A SAXS study of the gelation process of silicon and titanium alkoxides

The gelation process of silicon ethoxide and titanium iso-propoxide solutions was studied as a function of water content and reaction time by small-angle X-ray scattering (SAXS). Approaching the gelation points, the SAXS intensities for titanium tetra-iso-propoxide solutions start to follow a power-law decay in the Porod region, except for a H₂O/Ti ratio greater than 4. For silicon ethoxide solutions, the fractal dimension, d_f, measured for aggregated clusters increases continually with the H₂O/Si ratio and can be related to the spinnability of the solutions. For solutions of both silicon and titanium alkoxides, a solution of fractal dimension d_f < 1.79 shows spinnability, whereas solutions having d_f > 1.79 and no fractal structures do not show spinnability.     

Porous silica alcogel matrix entrapped with liquid electrolyte: Ionic conductivity and growth of whiskers

Highly porous silica alcogel, with pores entrapped with liquid electrolyte solutions of KH₂PO₄, has been successfully prepared by hydrolysis and polycondensation of tetraethylorthosilicate (TEOS) giving interesting “solid-liquid electrolyte composites”. The entrapped liquid electrolyte solution gives high liquid-like ionic conductivity (10⁻⁵ S·cm⁻¹). Further, on storage the entrapped solution slowly reaches the surface pore-heads where it evaporates resulting in the growth of long crystalline whiskers. Higher relative humidity (>60%) slows down the evaporation and has been found to be favorable for whisker growth.     

Rheology of sols and fiber drawing

The investigations on the viscosity of the metal alkoxide solutions in the course of hydrolysis and condensation reactions leading to the gelation of sols have been reviewed. All the solutions which gel finally show a continuous increase in viscosity with time until they gel at a certain viscosity higher than about 100 P which is dependent on the composition of the starting solution. When a metal alkoxide solution is catalyzed with an acid and its water content is small at less than 4 or 5 in the water to alkoxide mol ratio, the solution exhibits spinnability at viscosities above about 10 P and becomes drawable into gel fibers, whereas no spinnability appears when a solution contains a large amount of water or is catalyzed with an alkali like ammonia.

The investigations on the relation between the reduced viscosity and the concentration or the relation between the intrinsic viscosity and the number-averaged molecular weight have made it clear that the spinnable silicon alkoxide solutions have long-shaped siloxane particles and non-spinnable solutions have round particles.

It has been established that spinnable solutions exhibit Newtonian flow behavior up to high viscosities, where fibers can be drawn, while non-spinnable solutions exhibit marked structural viscosity and, sometimes, thixotropy. Similar behavior is confirmed in the alumina solutions prepared from inorganic salts. It has been reported that the viscosity measurements provide information on the rate of the reaction leading to gelation. It is also known that the viscosity of the alkoxide solution controls the thickness of the thin coating film made by the dip-coating technique using an alkoxide solution.     

Internal friction and structural relaxation of amorphous Fe---Mn---P alloys

Measurements of internal friction and dynamic modulus have been carried out on amorphous Fe_83−xMn_xP₁₇(x=9,12, or 15) alloys in the temperature range 300–800 K, as a function of applied frequency, by a forced oscillation method. The characteristic transition temperatures and activation energies for crystallization were measured by differential scanning calorimetry (DSC). The viscous flow of the sample was measured using a thermomechanical analyzer (TMA) under continuous heating conditions. Internal friction increases rapidly with temperature starting from 450 K for 0.1 Hz, 474 K for 0.5 Hz, 486 K for 1.0 Hz, 511 K for 5 Hz, and 525 K for 10 Hz for the Fe₇₄Mn₉P₁₇ specimen. It was found that the internal friction peak temperature was very closely the same as the steady state viscous flow temperature from the TMA curves for Fe₇₄Mn₉P₁₇ and Fe₆₈Mn₁₅P₁₇ but not for Fe₇₁Mn₁₂P₁₇. It is assumed that the internal friction peak does not correspond to the glass transition temperature or crystallization temperature for these alloy systems. Two maxima in the free-volume fraction and two minima in the viscosity were also found for the samples which exhibit a ‘mid-contraction’ in their TMA displacement curves. The internal friction peak occurred at the steady state viscous flow temperature. This occurrence means that the origin of the internal friction peak is related to the viscous flow behavior and free-volume fluctuation for this alloy system.     

The preparation of boron-doped silicon carbide powder by the carbothermal reduction of oxides derived from the hydrolyzed methyltriethoxysilane

A precursor prepared from a methyltriethoxysilane ((CH₃)Si(OC₂H₅)₃, MTES)-B(OC₂H₅)₃-polyacrylonitrile (PAN) composition was used for the synthesis of boron-doped SiC by carbothermal reduction. Initially, MTES was hydrolyzed with HCl (MTES: H₂O: HCl = 1 : 1 : 0.01) for 1 h in a sealed vessel. The number-average molecular weight measurement and a NMR spectrum revealed that the species in the solution were mainly oligometric. With the addition of B(OC₂H₅)₃, no significant changes in the distribution of the Si containing species were detected. The mixing of the hydrolyzed solution with a PAN-dimethylsulfoxide solution led to a homogeneous solution. After the evaporation of the solvents and the subsequent heat treatment at 220° C, brown precursor powder was obtained. By the heat treatment at 1600° C in Ar, it was converted to boron-doped SiC powder.     

Spinnablity and structure characterization of mullite fibers via sol–gel-ceramic route

Viscosity and rheology behaviors of the mullite sols prepared from aqueous solution of aluminum nitrate, aluminum isopropoxide and tetraethylorthosilicate has been investigated. Rheological measurement suggested that mullite sols exhibited good spinniabilty when the evaporation of the solvent is allowed during sol–gel process. Spinnable sols showed shear-thinning flow behavior with high viscosity to the time of gelation. By adjusting temperature, the gelation degree and viscosity of the sol could be stabilized at a certain value and the sol–gel transition could be transferred to the spinning line of a laboratory dry-spinning apparatus. Continuous mullite fibers were obtained from such sols using sol gel dry-spinning method. The final ceramic fibers had smooth surfaces with an average diameter of 50 μm. Structure evolution of mullite ceramic fibers were characterized by MAS NMR and specific surface area analyses.     

Properties of ZrO2---Al2O3 composite powders prepared from Zr---Al metallo-organic compounds

Zr---Al metallo-organic compounds (zircoaluminates), having (CH₂)₄COOH, (CH₂)₁₂CH₃ and (CH₂)₂NH₂ as the organofunctional groups, were treated preliminary by (1) spray-drying, (2) gelation of addition of 10% NH₄OH aqueous solution followed by spray-drying and (3) rotary evaporation under a reduced pressure. After the treatment they were heated in air to prepare ZrO₂---Al₂O₃ composite powders. The IR and DTA profiles for the treated compounds indicated that the procedures modified the structures for the zircoaluminates. The stability of tetragonal ZrO₂ for the ZrO₂---Al₂O₃ composite powder were dependent on the modification in the structure for the zircoaluminates. Balloon shaped particles, 0.5–2 μm in diameter, were obtained through procedure (1) and spherical particles, 1–4 μm in diameter, through (2). Tetragonal ZrO₂ grains, 0.1–0.2 μm in diameter, were dispersed in the particles when heated at 1400°C.     

Synthesis, growth, thermal, optical, dielectric and mechanical properties of semi-organic NLO crystal: Potassium hydrogen malate monohydrate

Potassium hydrogen malate monohydrate (PHMM), a semi-organic nonlinear optical material, has been synthesized and single crystals were grown from aqueous solution. Single crystals of PHMM have been grown by slow evaporation of solvent at room temperature up to dimensions of 22 mm×16 mm×14 mm. Single-crystal X-ray diffraction study on grown crystals shows that they belong to monoclinic system and non-centrosymmetry spacegroup Cc. The structural perfection of the grown crystals has been analyzed by high-resolution X-ray diffraction (HRXRD) rocking curve measurements. Fourier transform infrared (FTIR) spectroscopic study was performed for the identification of different modes of functional groups present in the compound. The UV–Vis transmission spectrum has been recorded in the range 200–1100 nm. The thermal stability of the compound has been determined by TG-DTA curves. The dielectric studies were performed. From the microhardness measurements, Vicker's hardness number (H_v), Stiffness constant (C₁₁), fracture toughness (k_c), Brittle index (B_i) and yield strength (σ_y) have been calculated. The Young's modulus was calculated using the Knoop hardness measurement. The SHG relative efficiency of PHMM crystal was found to be 1.2 times higher than that of KDP.     

微筛孔反应器液相沉淀法制备纳米CaCO3

采用微筛孔反应器,以Ca(NO₃)₂·4H₂O为钙源连续相、(NH₄)₂CO₃为碳源分散相,液相沉淀法制备纳米CaCO₃。利用XRD、TEM等表征手段分析研究分散相与连续相流量、浓度和停留时间等制备条件对碳酸钙的粒径、产率和形貌的影响。结果表明,使用微筛孔反应器通过液相沉淀法可制得平均粒径45~92 nm、产率达80%以上的方解石型纳米CaCO₃。适宜的制备条件为:连续相进料流量F_C=150 mL/min、分散相进料流量F_D=150 mL/min、连续相浓度[Ca²⁺]=0.05 mol/L、分散相浓度[CO^2-₃]=0.2 mol/L、停留时间τ=5 s。微筛孔反应器特有的孔道结构能够均匀分散液相体系,从而避免了一般微反应器在液相沉淀反应中出现的堵塞问题,微筛孔反应器的分子扩散混合模式可大幅度强化液相体系的扰动程度并提高CaCO₃过饱和度,使制得样品粒径较小且分布极窄。同时,通过改变制备条件可灵活调控样品的形貌与粒径。     

Silica glass tubes by new sol-gel method

Silica glass tubes were prepared by following a new sol-gel method. The pH of the sol containing hydrolyzed Si(OC₂H₅)₄ with HCl and colloidal silica was adjusted by adding ammonia solution. Sol was poured into a cylindrical tube and gelled while rotating cylinder at 1000 rpm to form a tube-shaped gel. Then the gel was dried carefully to be tube dry-gel and finally sintered to become a clear silica glass tube.

The effects were examined of the speed of rotation before and after gelation, to form the tubular gel, upon the shape and appearance of the derived tubes. The best speed of rotation was about 1000 rpm, and an adequate long period of rotation after gelation was necessary to maintain the tube shape. One of the large silica tubes had dimensions of 26 mm outside diameter, 13 mm internal diameter and 1000 mm length, and the ovality of the silica glass tube was 0.02%.

The derived tube can be applied in a silica glass tube for an optical fiber fabrication process or in a furnace tube for IC production.     

Dynamical properties of an alkali chloride mixture in the glassy and liquid states

Molecular dynamics calculations have been carried out to reveal the dynamical properties of an alkali chloride mixture (50 mol% LiCl---40KCl---10CsCl) and pure LiCl in the liquid and glassy states. It is found that the mobility of Li⁺ ions in the mixture is significantly lower than that in LiCl, not only in liquid state but also in the glassy state. The partial dynamic structure factors, S_Li---Li (Q, ω) and S_{Cl---Cl (Q, ω)}, are evaluated to investigate the dynamical correlation between the Li⁺ and Cl⁻ ions. In LiCl glass, it is shown that the motions of the Li⁺ and Cl⁻ ions are highly correlated with each other, and both the acoustic and optic modes are spatially delocalized (Q < 1.8 Å⁻¹). On the other hand, in the mixture glass, the motion of the Li⁺ ions is almost independent of that of the Cl⁻ ions, and at small wavelengths there are the intense vibrations localized on single Li⁺ ions similar to an Einstein oscillation.     

XPS studies of polyhedral linkages in binary fluoride films

Amorphous thin films of the ZrF₄---PbF₂ binary composition system fabricated by thermal evaporation and studied by X-ray photoelectron spectroscopy. The chemical shift of the F 1s peak is analyzed to yield the distribution of polyhedral linkages in terms of Zr---F---Zr, Pb---F---Pb and Zr---F---Pb bridges. The predominance of cross-species bridging suggests a large negative enthalpy of mixing between ZrF₄ and PbF₂.     

零维钙钛矿结构Cs3Cu2Br5单晶的生长和X射线探测性能

金属卤化物低维钙钛矿具有高效的发光性能,并且作为闪烁体在辐射探测领域表现出极大的潜力。本文采用布里奇曼坩埚下降法生长出全无机零维钙钛矿结构Cs₃Cu₂Br₅单晶。研究了Cs₃Cu₂Br₅的光学吸收、光致激发和发射,时间分辨光致发光和以及X射线探测性能。Cs₃Cu₂Br₅晶体结构为正交晶系,空间群为Pnma。在X射线激发下,Cs₃Cu₂Br₅晶体具有峰值约为467 nm的宽带发射,该发射来自自陷激子发射。Cs₃Cu₂Br₅的稳态光产额约为4 000 ph./MeV,且X射线余辉性能表现与BGO晶体相当。     

SAXS investigations of structure of formation in alcoholic ZrO2---SiO2 solutions

Small-angle X-ray scattering was used to examine in situ formation of ZrO₂---SiO₂ structures in alcoholic solution of tetraethoxysilan (TEOS) as a function of the ratio of ZrO₂ to SiO₂. For the moment of the first measurement (15 min after the preparation) primary particles with R_g ≈ 1.5 nm exist in all investigated mixed gels. These particles aggregated to secondary clusters. The resulting clusters can be described by means of fractal theory, where the determining mechanism of formation is cluster-cluster aggregation (diffusion or chemical limited). The time of gelation is a function of the ZrO₂ concentration. The higher the ZrO₂ concentration in the solution, the faster is the aggregation to secondary clusters. Gelation times were between 170 and 970 h.     

Vibrational and structural properties of glass and crystalline phases of TeO2

A wide-spread opinion regarding the paratellurite (-TeO₂) lattice as a parent structure of TeO₂ glass is questioned. Consequently, the Raman and infrared spectra of TeO₂ glass are contrasted with those of three crystalline lattices (, β, γ) of TeO₂ and their vibrational state density distribution functions. Additionally, the data on the crystallization of the liquid and glassy states of TeO₂ are considered. As a result, of the known crystalline phases of TeO₂, the γ-phase is proposed as the closest to TeO₂ glass.     

Hydrolysis and condensation reactions of Si(OC2H5)4 related to silica fiber drawing

The hydrolysis and condensation reactions of Si(OC₂H₅)₄ (TEOS) at 80°C in the TEOS---H₂O---C₂H₅OH---HCl solutions with H₂O/TEOS molar ratios (r) from 1.0 to 2.0 were followed by gas chromatography (GC) and measurement of molecular weight ( ) of the hydrolyzates, in order to explain the viscosity change of the solutions. It has been found that the siloxane oligomers with average polymerization degree (n) from 2 to 7 are formed in the early stage of reaction and undergo condensation to form higher polymers. The n and the number of silanol groups of the oligomers are increased with increasing r. The fact that the solution viscosity increased once rapidly around the so-called gelation point followed by a sluggish increase with the increase of reaction time for an r of 1.7, while it increased rapidly without a break till gelation for an r of 2.0, was attributed to fewer silanol groups and higher steric hindrance as a result of more −OC₂H₅ groups remaining in the oligomers for an r of 1.7.     

Ca(H2PO4)2-H3PO4-K2SO4体系中石膏晶型及形貌调控

为将Ca(H₂PO₄)₂制备KH₂PO₄过程中的石膏资源化利用,以H₃PO₄与CaCO₃反应制备Ca(H₂PO₄)₂溶液,并与K₂SO₄溶液反应,进行Ca(H₂PO₄)₂-H₃PO₄-K₂SO₄体系中石膏晶型和形貌调控研究。结果表明:通过改变反应时间、反应温度、SO^2-₄过量系数和CaO含量等参数可对Ca(H₂PO₄)₂-H₃PO₄-K₂SO₄体系中石膏晶型和形貌进行调控,制得短柱状α-CaSO₄·0.5H₂O。体系在温度高于95 ℃和CaO含量为3.0%~5.0%(质量分数,下同)时形成α-CaSO₄·0.5H₂O,在CaO含量为5.5%主要形成CaSO₄·2H₂O;反应时间长于20 min和SO^2-₄过量系数大于1.4将形成K₂SO₄(CaSO₄)₅·H₂O,导致石膏晶体表面缺陷增加。本实验条件下,适宜反应条件为:反应时间10 min、反应温度95 ℃、SO^2-₄过量系数1.2和CaO含量5.0%,此条件下可制得长度42~70 μm、直径13~24 μm的短柱状α-CaSO₄·0.5H₂O,其抗折和抗压强度分别可达5.61 MPa和33.74 MPa,滤液中钾收率和脱钙率分别可达94.23%和83.80%。     

Densification kinetics of porous colloidal P2O5-doped silica gels using constant heating rate measurements

Commercially available fumed colloidal silica was gelled in an aqueous solution containing PO₄H₃. Instantaneous gelation was obtained by adding several drops of HF (48 wt%). The objective of this paper was to study the gel-to-glass conversion of these colloidal gels using constant heating rate (CHR) experiments.

Gel densification was measured at temperatures ranging from 50 to 1550°C at different heating rates (1 to 10°C/min) using a dilatometer.

Shrinkage and shrinkage rate as a function of temperature were measured and CHR equations were used to derive information on the densification mechanisms.

The experimental results show that small additions of PO₄H₃ into pure silica dispersions give rise to gels which densify to high silica glass at much lower temperatures than pure colloidal silica gels. The bloating effects produced by pure colloidal silica gels at temperatures above 1280°C were also eliminated. For these P₂O₅-doped silica gels maximum shrinkage rates were found at temperatures between 1050 and 1150°C according to the heating rate used.

The CHR analysis showed that several different mechanisms seem to operate in a complex interdependence in the whole range of temperature studied. This CHR analysis was compared with those results obtained from isothermal shrinkage experiments in the range where viscous sintering is the predominant shrinkage-controlling mechanism (between 1000 and 1100°C).     

Multinuclear NMR study of aluminosilicate sol-gel synthesis using the prehydrolysis method

Tetraethoxysilane (TEOS), water and aluminum sec-butoxide (Al(OBu^s)₃) are combined in several stages of prehydrolysis technique, and reaction intermediates at each stage were examined by means of both liquid and solid nuclear magnetic resonance of ¹³C, ²⁹Si, ¹⁷O, and ²⁷Al nuclei. The spectra indicate that when Al(OBu^s)₃ is added to a prehydrolyzed TEOS solution an aluminosilicate precursor is formed in which the aluminum is tetrahedrally coordinated by four silicate ligands. When further water is added, gelation is accompanied by the expansion of aluminum coordination; the spectra indicate that this occurs by the nucleophilic attack of silanol groups. At water contents for which gels of low transparency result, this coordination expansion is accompanied by the formation of new siloxane linkages, but at water contents so high that opaque gels result, the coordination expansion proceeds much more quickly and no new siloxane linkages are observed.     

气相输运沉积制备c轴择优取向的碘化铋薄膜

铋基卤化物材料因其无毒和优良的光电性能而显示出巨大的应用潜力。BiI₃作为一种层状重金属半导体,已被用于X射线检测、γ射线检测和压力传感器等领域,最近其作为一种薄膜太阳能电池吸收材料备受关注。本文采用简单的气相输运沉积(VTD)法,以BiI₃晶体粉末作为蒸发源,在玻璃基底上得到高质量c轴择优取向的BiI₃薄膜。并通过研究蒸发源温度和沉积距离对薄膜物相和形貌的影响,分析了BiI₃薄膜择优生长的机理。结果表明VTD法制备的BiI₃薄膜属于三斜晶系,其光学带隙为~1.8 eV。沉积温度对薄膜的择优取向有较大影响,在沉积温度低于270 ℃时,沉积的薄膜具有沿c轴择优取向生长的特点,超过此温度,c轴择优取向生长消失。在衬底温度为250 ℃、沉积距离为15 cm时制备的薄膜结晶性能最好,晶体形貌为片状八面体。