Preparation and characterization of agglomerated porous hollow silica supports for olefin polymerization catalyst

Self-prepared porous hollow silica (PHS) nanoparticles were agglomerated with an oil (kerosene)–ammonia method and used as a novel support of metallocene catalysts for olefin polymerization. Transmission electron microscopy (TEM), scanning electron microcopy (SEM), small-angle X-ray diffraction (SA-XRD) and nitrogen adsorption–desorption were employed to characterize the morphologies and mesostructures of the PHS particles and agglomerated PHS particles. It was found that the agglomerated PHS particles had an average diameter between 15 and 30 μm, a specific surface area of 214 m²/g, a pore diameter of 11–18 nm and a pore volume of 1.41 mL/g. Metallocene catalysts prepared with the agglomerated PHS as support demonstrated a very high activity of 8350 g PE/gCata. for ethylene polymerization due to their particular morphology and mesostructures. Analysis with Differential Scanning Calorimetry (DSC), SEM, TEM and molecular weight analysis indicated that the polyethylene product was composed of tiny spherical particles with good crystalline and narrow molecular weight distribution, and the morphology and structure of the individual PHS support particle remained unchanged in polyethylene following the polymerization.     

Uncommon features in the dynamic structure factor of a molten transition metal

The collective S_C(Q, ω), single-particle S_S(Q, ω) dynamic structure factors as well as the spectra for transverse-current correlations C_T(Q, ω) for molten nickel close to melting have been calculated from a massive molecular dynamics simulation using an Embedded Atom Model potential. A number of features are found in the structure factors that are absent in the spectra of simpler liquids such as molten alkali metals. Estimates for the shear component of the generalized, wavevector-dependent viscosity are obtained from analysis of C_T(Q, ω). Such data together with those concerning the strength of the thermal conduction channels for the excitation decay enable us to subtract such contributions to form the linewidths of Brillouin peaks and thus to evaluate the Q-dependent bulk viscosity coefficient. The result shows that contrary to inferences based upon geophysical data, both bulk and shear-viscosity coefficients are of the same order of magnitude.     

Intermediate Phases,structural variance and network demixing in chalcogenides: The unusual case of group V sulfides

We review intermediate phases (IPs) in chalcogenide glasses and provide a structural interpretation of these phases. In binary group IV selenides, IPs reside in the 2.40 < r < 2.54 range, and in binary group V selenides they shift to a lower r, in the 2.29 < r < 2.40 range. Here, r represents the mean coordination number of glasses. In ternary alloys containing equal proportions of group IV and V selenides, IPs are wider and encompass ranges of respective binary glasses. These data suggest that the local structural variance contributing to IP widths largely derives from four isostatic local structures of varying connectivity r, two include group V based quasi-tetrahedral (r = 2.29) and pyramidal (r = 2.40) units, and the other two are group IV based corner-sharing (r = 2.40) and edge-sharing (r = 2.67) tetrahedral units. Remarkably, binary group V (P, As) sulfides exhibit IPs that are shifted to even a lower r than their selenide counterparts; a result that we trace to excess S_n chains either partially (As–S) or completely (P–S) demixing from network backbone, in contrast to excess Se_n chains forming part of the backbone in corresponding selenide glasses. In ternary chalcogenides of Ge with the group V elements (As, P), IPs of the sulfides are similar to their selenide counterparts, suggesting that presence of Ge serves to reign in the excess S_n chain fragments back in the backbone as in their selenide counterparts.     

Experimental studies of phase equilibria in high-temperature ternary immiscible metallic melts

Shear viscosity measurements were carried out for a liquid immiscible ternary system In–Se–Te in a temperature range from the monotectic to about 1200 K using an oscillating-cup viscometer. It was revealed that the ternary In₈₀Se_xTe_20−x (0 ⩽ x ⩽ 20 at.%) system may be considered as a set of quasibinary In–(Se/Te) alloys of almost critical concentrations. A variation of the Se to Te ratio at constant content of In changes the properties of coexisting liquids and affects the binodal temperature. The critical parameters describing the peculiarities of viscosity behavior in the vicinity of the critical point are evaluated. The analysis based on the dynamic theory of phase transitions for viscosity in the phase separation region is proposed. The results are compared with available data for immiscible dielectric solutions and metallic melts.     

Glass formation of Ti–Ni–Sn ternary alloys correlated with TiNi–Ti3Sn pseudo binary eutectics

Glass-forming ability (GFA) of Ti–Ni–Sn ternary alloys was investigated. Applying recent models based on atomic size ratio and efficient packing, the composition favoring the glass formation is predicted. Our experiments indicate that the optimized glass-forming composition is located at Ti₅₆Ni₃₈Sn₆, with the critical thickness of complete glass formation approaching 100 μm for the melt-spun ribbons. The Ti₅₆Ni₃₈Sn₆ metallic glass exhibits a sizable supercooled liquid region (ΔT_x) of about 35 K and a reduced glass transition temperature (T_rg) of 0.52. We demonstrate that the glass formation of the Ti₅₆Ni₃₈Sn₆ alloy correlates with the (L → TiNi + Ti₃Sn) pseudo binary eutectic reaction in Ti–Ni–Sn ternary system, which has an invariant temperature and composition at ～1370 K and ～Ti₅₈Ni₃₄Sn₈, respectively. With respect to Sn-free Ti–Ni binary alloys, the GFA is enhanced for the Ti–Ni–Sn ternary alloys, but the improvement is limited possibly due to changes in the crystalline phases competing with glass formation.     

Isobaric and isochoric properties of decahydroisoquinoline,an extremely fragile glass-former

Pressure–volume–temperature (PVT) measurements were obtained on decahydroisoquinoline (DHIQ). From the resulting equation of state in combination with previously reported dielectric relaxation data, an analysis of the volume contribution to the dynamics was carried out for this very fragile glass-former (isobaric fragility, m_P = 163). We find that the ratio of the isochoric and isobaric fragilities equals 0.71 ± 0.02, reflecting a strong temperature effect, consistent with the large fragility. The relaxation times superpose when plotted versus temperature times the specific volume raised to the 3.55 power. This is a larger value of the exponent than expected based on the fragility of DHIQ. The implication is that for molecular glass-formers, the classical Lennard-Jones 6–12 repulsive potential may represent the limit for fragile liquids.     

Experimental ordering potential of manganese-polyvalent metals

Manganese is one of the scarce metals which presents a negative scattering length. It is thus possible, by measuring the total structure factor at a given concentration corresponding to that of the ‘zero alloy’, to obtain experimentally the Bhatia–Thornton concentration–concentration partial structure factor S_CC(q), from which the ordering potential can be obtained. We present three experimental ordering potentials of Mn₆₀Sb₄₀ (950 °C), Mn₆₉Ge₃₁ (980 °C) and Mn₆₆Ga₃₄ (1050 °C), which govern the order in the binary alloys. The comparison between these three potentials reveals interesting features especially when their depth and shape is analysed in relation with the electronegativity and the size differences of the considered atoms.     

Dielectric properties of binary and ternary mixtures of alcohols: Analysis of H-bonded interaction in complex systems

The heterogeneous H-bonded interactions in mixtures of glass-former liquids, i.e., binary mixtures of ethyl alcohol (EA) with ethylene glycol (EG) and ternary mixtures of equi-molar EA + EG system with glycerol (Gly) have been investigated at 21 concentrations by using precisely measured values of static and high frequency limiting dielectric constants at 25 °C. Concentration dependent observed negative values of excess dielectric constant (ε^E) and effective Kirkwood correlation factor (g^eff) implies the formation of H-bonded complexes between EA and EG molecules which reduces the effective number of dipoles. The EA + EG system forms the strongest complexes corresponding to the molar ratio ∼1:1. The observed positive ε^E values of the (EA + EG) + Gly ternary mixtures confirm the increase in number of effective dipoles contributed to the dielectric constant values due to the formation of the ternary complexes. Critical analysis of the experimental results of the EA + EG and the (EA + EG) + Gly mixtures suggest the suitability of ε^E and g^eff study in order to explain the dipolar ordering mechanism formed during the complexes between the alcohol molecules in their ternary mixtures.     

Electrical properties of a-Se85−xTe15Snx thin films

Se–Te alloys are an important system of chalcogenide glasses from application point of view. The incorporation of Sn additive alters the electrical properties of these alloys. The conductivity measurements have been done on the thin films of a-Se_85−xTe₁₅Sn_x (x = 0, 2, 4, 6 and 10 at.%) deposited using vacuum evaporation technique. Both dark (σ_d) and photoconductivity (σ_ph) show a maximum for x = 6 at.% of Sn, which, decreases on further Sn addition to the binary Se–Te alloy. The dark activation energy (ΔE_d) shows a minimum for x = 2 at.% of Sn, but increases on further Sn addition. There is a sharp decrease in photosensitivity (σ_ph/σ_d) on Sn addition to Se₈₅Te₁₅ alloy. The charge carrier concentration (n_σ) calculated with the help of dc conductivity measurements also show a maximum at x = 6 at.% of Sn. The results are explained on the basis of increase in the density of localized states present in the mobility gap on Sn incorporation.     

Structure of titanophosphate glasses studied by X-ray and neutron diffraction

The structure of binary (TiO₂)_x(P₂O₅)_1−x glasses with x = 0.60, 0.65 and a ternary K₂O–TiO₂–P₂O₅ (KTP) glass were studied by X-ray and neutron diffraction. The experiments were performed at the high-energy beamline BW5 of the synchrotron DORIS (Hamburg/Germany) and at the GEM instrument of the neutron source ISIS (Chilton/UK). Gaussian fitting of well-resolved first-neighbor peaks in the correlation functions of the binary glasses with TiO₂ contents of 0.65 and 0.60 result in Ti–O coordination numbers of 5.65 ± 0.2 and 5.9 ± 0.2, respectively. Distorted TiO₆ octahedra and isolated PO₄ units form the glassy networks, with a small number of lower coordinated Ti sites for the 0.65 TiO₂ glass. For comparison, only TiO₆ octahedra are found for a ternary K₂O–TiO₂–P₂O₅ glass. The Ti–O coordination numbers are compared with a structural model where all oxygen atoms occupy sites in Ti–O–Ti, Ti–O–P or P–O–P bridges. The presence of three-coordinated oxygens must be assumed for the binary glasses, whereas a structure with nearly all oxygen atoms forming network bridges exists for the ternary KTP glass.     

Preparation of TiO2–Na2O glass by sol–gel method and structural characterization

The applicability of sol–gel process in glass formation of binary system, (100 − x)TiO₂–xNa₂O (x = 10, 20, 30), was investigated and the glasses were prepared successfully by the sol–gel process for the first time. The process of glass formation was checked by using X-ray diffraction measurement and DTA–TG analysis. In the baking step, a DTA peak related to the crystallization of gel was found. The short-range structure of glassified samples was studied by neutron scattering measurement. It is found from the results of neutron scattering measurement that the coordination number of O atom around Ti atom is about 4, and the O atoms around Ti atom form a planer square rather than a regular tetrahedron.     

Effect of glass composition on activation energy of viscosity in glass-melting-temperature range

In the high-temperature range, where the viscosity (η) of molten glass is < 10³ Pa s, the activation energy (B) is virtually independent of temperature (T). Moreover, the coefficient A in the Arrhenius relationship, ln(η) = A + B/T, is nearly independent of melt composition. Hence, the viscosity–composition relationship for η < 10³ Pa s is defined by B as a function of composition. Using a database encompassing over 1300 compositions of high-level waste glasses with nearly 7000 viscosity data, we developed mathematical models for B(x), where x is the composition vector in terms of mass fractions of components. In this paper, we present 13 versions of B(x) as first- and second-order polynomials with coefficients for 15 to 39 components, including Others, a component that sums constituents having little effect on viscosity.     

Structural evolution in the solidification process of Cu–Sn alloys

The liquid structures in the solidification process of the Cu_100−xSn_x (x = 10, 20, 30, 40) alloys were investigated by X-ray diffraction method. The results show that the Cu₃Sn and quasi Cu₃Sn structures exist in the Cu–Sn liquids. Which arouses an obvious structure change indicated by the correlation radius r_c at about 900 °C. In addition, the structure change induced by the liquid–solid transition at about 30–40 °C below the liquidus is also observed.     

Investigation of directional solidified Al–Ti alloy

Al–1 wt% Ti alloy was directionally solidified upwards under argon atmosphere under the two conditions; with different temperature gradients (G = 2.20–5.82 K/mm) at a constant growth rate (V = 8.30 μm/s) and with different growth rates (V = 8.30–498.60 μm/s) at a constant temperature gradient (G = 5.82 K/mm) in a Bridgman furnace. The dependence of characteristic microstructure parameters such as primary dendrite arm spacing (λ₁), secondary dendrite arm spacing (λ₂), dendrite tip radius (R) and mushy zone depth (d) on the velocity of crystal growth and the temperature gradient were determined by using a linear regression analysis. A detailed analysis of microstructure development with models of dendritic solidification and with previous similar experimental works on dendritic growth for binary alloys were also made.     

Relation between β relaxation and fragility in LaCe-based metallic glasses

The studies of the dynamical mechanical properties of a series of (Ce_xLa_1-x)₆₈Al₁₀Cu₂₀Co₂ (where 0 ≤ x ≤ 1) metallic glasses show that the behaviors of β relaxation are closely correlated with the properties of their corresponding supercooled liquids. Metallic glasses quenched from fragile liquids show pronounced β relaxation humps whereas unobvious excess wings are associated with the metallic glasses quenched from strong liquids. Our result suggests he behaviors of β relaxations in the metallic glasses are correlated with the fragility of their supercooled liquids.     

Bulk metallic glass formation in Cu–Zr–Ti ternary system

The formation of bulk metallic glasses (BMG) in the Cu-rich Cu–Zr–Ti ternary system is studied by using the ‘e/a-variant line criterion’. Three such lines, (Cu₉Zr₄)_1−xTi_x, (Cu_61.8Zr_38.2)_1−xTi_x and (Cu₅₆Zr₄₄)_1−xTi_x, are defined in the Cu–Zr–Ti system by linking three binary compositions Cu₉Zr₄, Cu_61.8Zr_38.2 and Cu₅₆Zr₄₄ to the third element Ti. The binary compositions Cu₉Zr₄, Cu_61.8Zr_38.2 and Cu₅₆Zr₄₄ correspond to specific Cu–Zr binary clusters. BMGs are obtained by copper mould suction casting method with Ti contents of 7.5–15 at.%, 7.5–12.5 at.% and 5–12 at.%, respectively along the (Cu₉Zr₄)_1−x Ti_x, (Cu_61.8Zr_38.2)_1−xTi_x and (Cu₅₆Zr₄₄)_1−xTi_x lines. The BMGs on each composition line manifest decreased thermal stabilities and glass forming abilities (GFAs) with increasing Ti contents. The maximum GFA appears at Cu₆₄Zr_28.5Ti_7.5, with characteristic thermal parameters of T_g = 736 K, T_x = 769 K, T_g/T_l = 0.627 and γ = 0.403, which are all superior to those reported for the known Cu₆₀Zr₃₀Ti₁₀ BMG.     

Silica xerogels and aerogels synthesized with ionic liquids

The synthesis of silica gels with ionic liquids (IL) as either additives or co-solvents is described. The wet gels were either dried by supercritical CO₂ or by evaporation to obtain aerogels or xerogels, respectively. The effects of two ionic liquids: 1-butyl-3-methyl imidazolium tetrafluororate (IL1) and 1-butyl-4-methyl pyridinium tetrafluoroborate (IL2), on the structural and textural characteristics of gels were investigated. IL2 showed a more important influence than IL1, on the gelation time and gel structure, according to solid state NMR investigations. With both types of ionic liquids, the average pore radius of xerogels increased from ≈2 nm at an IL to Si molar ratio n_IL/n_Si = 0.07, to ≈4 nm at n_IL/n_Si ≈ 1.5 and the size distributions were rather well centered about each mean radius. Hence, ionic liquids appeared as interesting additives to target gels with a given pore size.     

Electronic properties of liquid noble metal–Si alloys

The electrical resistivity, ρ, of liquid noble metal–Si alloys (M_1−cSi_c, M = Cu, Ag, Au) increases rapidly with the addition of Si to liquid noble metals. The composition dependence of ρ exhibits a maximum at the composition c = 0.3, 0.4 and 0.4 for liquid Cu–Si, Ag–Si and Au–Si, respectively. A positive to negative transition of thermoelectric power, S, is observed at c = 0.3, 0.15 and 0.1 for liquid Cu–Si, Ag–Si and Au–Si, respectively. Their composition dependence of S reaches a minimum value in the composition range c = 0.6–0.8. The experimental results of ρ and S have been analyzed using the Faber–Ziman theory. The composition dependence of χ for liquid Cu–Si and Au–Si alloys exhibits a clear deviation from a straight line on the noble metal-rich side. As a result, liquid Cu–Si and Au–Si alloys have a minimum in the composition dependence of paramagnetic susceptibility.     

Kinetic fragility of hydrous soda-lime-silica glasses

The effect of hydration on the kinetic fragility of soda-lime-silica glasses was investigated by viscometry in the glass transition range. Water-bearing glasses were prepared from industrial float glass (FG) and a ternary model glass (NCS = 16Na₂O 10CaO 74SiO₂ in mol%) by bubbling steam through the melt at 1480 °C and up to 7 bar. Additionally, a sodium borosilicate glass (NBS = 16Na₂O 10B₂O₃ 74SiO₂ in mol%) was hydrated under equal conditions. As detected by infrared spectroscopy water dissolves in the glasses exclusively as OH-groups. The hydration resulted in a total water content C_W up to ≈ 0.2 wt% for FG, NCS and NBS glasses. Kinetic fragility, expressed by the steepness index m, was determined from the temperature dependence of η at the glass transition. Viscosity data from previous studies on hydrous float glasses (C_W > 1 wt%) were surveyed together with literature data on the (H₂O)–Na₂O–CaO–SiO₂, (H₂O)–Na₂O–SiO₂ and (H₂O)–SiO₂ systems to expand the range of water concentration and bulk composition. We could demonstrate that m decreases for all glasses although water is dissolved as OH and should depolymerize the network. An empirical equation of the general type m = a ? b logC_W where a, b are fitting parameters, enables m to be predicted, for each glass series as function of the water content C_W. The enlarged data base shows that the parameter B of the Arrhenius viscosity-temperature relation decreases much stronger than the isokom temperature at the glass transition.