Thermal expansion and characteristic points of –Na2O–SiO2 glass with added oxides

A differential method with an optical lever system was used to determine the thermal expansion of the glasses based on Na₂O–SiO₂ and containing the following oxides: Al₂O₃, CaO, TiO₂, ZnO, Al₂O₃–TiO₂, CaO–TiO₂, or ZnO–TiO₂. The determination was carried out on both as-drawn and annealed rods. The influence of the thermal history as well as of the added oxide(s) on the thermal expansion of glasses is dealt with in this paper. The experimental results for the thermal expansion of annealed rods show that the addition of CaO–TiO₂ in the glass has the lowest value while the addition of CaO in the glass has the highest value for the coefficient of linear expansion. At the same time, the characteristic points of the annealed glasses, determined from the expansion-temperature curves, show that the addition of ZnO in the glass has the lowest values while the addition of TiO₂ in the glass has the highest values.     

Photoluminescence mechanism of annealed ZnO/Zn/Al2O3 sandwich structures deposited on glass substrates

ZnO/Zn/Al₂O₃ sandwich structures are grown on glass substrates by magnetron sputtering. The effect of Al₂O₃ layers on optical properties of ZnO/Zn/Al₂O₃ sandwich structures is investigated. Results indicated that as the deposition time of Al₂O₃ increases, violet peak centered at 402 nm gradually shifted to 412 nm and the intensity firstly decreases and then increases. We discuss the intensity change and shift of violet peak relating to V_Zn defects and the band alignment of ZnO/Zn/Al₂O₃ sandwich structures, respectively. We proposed that ZnO/Zn/Al₂O₃ sandwich structures can be approximately regarded as a quasiquantum-well-like structure. So the electron tunneling from Zn to Al₂O₃ layer is suppressed and the photogenerated carriers can be confined in the Zn Fermi level. In order to further understand the effect of posttreatment on optical properties of samples, samples are annealed in vacuum at 350 °C for 1 h. PL emissions are weakened with the increase of Al₂O₃ deposition time. Interestingly, at a same deposition condition, PL emissions are still improved after posttreatment. Combined Al₂O₃ layer modulation with annealing treatment, steady PL properties can be effectively improved.     

Understanding the structure,thermal, and optical properties in Al2O3-incorporated La2O3-TiO2-Nb2O5 glasses

Glasses in the 30La₂O₃-40TiO₂-30Nb₂O₅ system are known to have excellent optical properties such as refractive indices over 2.25 and wide transmittance within the visible to mid-infrared (MIR) region. However, titanoniobate glasses also tend to crystallize easily, significantly limiting their applications in optical glasses due to processing challenges. Therefore, the 30La₂O₃-40TiO₂-(30−x) Nb₂O₅-xAl₂O₃ (LTNA) glass system was successfully synthesized using a aerodynamic containerless technique, which improves glass thermal stability and expands the glass-forming region. The effects of Al₂O₃ on the structure, thermal, and optical properties of base composition glasses were investigated by XRD, DSC, NMR, Raman spectroscopy, and optical measurements. DSC results indicated that as the content of Al₂O₃ increased, the thermal stability of the glasses and glass-forming ability increased, as the 30La₂O₃-40TiO₂-25Nb₂O₅-5Al₂O₃ (Nb-Al-5) glass obtained the highest ΔT value (103.5°C). Structural analysis indicates that the proportion of [AlO₄] units increases gradually and participates in the glass network structure to increase connectivity, promoting more oxygen to become bridging oxygen and form [AlO₄] tetrahedral linkages to [TiO₅] and [NbO₆] groups. The refractive index values of amorphous glasses remained above 2.1 upon Al₂O₃ substitution, and a transmittance exceeding 65% in the visible and mid-infrared range. The crystallization activation energies of 30La₂O₃-40TiO₂-30Nb₂O₅ (Nb-Al-0) and Nb-Al-5 glasses were calculated to be 611.7 and 561.4 kJ/mol, and the Avrami parameters are 5.28 and 4.96, respectively. These results are useful to design new optical glass with good thermal stability, high refractive index and low wavelength dispersion for optical applications such as lenses, endoscopes, mini size lasers, and optical couplers.     

Thermal Stability,Optical Transmittance,and Refractive Index Dispersion of La2O3–Nb2O5–Al2O3 Glasses

La₂O₃–Nb₂O₅–Al₂O₃ high‐refractive‐index glasses were fabricated by containerless processing, and the glass‐forming region was determined. The thermal stability, density, optical transmittance, and the refractive index dispersion of these glasses were investigated. All the glasses were colorless and transparent in the visible to near infrared (NIR) region and had high refractive index with low wavelength dispersion. Some of these glasses were found to have significantly high glass‐forming ability. These results indicate that the ternary glasses are suitable for optical applications in the visible to NIR region. The effects of the substitution of Al₂O₃ for Nb₂O₅ on optical properties were discussed on the basis of the Drude–Voigt equation. It was suggested that the substitution of Al₂O₃ for Nb₂O₅ increased the molecular density and suppressed a decrease in the refractive index, even when both the average oscillator strength and inherent absorption wavelength decreased in La₂O₃–Nb₂O₅–Al₂O₃ glasses. These results are helpful for designing new optical glasses controlled to have a higher refractive index and lower wavelength dispersion.     

Synergetic effect of combined use of Cu–ZnO–Al2O3 and Pt–Al2O3 for the steam reforming of methanol

Commercial Cu–ZnO–Al₂O₃ catalysts are used widely for steam reforming of methanol. However, the reforming reactions should be modified to avoid fuel cell catalyst poisoning originated from carbon monoxide. The modification was implemented by mixing the Cu–ZnO–Al₂O₃ catalyst with Pt–Al₂O₃ catalyst. The Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture created a synergetic effect because the methanol decomposition and the water–gas shift reactions occurred simultaneously over nearby Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalysts in the mixture. A methanol conversion of 96.4% was obtained and carbon monoxide was not detected from the reforming reaction when the Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture was used.     

Elucidating the influences of Tantalum (V) oxide in Bi2O3–TeO2–ZnO ternary glasses: An experimental characterization study on optical and nuclear radiation transmission properties of high-density glasses

We report the optical and experimental gamma-ray and neutron attenuation properties of tantalum pentoxide reinforced Bi₂O₃–TeO₂–ZnO ternary glasses with a nominal composition of 10Bi₂O₃–70TeO₂-(20-x)ZnO-xTa₂O₅ (where x = 0,2,4, and 6 mol%). Measurements of transmittance and absorbance spectra for all of the synthesized samples are performed with Analytik Jena Specord 210 plus device between the range of 190–1100 nm. Moreover, ¹³³Ba and ²⁴¹Am/Be sources are utilized for experimental gamma-ray and neutron attenuation studies of BTZT glasses. According to results, the absorption edge is consistently moved from 380 nm to 390 nm as a result of ZnO/Ta₂O₅ translocation. In addition to decrease in optical band gap values of glass series, the fact that doping the structure containing Ta₂O₅ is lead to an increase in Urbach energies. The obtained irregularity through an increasing Ta₂O₅ additive is also changed the overall nuclear radiation attenuation properties of the BTZT glasses. The gamma-ray attenuation properties are obviously enhanced within the energy range of ¹³³Ba radioisotope. The attenuation properties against fast neutron emitted from ²⁴¹Am/Be were significantly enhanced through increasing Ta₂O₅ contribution. It can be concluded that BTZT6 glass sample may be regarded as a beneficial glass composition for multifunctional applications. It can be also concluded that ZnO/Ta2O5 translocation in Bi₂O₃–TeO₂–ZnO ternary glasses may be regarded as a monotonic tool where the neutron attenuation properties should be strengthened in addition to gamma attenuation properties.     

Carbothermal Synthesis of the Nanostructures of Al2O3 and ZnO

Nanostructures of Al₂O₃ and ZnO have been synthesized by a carbothermal route involving the reaction of the metal or the metal oxide with carbon. In the case of Al₂O₃, nanowires and nanotubes are obtained starting with Al metal and active carbon or graphite. ZnO nanowires are obtained by the reaction of zinc oxalate or ZnO with active carbon or multiwalled carbon nanotubes. The Al₂O₃ and ZnO nanostructures obtained have been characterized by X-ray diffraction, electron microscopy and photoluminescence spectroscopy. These nanostructures are likely to be of use as catalyst supports and in other technological applications.     

Glass forming,crystallization, and physical properties of MgO-Al2O3-SiO2-B2O3 glass-ceramics modified by ZnO replacing MgO

This study focused on the glass forming, crystallization, and physical properties of ZnO doped MgO-Al₂O₃-SiO₂-B₂O₃ glass-ceramics. The results show that the glass forming ability enhances first with ZnO increasing from 0 to 0.5 mol%, and then weakens with further addition of ZnO which acted as network modifier. No nucleating agent was used and the crystallization of studied glasses is controlled by a surface crystallization mechanism. The predominant phase in glass-ceramics changed from α-cordierite to spinel/gahnite as ZnO gradually replaced MgO. The phase type did not change; however, the crystallinity and grain size in glass-ceramics increased when the glasses were treated from 1030 °C to 1100 °C. The introduction of ZnO can improve the thermal, mechanical, and dielectric properties of the glass-ceramics. The results reveal a rational mechanism of glass formation, crystal precipitation, and evolution between structure and performance in the xZnO-(20-x)MgO-20Al₂O₃-57SiO₂-3B₂O₃ (0 ≤ x ≤ 20 mol%) system.     

Effects of TeO2/B2O3 substitution on synthesis,physical, optical and radiation shielding properties of ZnO–Li2O-GeO2-Bi2O3 glasses

Tellurite glass is a model material having superior features for several applications. It can be considered as a potential host matrix for different oxides, and this paper aims to study the effects of TeO₂/B₂O₃ substitution on synthesis, physical, optical and radiation shielding properties of ZnO–Li₂O-GeO₂-Bi₂O₃ glasses produced by melt quenching technique. The physical and optical features of the fabricated glasses were experimentally investigated by determining pivotal parameters such as density, XRD, tellurium ion concentration (N_i), linear refractive index (n_o), polaron radius (r_p) and inter nuclear distance (r_i). Moreover, the relative radiation deposition within the glasses was assessed via the attenuation coefficients (e.g. MAC), specific gamma ray constant (ᴦ), total stopping power (TSP), neutron cross sections, and dose rate (D). Our results suggest that both TeO₂ and B₂O₃ additives have a significant effect on the fundamental properties of the ZnO–Li₂O-GeO₂-Bi₂O₃ glasses. It also found that the lower thicknesses of the present glasses are required to provide the same level of shielding than ordinary, ilmenite, steel scrap, hematic-serpentine, ilmenite-limonite and basalt-magnetite concretes, RS253-G18 and RS360 glass shields. Therefore, presently investigated glasses are promising photon shields in different technological applications of gamma- and x-rays.     

Zinc Oxide in Borate Glass-Forming Systems

Glasses based on the system ZnO - SrO - B₂O₃ with additional introduction of PbO, Al₂O₃, and Li₂O are investigated; an elemental analysis of the heterogeneities is performed. The effect of ZnO on the physicochemical properties of glasses is considered. Fluxes with a decreased PbO content are developed. __________ Translated from Steklo i Keramika, No. 6, pp. 16 – 18, June, 2005.     

Role of ZnO in Cu/ZnO/Al2O3 catalyst for hydrogenolysis of butyl butyrate

For hydrogenolysis of butyl butyrate (BB), a series of Cu/ZnO/Al₂O₃ catalysts with different metal compositions were prepared, and characterized by N₂O chemisorption for measuring Cu surface area and by chromatographic experiment for determining the heat of BB adsorption. As a result, the presence of ZnO in Cu-based catalysts was found to enhance the catalytic activity of Cu due to dual function of ZnO. The Cu surface area was linearly correlated with the butanol productivity, demonstrating that ZnO exerts the structural function in Cu/ZnO/Al₂O₃ catalysts. Additionally, the role of ZnO as a chemical contributor was revealed such that its presence leads to lower activation energy of the surface reaction, thus resulting in higher Cu catalytic activity obtained at a low temperature such as 200 °C. Consequently, optimizing the Cu/Zn ratio in Cu/ZnO/Al₂O₃ catalyst is required to tune its structural and chemical characteristics of Cu metals, and thus to obtain a higher activity on the hydrogenolysis reaction.     

Electrical and optical properties of Al-doped ZnO and ZnAl2O4 films prepared by atomic layer deposition

ZnO/Al₂O₃ multilayers were prepared by alternating atomic layer deposition (ALD) at 150°C using diethylzinc, trimethylaluminum, and water. The growth process, crystallinity, and electrical and optical properties of the multilayers were studied with a variety of the cycle ratios of ZnO and Al₂O₃ sublayers. Transparent conductive Al-doped ZnO films were prepared with the minimum resistivity of 2.4 × 10⁻³ Ω·cm at a low Al doping concentration of 2.26%. Photoluminescence spectroscopy in conjunction with X-ray diffraction analysis revealed that the thickness of ZnO sublayers plays an important role on the priority for selective crystallization of ZnAl₂O₄ and ZnO phases during high-temperature annealing ZnO/Al₂O₃ multilayers. It was found that pure ZnAl₂O₄ film was synthesized by annealing the specific composite film containing alternative monocycle of ZnO and Al₂O₃ sublayers, which could only be deposited precisely by utilizing ALD technology.     

Enhancing the thermoelectric properties of super-lattice Al2O3/ZnO atomic film via interface confinement

Aluminum oxide (Al₂O₃)/zinc oxide (ZnO) thin films deposited via atomic layer deposition (ALD) are demonstrated to enhance their thermoelectric properties by manipulating them with a nano-thick Al₂O₃ interface. The overall superlattice structure is tuned by varying the ZnO ALD sequence and the Al₂O₃ ALD sequence while maintaining the same composition. An aluminum-doped zinc oxide (AZO) thin film is deposited at 250 °C, and the Al₂O₃ thickness in the superlattice is gradually increased from 0.13 nm to 1.23 nm. The total film composition is fixed at 2% AZO. We observe that an efficient superlattice structure is made with a specific Al₂O₃ thickness. The thermal conductivity is significantly decreased from 0.57 W/mK to 0.26 W/mK as the thickness of the Al₂O₃ layer is increased. Additionally, the absolute Seebeck coefficient is increased from 14 μV/K to 65 μV/K. This may be caused by the interface confinement effect and interface scattering between the ZnO layer and the Al₂O₃ layer. The figure of merit ZT value is 0.14 for the most efficient structure.     

A closer-look on Copper(II) oxide reinforced Calcium-Borate glasses: Fabrication and multiple experimental assessment on optical,structural, physical,and experimental neutron/gamma shielding properties

This study aimed to fabricate six different Copper(II) oxide reinforced Calcium-Borate glasses with different types of substitutions such as Al₂O₃/V2O₅, BaO₂/V₂O₅, and ZnO/V₂O_5. Accordingly, a depth characterization process has been performed for ACV, BCV and ZCV glasses with a nominal composition of 55B₂O₃–35CaO–9Al₂O₃-0.5CuO-0.5V₂O₅, 55B₂O₃–35CaO-8.5Al₂O₃-0.5CuO–1V₂O₅, 55B₂O₃–35CaO–9BaO₂-0.5CuO-0.5V₂O₅, 55B₂O₃–35CaO-8.5BaO₂-0.5CuO–1V2O5, 55B2O3–35CaO–9ZnO-0.5CuO-0.5V2O5, 55B2O3–35CaO-8.5ZnO-0.5CuO–1V₂O₅. Optical, structural, physical, and experimental neutron/gamma shielding properties of synthesized glasses were determined, respectively. Experiments measuring neutron exposure indicated how well glass samples attenuated fast neutrons. The RADACS software was used to record data from a BF3 gas proportional detector from the Canberra NP-100B series and a 241Am/Be neutron source with a 10 mCi activity. The absorption edge belonging to the samples are found between 420 nm and 480 nm. Our findings showed that the optical band gaps for the samples ranged from 1.179 to 2.022 eV. The wavenumber range of 400–1600 cm^-1 was evaluated for the resulting peaks. The region with the highest band formation was approximately 760–1170 cm^-1. While BCV0.5 and BCV1 glasses with 9% and 8.5% BaO₂ insertion have the largest MAC values ranging between 2.255–0.076 and 2.156–0.076 cm²/g, the lowest MAC values varying between 0.361–0.0761 and 0.366–0.076 cm²/g belong to ACV0.5 and ACV1 glasses with 9% and 8.5% Al₂O₃ addition. Our results showed that the BCV glass family has superior material properties among the fabricated glasses. It can be concluded that BaO₂/V₂O₅ glasses may be used in replacement of Copper(II) oxide glasses to provide monotonic behavior on crucial characteristics while maintaining the greatest density increase for large gamma ray shielding properties.     

Methanol Synthesis

Methanol, like ammonia, is one of the key industrial chemicals produced by heterogeneous catalysis. As with the original ammonia catalyst (Fe/K/Al₂O₃), so with methanol, the original methanol synthesis catalyst, ZnO, was discovered by Alwin Mittasch. This was translated into an industrial process in which methanol was produced from CO/H₂ at 400?°C and 200 atm. Again, as with the ammonia catalyst where the final catalyst which is currently used was achieved only after exhaustive screening of putative “promoters”, so with methanol, exhaustive screening of additives was undertaken to promote the activity of the ZnO. Early successful promoters were Al₂O₃ and Cr₂O₃ which enhanced the stability of the ZnO but not its activity. The addition of CuO was found to increase the activity of the ZnO but the catalyst so produced was short lived. Current methanol synthesis catalysts are fundamentally Cu/ZnO/Al₂O₃, having high CuO contents of?~60?% with ZnO?~?30?% and Al₂O₃?~?10?%. Far from promoting the activity of the ZnO by incorporation of CuO, the active component of these Cu/ZnO/Al₂O₃ catalysts is Cu metal with the ZnO simply being involved as the preferred support. Other supports for the Cu metal, e.g. Al₂O₃, MgO, MnO, Cr₂O₃, ZrO₂ and even SiO₂ can also be used. In all of these catalysts the activity scales with the Cu metal area. The original feed has now changed from CO/H₂ to CO/CO₂/H₂ (10:10:80), radiolabelling studies having provided the unlikely discovery that it is the CO₂ molecule which is hydrogenated to methanol; the CO molecule acts as a reducing agent. The CO₂ is transformed to methanol on the Cu through the intermediacy of an adsorbed formate species. These Cu/ZnO/Al₂O₃ catalysts now operate at?~230° and between 50 and 100 atm. This important step change in the activity of methanol synthesis has resulted in a significant reduction in the energy required to produce methanol. The “step change” however has been incremental. It has been obtained on the basis of fundamental knowledge provided by a combination of surface science techniques, e.g. LEED, scanning tunnelling microscope, TPD, temperature programmed reaction spectroscopy, combined with catalytic mechanistic studies, including radiolabelling studies and chemisorption studies including reactive chemisorption studies, e.g. N₂O reactive frontal chromatography.     

Enhancement of luminescence properties and the role of ZnO in Tb3+ ions doped zinc aluminum phosphate glasses

Terbium ion doped zinc aluminum phosphate (ZAP) glasses with composition (90−x)((90−y)P₂O₅–10Al₂O₃–yZnO)–xTb₂O₃ (x=0.5–9 in mol% and y=30, 35, 40 in mol%) have been prepared by melt quenching method, and the effects of the Tb₂O₃ and ZnO content on the luminescence properties have been studied by photoluminescence spectroscopies. It was found that the green emission peaked at 544 nm is significantly enhanced under higher Tb₂O₃ content, meanwhile the sensitization effect of ZnO content is confirmed from the enhanced main emission. The quenching effect attributed to the resonant energy transfer through the cross-relaxation mechanism is observed when Tb₂O₃ concentration is beyond 2.5 mol% due to the fact that more Tb³⁺ ions enhance the 4f→5d and 4f→4f electronic transitions through the dipole–dipole (d–d) interaction. Also, ZnO plays a role of the disperser to prevent non-radiative de-excitation process. A characteristic luminescence image of the (100−x)(60P₂O₅–10Al₂O₃–30ZnO)·xTb₂O₃ series glasses under UV excitation at 366 nm is presented for the first time, and the transition of luminescence suggests that the Tb³⁺-doped ZAP glasses are suitable for green and dual-color blue/green LED applications by modulation of Tb and ZnO composition.     

Tailoring UV emission from a regular array of ZnO nanotubes by the geometrical parameters of the array and Al2O3 coating

Self-aligned and equal-spaced zinc oxide (ZnO) nanotube arrays were fabricated with anodic aluminum oxide (AAO)-assisted growth and the ALD technique. The near band-edge (NBE) emission was strongly affected by the nanotube's geometrical parameters, such as a packing density and thickness of the nanotube walls. The NBE emission was further enhanced with Al₂O₃ coating. The effect was analyzed by X-ray photoelectron spectroscopy (XPS) and ascribed to the surface defect passivation and a ZnAl₂O₄ spinel formation. The NBE emission enhancement was greater in ZnO nanotubes with thicker walls. A smaller UV enhancement factor was explained by less uniform and integral Al₂O₃ coverage of the ZnO nanotubes with thinner walls; this, possibly induced a variation of the Al₂O₃ refractive index along the nanotubes. As a result, the optical conditions at the ZnO/Al₂O₃/air interfaces was changed and the light extraction efficiency was reduced in the latter samples.     

Transparent polycrystalline nanoceramics consisting of triclinic Al2SiO5 kyanite and Al2O3 corundum

Transparent polycrystalline nanoceramics consisting of triclinic Al₂SiO₅ kyanite (91.4 vol%) and Al₂O₃ corundum (8.6 vol%) were fabricated at 10 GPa and 1200‐1400°C. These materials were obtained by direct conversion from Al₂O₃‐SiO₂ glasses fabricated using the aerodynamic levitation technique. The material obtained at 10 GPa and 1200°C shows the highest optical transparency with a real in‐line transmission value of 78% at a wavelength of 645 nm and a sample‐thickness of 0.8 mm. This sample shows equigranular texture with an average grain size of 34 ± 13 nm. The optical transparency increases with decreasing mean grain size of the constituent phases. The relationship between real in‐line transmission and grain size is well explained by a grain‐boundary scattering model based on a classical theory.     

Coloration and Nonlinear Optical Properties of ZnTe Quantum Dots in ZnO–TeO2–P2O5 Glasses

ZnO–TeO₂–P₂O₅ glasses were prepared by melt‐quenching method. The color of the glass samples changed from colorless to pale red and dark red with increasing TeO₂ content. Coloration mechanism and nonlinear optical properties of ZnO–TeO₂–P₂O₅ glasses have been investigated. Raman spectra and transmission electron microscope measurements indicated the precipitation of ZnTe quantum dots in the glasses and ZnTe quantum dots are the origin of coloration. Z‐scan technique was used to examine the nonlinear optical properties of the glasses. The glass sample with 30 mol% TeO₂ exhibits large third‐order nonlinear optical susceptibility of 10^?11 esu.     

Mechanism of Nanovoid Formation at the ZnO–Glass Interface in Planar Multilayered Structures of AlOx–ZnO–Glass

Functional porous materials require easy fabrication methods with controllability of a wide range of pore size and its density for practical applications including optical devices. The Kirkendall effect based on unbalanced material diffusion provides such a possibility in conjunction with material configurations of multilayers. This study reports a formation of nanoscale pores within ZnO films in planar multilayered structures of Al₂O₃–ZnO‐aluminosilicate glass and demonstrates the mechanism of forming relatively large nanopores in ZnO near the ZnO–glass interface via stress‐promoted Kirkendall diffusion. Experimental characterizations supported by atomic simulation reveal that an enhanced in‐plane tensile stress in the ZnO films with increasing the thickness of the neighboring Al₂O₃ films can promote the diffusivity of the Zn atoms and the pore growth in the ZnO films. The pore size and location in the intermediate ZnO layer of the Al₂O₃–ZnO–glass is alterable by simply selecting the thickness of the Al₂O₃ layer. Promoted diffusion of the Zn atoms enables to fabricate porous planar ZnO films with pore sizes up to a few hundred nm with an enhanced light scattering ability. These findings offer a promising route to produce porous planar films through in‐depth understanding of diffusivity enhancement in glass–metal oxide couples.