The glaze layer is homogeneous without cracks, pores, and crystals.

Structural investigation and physical properties of RO-ZnO-Li2B4O7-K2B4O7 (RO= SrO and BaO) glasses

Glass samples 10RO-30ZnO-xLi2B4O7-(60-x) K2B4O7 (RO=SrO and BaO) with alkali tetra borates varying from 0 to 60 mol% were produced by traditional quenching procedure. Peak free broad X-ray diffraction patterns established the amorphous feature of glass samples. FTIR and Raman spectroscopic analysis had shown existence of BO3 and BO4 structural groups along with other borate units. The BO3 ⇔ BO4 conversion rate was not much affected with variation in one of the alkali-tetraborates. EPR spectra of copper doped glasses confirmed the ground state of Cu2+ ions as 2B1g. Physical and optical properties namely density, molar volume, refractive index, molar refractivity, optical band gap and Urbach energy values were found to be composition dependent. The inflections observed in density, and other optical properties around equal mol% of alkali oxides in the glass system were attributed to structural modifications and mixed alkali effect. These results exposed the structural variations caused due to competitiveness between the two different alkali and alkaline oxides in occupying the geometrical positions of the borate glass network.

Mechanisms of interface electrostatic potential induced asphalt-aggregate adhesion

The electrostatic potential at the interface of the asphalt molecular and aggregate oxides is the primary factor generating the adhesion between the asphalt-aggregate contact surfaces. However, the route of electrostatic potential affecting the asphalt-aggregate adhesion is yet to be determined at the molecular level. This study proposed that the electron accumulation at the interface of the asphalt molecular and aggregate oxides generates a significant electrostatic potential hence to induce the adhesion between the asphalt and aggregate in asphalt pavement. A microscopic molecular dynamics (MD) simulation incorporated with macroscopic adhesion work experiments is conducted to analyze the interface adhesive performance between the asphalt and aggregate. The adhesion work experiment demonstrated the effect of aggregate surface oxides on asphalt adhesion at the macro level and further verified the simulation results. The result demonstrated that a notable electron accumulation can be observed by MD at the interface of asphalt molecular and multiple oxides which generates the electrostatic potential. The strong electrostatic attractions and hydrogen bonds between alkaline oxides (MgO, CaO, CaCO3) and asphalt molecules enhance the relative concentration distribution, diffusion coefficient, and adhesion of asphalt on the aggregate surface. The significant electrostatic potential difference at the interface of the asphalt molecular and the oxide enables a strong adhesion between them due to the near-surface failure potential. Besides, the negative charge accumulation on both the benzene ring structure and oxygen atoms in the asphalt molecules results in poor adhesion at the interface of asphalt molecules and multiple oxides. It was found that a high correlation exists between the MD prediction and experimental testing results. Thus, this research provides a valuable tool for guiding the pairing and selection of asphalt with various minerals for pavement design, construction, and maintenance agencies.

Experimental study on strengthening the hydrogen reduction process of pyrite in the presence of alkaline oxide

ABSTRACT In this study, an innovative approach is proposed for the hydrogen reduction of pyrite in the presence of alkaline oxide, suitable for desulfurisation of high-sulfur bauxite and iron extraction from pyrite. This approach has the advantage of efficiently utilising high-sulfur bauxite, solving the issue of SO2 flue gas pollution. Stirred fluidised beds were used as reactors to promote uniform particle distribution. The impact of hydrogen concentration and spatial velocity of the gas on the reduction process of pyrite and the sticking behaviour between particles in a side-stirred fluidised bed were investigated using a single-factor experimental method. The effects of various experimental conditions on the pyrite reduction percentage, sticking ratio, phase composition, and microstructure of the reduction products were examined using chemical, XRD, and SEM analyses. The results demonstrated that, when agitated, modifying the hydrogen concentration and spatial velocity of the gas significantly enhanced the reduction of pyrite in the presence of alkaline oxide and increased the reduction efficiency. A hydrogen concentration of 37.5% and spatial velocity of the gas of 0.115 m·s−1 were the ideal values, respectively. In addition, kilogram-scale experiments were performed to confirm the viability of the approach.

CONDUCTOMETRY ANALYSIS – BENEFICIAL METHOD FOR DETERMINING THE CHEMICAL COMPOSITION OF ALKALINE SILICATE SOLUTIONS

The study deals with the methodology for determining the chemical composition of alkaline silicate solutions. Nowadays, the most widely used method in industry is titration, using the color change of an acid-base indicator. This technique is very accurate for the determination of the total alkalinity (i.e., Na2O, K2O, or Li2O). However, a problem arises in the determination of the SiO2 content, since the color change of the methyl red indicator is very slow and therefore the equivalence point is unclear. The main aim of this work is to present the benefits of conductometric titration, where the equivalence point is indicated by a sudden change in the conductivity. The applicability of the method was verified with other analytical techniques, such as ICP-OES and gravimetric analyses. Their results confirmed the values of the obtained silicate module (the molar ratio of SiO2 and alkaline oxide) in the cases of sodium, potassium and lithium water glasses. Based on the obtained results, one can say that conductometry is a very promising method providing an accurate, fast and instrumentally undemanding chemical characterization of alkaline silicate solutions, usable even in a manufacturing process.

Heterogeneous alkaline catalyst synthesized from local bovine bone wastes for transesterification of palm oil into biodiesel

Abstract Local bovine bone wastes, which are abundant in Aceh Province, have been successfully used as biomineral sources to produce heterogeneous catalysts that result in alkaline oxide. This study aimed to produce alkaline oxides by employing a high heat breakdown approach on local bovine bone particles at atmospheric pressure. The physicochemical analysis of the obtained inorganic particles revealed that the predominant component of those obtained inorganic oxide particles was calcium oxides (CaO). Furthermore, the produced alkaline oxide was employed as an alkali oxide catalyst for the transesterification of palm oil (RPDPO) with methanol, yielding methyl ester compounds, which are well recognized as a sustainable and green diesel energy source.

A multiscale study of the influence of aggregate type on adhesion at the asphalt–aggregate interface

In order to examine the influence of aggregate type on the asphalt–aggregate interface, the adhesion performance between asphalt and aggregate was investigated at three scales. The pull-out test was conducted on asphalt and three kinds of aggregates at the macroscale to directly estimate the adhesion performance between them. At the microscale, the surface energies between asphalt and limestone, basalt, and andesite were examined through a surface energy experiment, and then the adhesion and debonding work were assessed. At the nanoscale, the interfacial behavior between six mineral compositions (SiO2, CaO, MgO, Al2O3, Fe2O3, and Na2O) of these aggregates and asphalt was determined using molecular dynamics simulation. The correlation of adhesion work at the microscale and nanoscale was further explored to unveil the bonding mechanisms between asphalt and aggregate. The macroscale results indicate that the adhesion force of andesite is slightly greater than that of limestone, probably because andesite has a greater surface roughness than limestone. The microscale results show the best adhesion and water stability between asphalt and limestone. The finding further explains that alkaline aggregates exhibit superior interfacial adhesion to asphalt. The nanoscale results show that the adhesion work of alkaline oxides with asphalt is more significant than that of acidic oxides with asphalt. Limestone and basalt have better adhesion to asphalt due to higher alkaline oxide content, while andesite has poorer adhesion to asphalt due to lower alkaline oxide and higher SiO2 content. The interfacial adhesion work increases from the microscale to the nanoscale by a factor of 2.91–4.75.

Formation Mechanism of Deposits in Rotary Kiln during Steelmaking Dust Carbothermic Recycling

Rotary kiln has been widely used in hazardous waste treatment because of its strong adaptability to raw materials, high productivity, and simple processing technology. However, the formation of deposits reduces its performance period and profitability. This study characterized the deposit mineralogy and thermodynamically and experimentally investigated its formation mechanism. The results show that the main phases of the deposit are magnetite, monolithic iron, olivine, and yellow feldspar. They indicate that the deposit formation process was accompanied by the participation of alkaline and iron oxides. The intermediate product Ca2SiO4 can promote the generation of low melting point phases, such as CaFeSiO4 and Ca2Al2SiO7, which are the main phases of deposit materials. Additionally, the reduction intermediate product FeO facilitated the generation of a liquid ferrous mixture (Fe3O4-FeO and Fe3O4-FeO-Fe mixture), which in turn further promoted the growth of the initial deposit phase. The solid deposit formed and attached to the kiln inner wall, along with a decrease in temperature. These results are expected to provide an idea or approach for fundamentally solving the problem of deposits in the rotary kiln.

Highly efficient selective hydrogenation of adiponitrile to hexamethylene diamine over barium and melamine formaldehyde resin-modified nickel–cobalt-based zeolitic imidazolate framework-derived catalyst

In the present study, the catalyst modified with alkaline oxide can enhance the selectivity to primary amines. However, the addition of alkaline oxide inevitably reduces catalytic activity. In this study, NiCo-NC@BaO-MFC catalyst derived from zeolitic imidazolate framework-67, Ba(CH3COO)2, and melamine formaldehyde (MF) resin was prepared and used for the hydrogenation of adiponitrile (ADN) to hexamethylene diamine (HDMA). The carbon layer obtained from the MF resin effectively prevents the interaction between barium (Ba) and the active center, thus improving target product selectivity without decreasing catalytic activity. The results of the density functional theory (DFT) calculation and characterization indicated that the effect of synergy between nickel (Ni) and cobalt (Co) bimetals induces an electron density growth on the Ni surface, bringing the d-band center toward the Fermi surface. Meanwhile, the high electron density of the active center compensates for the electron-deficient state of the carbon atom in –CN, thus improving the catalytic activity. Furthermore, it was found that the introduction of Ba promotes the formation of nucleophilic hydrogen anions, which facilitates the hydrogenation of 6-aminohexylimine (AHIM) to HDMA and inhibits the intramolecular condensation of AHIM, hence improving the selectivity to HDMA. The NiCo-NC@BaO-MFC catalyst gives 98.6 % ADN conversion and 97.2 % selectivity to HDMA in an alkali-free system.

Effect of B2O3 and Basic Oxides on Network Structure and Chemical Stability of Borosilicate Glass

Glass properties play crucial roles in ensuring the safety and reliability of electronic packaging. However, challenges, such as thermal expansion and resistance to acid corrosion, pose long-term service difficulties. This study investigated the impact of the microstructure on acid resistance by adjusting the glass composition. A glass material with excellent acid resistance was obtained by achieving a similar coefficient of thermal expansion to tantalum; it exhibited a weight loss rate of less than 0.03% when submerged in 38% sulfuric acid at 85 °C for 200 h. Theoretically, this glass can be used to seal wet Ta electrolytic capacitors. Differential scanning calorimetry (DSC) was used to analyze the glass transition temperature and thermal stability of borosilicate glasses. X-ray diffractometry (XRD), scanning electron microscopy (SEM), and Raman spectroscopy were used to study the microstructure of the amorphous phase of the borosilicate glass, which revealed a close relationship between the degree of network phase separation in the borosilicate glass and the degree of polymerization (isomorphic polyhedron value, IP) of the glass matrix. The IP value decreased from 3.82 to 1.98 with an increasing degree of phase separation. Boron transitions from [BO4] to [BO3] within the glass network structure with increasing boron oxide content, which diminishes the availability of free oxygen provided by alkaline oxide, resulting in a lower acid resistance. Notably, the glass exhibited optimal acid resistance at boron trioxide and mixed alkaline oxide contents of 15% and 6%, respectively. Raman experiments revealed how the distributions of various bridging oxygen atoms (Qn) affect the structural phase separation of the glass network. Additionally, Raman spectroscopy revealed the depolymerization of Q4 into Q3, thereby promoting high-temperature phase separation and highlighting the unique advantages of Raman spectroscopy for phase recognition.

Preparation and characterizations of glasses in the TeO2–Ga2O3–M2O (M═Li, Na, K) systems

AbstractGlasses in the TeO2–Ga2O3–M2O (M═Li, Na, or K) systems were synthesized by a melt‐quenching technique. The glass forming areas were delimited for each system. Systematic analyses were performed on two series of samples—the first one with a constant TeO2/Ga2O3 ratio of 85/15, that is, [(TeO2)0.85(Ga2O3)0.15]100−x[M2O]x with 0 ≤ x ≤ 25 (with a step of 5 mol%), the second one with a constant alkaline oxide concentration of 10 mol%, that is, [TeO2]90‐y[Ga2O3]y[M2O]10 with 5 ≤ y ≤ 15 (with step of 2.5 mol%). The values of the glass transition temperature, density, and optical transmission parameters (the positions of short‐ and long‐wavelength absorption edge and the maximum transmittance value) were determined. The changes in these parameters were studied for varying glass compositions. In addition, the values of refractive index were measured at various wavelengths across the whole transparency region reaching from the visible up to the mid‐infrared range.

Comparison of Mechanical Properties of the Geopolymer-Solidified Soils Activated by Two Alkaline Oxides

Comparison of Mechanical Properties of the Geopolymer-Solidified Soils Activated by Two Alkaline Oxides

TWO-STAGE PALM KERNEL SHELL WASHING WITH WATER AND ACETIC ACID AS PREPARATION OF CO-FIRING SYSTEM WITH COAL

Palm kernel shells (PKS) were washed with water and glacial acetic acid (CH3COOH) gradually to prepare them for co-firing with coal. They were then torrefied at 450ºC for one hour. Washing was done to reduce the concentration of ash and alkaline oxides, which would reduce the chance of slagging and fouling. The research was conducted considering that information about washing the PKS with acetic acid and then having them torrefied is very limited and unclear. The results showed that washed and torrefied PKS had better characteristics than those of raw PKS or PKS washed with water. PKS that is washed with acid, torrefied and then blended with coal has low slagging and medium fouling tendencies. However, based on ash fusion temperature, the inclination towards slagging and fouling is high under reducing conditions and medium under oxidation conditions.

An investigation on 45S5 nanobioactive glass using FTIR and Raman spectroscopy

Bioactive materials are those that cause a number of interactions at the biomaterial-living tissue inter-face that result in the evolution of a mechanically strong association between them. For this reason, an implantable material’s bioactive behavior is highly advantageous. Silicate glasses are encouraged to be used as bioactive glasses due to their great biocompatibility and beneficial biological effects. The sol-gel method is the most effective for preparing silicate glasses because it increases the material’s bioactivity by creating pores. Glass densities are altered by the internal network connectivity between network formers and network modifiers. The increase in the composition of alkali or alkaline oxides reduces the number of bridging oxygens and increases the number of non-bridging oxygens by retaining the overall charge neutrality between the alkali or alkaline cation and oxygen anion. Higher drying temperatures increase pore densities, while the melt-quenching approach encourages the creation of higher density glasses. Band assignments for the BAG structure can be explained in detail using Fourier Transform Infrared (FTIR) and Raman spectroscopic investigations. Raman spectroscopy makes it simple to measure the concentration of the non-bridging oxygens in the silica matrix.