Phase equilibria and dielectric properties of Bi3+(5/2)xMg2−xNb3–(3/2)xO14−x cubic pyrochlores

Subsolidus pyrochlores with the proposed formula, Bi_3+(5/2)xMg_2−xNb_3−(3/2)xO_14−x (0.14≤x≤0.22) were successfully synthesised at the firing temperature of 1025 °C using conventional solid-state reaction. The excess Bi³⁺ charge was offset by removal of relative proportion of Mg²⁺ and Nb⁵⁺ together with creation of oxygen non-stoichiometry in order to preserve electroneutrality of the system. These samples were crystallised in cubic structure with space group of Fd3m, No. 227 and their refined lattice parameters were in the range of 10.5706 (3)–10.5797 (7) Å. The surface morphologies of the samples as confirmed by scanning electron microscopy analysis were of irregular shaped grains while their crystallite sizes of ~30–85 nm were calculated using the Scherrer equation and the Williamson–Hall method. No thermal event was discernable indicating these pyrochlores were thermally stable within a studied temperature range of ~30–1000 °C. The recorded dielectric constants of Bi_3+(5/2)xMg_2−xNb_3−(3/2)xO_14−x (0.14≤x≤0.22) subsolidus pyrochlores were generally above ~160 and their dielectric losses were in the order of 10⁻⁴–10⁻³ at the frequency of 1 MHz and temperature of ~30 °C. Meanwhile, these ceramic samples also exhibited negative temperature coefficient of relative permittivity between −528 and −742 ppm/°C in the temperature range of ~30–300 °C.     

Low temperature sintering and microwave dielectric properties of Ba3Ti5Nb6O28 with ZnO–B2O3 glass additions for LTCC applications

The effects of ZnB₂O₄ glass additions on the sintering temperature and microwave dielectric properties of Ba₃Ti₅Nb₆O₂₈ have been investigated using dilatometer, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and a network analyzer. The pure Ba₃Ti₅Nb₆O₂₈ system showed a high sintering temperature (1250 °C) and had the good microwave dielectric properties: Q × f of 10,600 GHz, ɛ_r of 37.0, τ_f of −12 ppm/°C. It was found that the addition of ZnB₂O₄ glass to Ba₃Ti₅Nb₆O₂₈ lowered the sintering temperature from 1250 to 925 °C. The reduced sintering temperature was attributed to the formation of ZnB₂O₄ liquid phase and B₂O₃-rich liquid phases. Also the addition of ZnB₂O₄ glass enhanced the microwave dielectric properties: Q × f of 19,100 GHz, ɛ_r of 36.6, τ_f of 5 ppm/°C. From XPS and XRD studies, these phenomena were explained in terms of the reduction of oxygen vacancies and the formation of secondary phases having the good microwave dielectric properties.     

Permeation of alkylbenzene isomers of molecular weight 120 through nitrile gloves

Factors determining the permeation of eight alkylbenzene isomers of molecular weight 120.19 (three ethyl toluenes, three trimethylbenzenes, and two propl benzenes) were investigated for a lined nitrile industrial type glove using an ASTM-type cell, liquid collection, and gas chromatography/mass spectrometry. The initial permeation rate P_i correlated inversely with the logarithm of the lag time t_l. The logarithm of the steady-state permeation rate P_s correlated inversely with the logarithm of the breakthrough time t_b. P_s/P_i for a given compound correlated directly with P_s and with t_l/t_b. P_i depended directly on the logarithm of the entropy of fusion divided by the square of the refractive index and divided by the solubility parameter. The t_b was inversely correlated to the logarithm of the water solubility. The logarithm of t_l was most directly correlated to the entropy of vaporization. High P_s for 1,2,4-trimethylbenzene, m-ethyltoluene, and p-ethyl toluene was linked to a common structural similarity to 1,2,4-trimethylbenzene relative to the unhindered geometry of the methyl group in the ethyl side chain. The existence of optimum radii of gyration for enhanced P_s and for long t_b suggested that the protective properties of nitrile followed discontinuous relationships rather than continuous ones and so are not explainable by correlative relationships of continuous functions. © 1996 John Wiley & Sons, Inc.     

Effects of CaSiO3 addition on sintering behavior and microwave dielectric properties of Al2O3 ceramics

The effects of CaSiO₃ addition on the sintering behavior and microwave dielectric properties of Al₂O₃ ceramics have been investigated. The addition of CaSiO₃ into Al₂O₃ ceramics resulted in the emergence of Ca₂Al₂SiO₇ and CaAl₂Si₂O₈, which acting as liquid sintering aids can effectively lower the sintering temperature of Al₂O₃ ceramic. The Q × f value of Al₂O₃-CaSiO₃ ceramics decreased with the CaSiO₃ addition increasing because of the lower Q × f value of Ca₂Al₂SiO₇ and CaAl₂Si₂O₈. Compared with the pure CaSiO₃ ceramic, the Al₂O₃-CaSiO₃ ceramic with 20 wt% CaSiO₃ addition possessed good dielectric properties of ?_r = 9.36 and Q × f = 13,678 GHz at the similar sintering temperature.     

Evolution with heat treatment of crystallinity in carbons

The variation with heat treatment of the dimensions L_a and L_c of the graphite-like crystallites of graphitizable and non-graphitizable carbons is studied. The increases of L_a and L_c with heat treatment temperature (HTT) owing to three processes (crystallite growth in-plane, coalescence of crystallites along the c-axis and coalescence of crystallites along the a-axis) are functionally separated. The evolution with HTT of the number of crystallites (N_cr), the mean volume of the crystallites (v_cr) and the total volume occupied by the crystallites (V_cr) are determined in terms of the changes of L_a, L_c and d₀₀₂. Since among other characteristics the crystallites form the electrical and thermal conducting phase of the carbon, N_cr, v_cr and V_cr are important parameters in many physical properties of these materials. The developed expressions were applied to a non-graphitizable and to a graphitizable carbon.     

Stabilization effect of Co for Mo phase in CoMoAl2O3 hydrodesulfurization catalysts studied with X-Ray photoelectron spectroscopy

The promotional effects of Co in $\text{CoMo}\text{Al}{}_2\text{O}{}_3$ hydrodesulfurization (HDS) catalysts were studied by means of X-ray photoelectron spectroscopy. The higher MoO₃-content $\text{Mo}\text{Al}{}_2\text{O}{}_3$ catalysts (10 and 20 wt% MoO₃) contain mobile Mo, which migrates from the pores to the outermost surface layers of the catalysts and segregates to form less active crystalline MoS₂ during the HDS reaction, while in the case of $\text{Mo}\text{Al}{}_2\text{O}{}_3$ (5 wt% MoO₃) catalyst: no migration of Mo was observed. It is revealed that the Co in $\text{CoMo}\text{Al}{}_2\text{O}{}_3$ catalyst inhibits the migration and segregation of Mo and that it keeps Mo effective for the HDS reaction, since no surface enrichment of Mo was observed. It is concluded that stabilization of the Mo monomolecular layer is the main role of Co. The active species of Mo is suggested to have the composition of S/Mo(IV) = 1 on the basis of the sulfur contents of the catalysts under the mild HDS reaction conditions.     

Flow microcalorimetry on dilute polymer solutions

A flow microcalorimeter designed to measure the heat of mixing of dilute polymer solutions is described. The instrument is sensitive to steady state heating rates of ～10 μJ/sec. Measurements of heats of mixing of solutions of differing concentrations of n-hexane and cyclohexane are reported and are compared with recommended data of McGlashan and Stoeckli. Values of:

$\text{K}{}_1\text{=}\text{lim}\text{V}{}_2\text{→ 0}$

$\text{(}\text{H}\text{?}{}_1\text{?}\text{H}\text{?}{}^0{}_1\text{RTv}{}^2{}_2$ are obtained for four polymer—solvent systems: polyisobutylene—benzene, 0.22; polystyrene (PS)—cyclohexane, 0.33; PS—n-butyl acetate, ?0.06 all at 25°C; and PS—toluene, ?0.05 at 40°C. Various theoretical calculations of second virial coefficients A₂ made with use of the calorimetric data are compared with previously measured A₂ for the first two mixtures.     

The kinetic evidence for the formation of multiple active species in a bis(phenoxy-imine) zirconium dichloride/MAO catalyst during ethylene polymerization

The effects of polymerization time and temperature on the molecular weight and molecular weight distribution of polyethylene, produced over homogeneous catalyst bis[N-(3-tert-butyl salicylidene)anilinato]zirconium(IV) dichloride ^tBu-L₂ZrCl₂/MAO have been studied. The data on the number of active centers (C_P) and propagation rate constants (k_P) at different polymerization time have been obtained as well. It was found that at a short polymerization time two types of active centers, producing low molecular weight PE (M_w = (4-10) × 10³ g mol⁻¹) are formed. The number of these centers was estimated to be 11% of total zirconium complex and their reactivity is very high (the k_P value was found to be 54 × 10³ L mol⁻¹ s⁻¹ at 35 °C). High initial activity of the catalyst fell with the increase in polymerization time, whereas the polydispersity values of the resulting PE increase due to formation of new centers, producing high molecular weight PE (M_w = (30-1300) × 10³ g mol⁻¹). It was found that the decrease in activity is caused by reducing the initial active centers number and lower reactivity of the new-formed centers (k_P = 17 × 10³ L mol⁻¹ s⁻¹).     

Temperature dependence of birefringence and stress for natural rubber vulcanizates at strained state

The temperature dependence of stress and birefringence for natural rubber vulcanizates under medium and large deformation was measured for the processes of cooling, heating and re-cooling. In order to investigate the relation between the stress and crystal phase, the observed birefringence, Δt, was converted into the crystallinity, X_v, by the following equation:

$\text{X}{}_{\mathrm{<mtext>v</mtext>}}\text{=}\text{Δt?Δn}{}_{\mathrm{<mtext>a</mtext>}}\text{°f}{}_{\mathrm{<mtext>a</mtext>}}\text{Δn}{}_{\mathrm{<mtext>c</mtext>}}\text{°f}{}_{\mathrm{<mtext>c</mtext>}}\text{?Δn}{}_{\mathrm{<mtext>a</mtext>}}\text{°f}{}_{\mathrm{<mtext>a</mtext>}}$

where Δn⁰_c, Δn⁰_a, f_a and f_c are the intrinsic birefringence of the crystal, that of the amorphous phase, the orientation factor of crystallites, and that of amorphous phase, respectively. The fusion of crystallites induced by the thermal crystallization resulted in the increasing contractile force, while the fusion of strain-induced crystallites induced the reduction of contractile force.     

Long terminal linear alkyl group as internal crystallization accelerating moiety of poly(l-lactide)

Poly(l-lactide) (PLLA) polymers having terminal n-alkyl groups with a wide variety of lengths (C₀–C₂₂) were synthesized by ring-opening polymerization of l-lactide in the presence of coinitiators of l-lactic acid (C₀), 1-hexanol (C₆), 1-dodecanol (C₁₂), and 1-docosanol (C₂₂) and their segmental mobility and non-isothermal and isothermal crystallization behavior were investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffractometry (WAXD). Glass transition and cold crystallization temperatures of melt-quenched samples during heating decreased with an increase in the length of terminal n-alkyl groups. The enhanced PLLA segmental mobility and hydrophobic interaction-based accelerated PLLA nucleation by the presence of terminal long n-alkyl groups should have caused the accelerated non-isothermal and isothermal crystallization of PLLA segments traced by cold crystallization temperature during heating and by radial growth rate of spherulites, respectively. The crystallization accelerating effect became higher with the length of terminal n-alkyl groups. The effects of the length of terminal n-alkyl group on the crystalline growth mechanism of PLLA at the lowest crystallizable temperature was insignificant, whereas the effects of the length of terminal n-alkyl group on the nucleation mechanism of PLLA chains were significant and insignificant for PLLA having M_n of 6–7 × 10³ of 2 × 10⁴ g mol⁻¹, respectively. WAXD measurements revealed that the transition crystallization temperature at which crystalline modification changes from δ-form to α-form was affected by the length of terminal n-alkyl group for PLLA having M_n of 6–7 × 10³ g mol⁻¹, but was not altered by the length of terminal n-alkyl group for PLLA having M_n of 2 × 10⁴ g mol⁻¹.     

The kinetics of the catalytic hydrogenolysis of ethane over Ni/SiO2

The rate of hydrogenolysis of ethane over a Ni/SiO₂ catalyst, studied over a large range of pressure and of temperature, is shown to be related to the degree of hydrogen coverage θ_H, by the equation: with K₀ nearly equal to the number of ethane molecules colliding with the Ni surface, E₀ = 14 ? 1 kcal/mole, Y = ?1 ? 2 and X = 15 ? 2. The rate-limiting step is believed to be the irreversible, dissociative adsorption of ethane on an ensemble of at least 12 adjacent Ni atoms, free from adsorbed hydrogen, resulting in the complete cracking of C₂H₆: C₂H₆ + 12Ni → 2

Irreversible adsorption of ethane is assumed to compete with the reversible adsorption of hydrogen. This mechanism, which is compared with those proposed earlier, is in good agreement with data on ethane adsorption studied by magnetic methods, and with a study of ethane hydrogenolysis over NiCu/SiO₂ catalysts.     

Oxidation-reduction mechanisms in iron-bearing phyllosilicates

Reviewed in this article are the effects of structural Fe oxidation states on the physicochemical properties of smectite clay minerals. Reducing agents selected were dithionite (S₂O₄²⁻), sulfide (S²⁻), thiosulfate (S₂O₃²⁻), hydrazine (N₂H₄), ascorbic acid (C₆H₈O₆), hydroquinone (C₆H₆O₂), and sodium oxalate (Na₂C₂H₂O₄). Clay samples were prepared as aqueous suspensions of < 2 μm particle-size fractions of Na-saturated, freeze-dried ferruginous smectite. The reductive strength of each reducing agent, as determined by measuring the resultant level of Fe(II) in the clay mineral crystal using either a photo-colorimetric method or Mössbauer spectroscopy, decreased in the order S₂O₄²⁻ > S²⁻ > C₆H₈O₆ > S₂O₃²⁻ > C₆H₆O₂ ≈ C₂H₂O₄. The heat of reaction of three of these reducing agents with the clay was measured, and decreased in the order S₂O₄²⁻ > S₂O₃²⁻ > S²⁻. Compared to the order of reductive strength, the heats of reaction with S₂O₃²⁻ and S²⁻ are reversed, suggesting that entropy changes are greater in the S²⁻ treatment. Electron spin resonance (ESR) revealed that free radicals may be responsible for the greatest levels of reductive potential, which provides an important attribute by which potential reducing agents can be screened. Measurements of rheological properties of oxidized and reduced clay suspensions indicated that structural Fe(II) increases the viscosity of clay suspensions as a result of greater attractive forces between clay particles. The type of bonding between particles has yet to be ascertained. Microbial reduction of the clay produces moderate to high levels of reduction and causes changes in physico-chemical properties similar to chemical reduction of the clay.     

Microwave dielectric properties of 0.85CaWO4–0.15SmNbO4 ceramics with sintering additives

Low-temperature sintering and microwave dielectric properties of 0.85CaWO₄–0.15SmNbO₄ (CWSN) ceramics were investigated as a function of Li₂MoO₄ and/or Li₂WO₄ content. With an addition of Li₂MoO₄ and/or Li₂WO₄, the sintering temperature could be reduced from 1150 °C for pure CWSN ceramics to 800 °C. The dielectric constant (K) was not changed remarkably with Li₂MoO₄ and/or Li₂WO₄ content. Quality factor (Qf) of the specimens was decreased with Li₂WO₄ content, while that of the specimens was increased with Li₂MoO₄ content. Qf values of the specimens with 1.0 wt.% Li₂WO₄ showed larger value than that of the specimens with 2.5 wt.% Li₂MoO₄. The temperature coefficient of resonant frequency (TCF) was shifted to the positive value with increasing Li₂WO₄ and/or Li₂MoO₄ content. Typically, K of 12.03, Qf of 13,300 GHz and TCF of −28.6 ppm/°C were obtained for the specimens with 1.0 wt.% Li₂WO₄ sintered at 800 °C for 1 h.     

Synthesis,characterization, and drug release properties of poly(N-isopropylacrylamide) gels prepared in methanol–water cononsolvent medium

Poly(N-isopropylacrylamide) (PNIPAM) hydrogels were simply prepared by free radical polymerization in different methanol–water mixture. A scanning electron microscopy study revealed that the freeze-dried hydrogels were macroporous. The swelling ratios in water at 20°C of the resulting hydrogels followed the order: X_0.43>X_0.21>X_0.76 ≈ X_0.57>X_0.31>X_0.13>X_0.06>X₀, where X_m denotes a gel prepared in a methanol–water mixture with m mole fraction of methanol (x_m). Below the lower critical solution temperature, the swelling ratio values of all of the hydrogels gradually decreased with the increase in the temperature. The complete collapse of the PNIPAM chain of all the gels occurred at about 38°C, whereas the same was observed at about 35°C for the conventional gel prepared in water. The swelling ratio values of all the PNIPAM gels in the methanol–water mixtures with different x_m values at 20°C passed through a minimum in the cononsolvency zone. The deswelling rates of the hydrogels decreased in the following order: X_0.43> X_0.31> X_0.21> X_0.57> X_0.76 ≈ X_0.13> X_0.06> X₀. The reswelling rates of these hydrogels decreased in the following order: X₀> X_0.31> X_0.06 ≈ X_0.13 > X_0.76> X_0.57> X_0.21> X_0.43. The release rates of the Tramadol Hydrochloride drug at 37°C from the drug-loaded hydrogels were almost same for all of the hydrogels. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Conformational studies of poly(N-methyl-l-alanine) by n.m.r. spectroscopy

Nuclear magnetic resonance (n.m.r.) and circular dichroism of $\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ in methylene $\text{chloride}\text{-d}{}_2\text{dichloroacetic acid}$ were investigated. In methylene chloride-d₂$\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ was found to consist of nearly all-trans amide bonds and assume a stable secondary structure. Trace amounts of cis amide bonds were also present. The addition of dichloroacetic acid destroyed the secondary structure and induced a drastic change of the n.m.r. spectrum, which was similar to that observed with the monomeric amide, $\text{N-}\text{acetyl}\text{-N-}\text{methyl-}\text{l}\text{-alanine}$ dimethylamide. In comparison of the polymer with the monomeric amide, it was concluded that the transition of $\text{poly}\text{(N-}\text{methyl-}\text{l}\text{-alanine}\text{)}$ was caused by the isomerization of amide bonds. The complex n.m.r. spectrum was interpreted in terms of the distribution along the polymer chain of various non-planar amide links as well as planar cis and trans amide links. The difference of the mechanism of conformational transition between poly(amino acid) and poly(imino acid) is also discussed.     

Corrosion of stepwise dissolving metals; corrosion mechanism of indium

The corrosion of a metal dissolving stepwise with formation of low-valency intermediates and Mⁿ⁺ ion as the final corrosion product proceeds by a complex electrochemical-chemical mechanism comprising following steps: M → M⁺ + e; M⁺ → Mⁿ⁺ + (n ? 1)O_x → Mⁿ + )n ? 1)O^?_x and O_x + e → O^?_x. A criterion of such a corrosion mechanism is the deviation of the experimental corrosion rate (i_c) from the reduction rate of oxidant O_x at the corrosion potential (i^extr._c) found by extrapolation. Cathodic polarization curves on indium have been measured and its corrosion rate has been determined by a radiotracer method in aqueous NaClO₄ + HClO₄ solutions of varying acidity. i_c is considerably higher than i^extr., the ratio i_c/i^extr._c approaching 3 with increasing acidity. In the same solutions containing O·M NaCl i_c = i^extr._c independent of acidity.     

Yield and yield components of cowpea (<Emphasis Type="Italic">Vigna unguiculata</Emphasis> (L.) Walp.) as influenced by Sokoto phosphate rock and placement methods in the semi-arid zone of Nigeria

Phosphate rock with proper management could be a sustainable source of phosphorus for increased cowpea production on the Entisols of Sokoto Semi-arid zone. Therefore, field experiments were conducted in 2004 and 2005 rainy seasons to determine the influence of Sokoto phosphate rock (SPR) and placement methods on the yield of cowpea varieties. Treatments consisted of factorial combination of two varieties (Ba’adare and IAR48), three levels of SPR (25, 50 and 75 kg SPR ha⁻¹) along with a control (0 kg SPR ha⁻¹) and three placement methods (plough sole, broadcast and side-band) laid out in a randomized complete block design replicated 3 times. Results of phosphate rock and placement methods are presented in this paper. The study indicated significant (P < 0.01) response to applied SPR compared to control (1074 kg grain ha⁻¹) in most parameters studied. Application of 25 kg SPR ha⁻¹ significantly (P < 0.05) influenced higher pod yield and number of pods plant⁻¹ only in 2004 trial. But, shelling percentage, grain yield, stover yield, 1000-grain weight, harvest index (HI) and number of seeds pods⁻¹ were not influenced by SPR levels. Significantly (P < 0.05) higher pod yield in 2004, grain yield, 1000-grain weight and number of pods per plant in 2004 and 2005, HI, shelling percentage and number of seeds pod⁻¹ in 2005, were observed in plough-sole than broadcast and band-side methods of fertilizer placement. Therefore, from this study, it was concluded that SPR could be directly used as a source of P to sustain cowpea production (1527 kg grain ha⁻¹ with 25 kg SPR compared to 1074 kg ha⁻¹with 0 kg SPR). Application of 25 kg SPR ha⁻¹ (3.74 kg P ha⁻¹) using plough-sole method of fertilizer placement was most efficient under Sokoto semi-arid condition.     

Pressure dependence of upper critical solution temperatures in the polystyrene - cyclohexane system

The pressure dependence of the upper critical solution temperature $\text{(}\text{d}\text{T}\text{d}\text{p}\text{)}{}_{\mathrm{c}}$ in the polystyrene-cyclohexane system has been measured over the pressure range of 1 to 50 atm. The value of $\text{(}\text{d}\text{T}\text{d}\text{p}\text{)}{}_{\mathrm{c}}$ determined over the molecular weight (M_w) range of 3.7 × 10⁴ to ～145 × 10⁴ greatly depends on the molecular weight of polystyrene. The value of $\text{(}\text{d}\text{T}\text{d}\text{p}\text{)}{}_{\mathrm{c}}$ for a polystyrene solution of low molecular weight (M_w = 3.7 × 10⁴) is positive (3.14 × 10^?3 degree atm^?1), while the values are negative (?0.52 × 10^?3～?5.64 × 10^?3 degree atm^?) for solutions of polystyrene over the high molecular weight range of 11 × 10⁴ to ～145 × 10⁴. The Patterson-Delmas theory of the corresponding state and the newer Flory theory have been used to explain this behaviour.     

Room temperature living cationic polymerization of styrene with HX-styrenic monomer adduct/FeCl3 systems in the presence of tetrabutylammonium halide and tetraalkylphosphonium bromide salts

Living cationic polymerization of styrene was achieved with a series of initiating systems consisting of a HX-styrenic monomer adduct (X = Br, Cl) and ferric chloride (FeCl₃) in conjunction with added salts such as tetrabutylammonium halides (nBu₄N⁺Y⁻; Y⁻ = Br⁻, Cl⁻, I⁻) or tetraalkylphosphonium bromides [nR′₄PBr; R′ = CH₃CH₂-, CH₃(CH₂)₂CH₂-, CH₃(CH₂)₆CH₂-] or tetraphenylphosphonium bromide [(C₆H₅)₄PBr] in dichloromethane (CH₂Cl₂) and in toluene. Comparison of the molecular weight distributions (MWDs) of the polystyrenes prepared at different temperatures (e.g., −25 °C, 0 °C and 25 °C) showed that the polymerization is better controlled at ambient temperature (25 °C). The polymerization was almost instantaneous (completed within 1 min) and quantitative (yield ∼100%) in CH₂Cl₂. In CH₂Cl₂, polystyrenes with moderately narrow (M_w/M_n ∼ 1.33-1.40) and broad (M_w/M_n ∼ 1.5-2.4) MWDs were obtained respectively with and without nBu₄N⁺Y⁻. However, in toluene, the MWDs of the polystyrenes obtained respectively with and without nBu₄N⁺Y⁻/nR′₄P⁺Br⁻ were moderately narrow (M_w/M_n = 1.33-1.5) and extremely narrow (M_w/M_n = 1.05-1.17). Livingness of this polymerization in CH₂Cl₂ was confirmed via monomer-addition experiment as well as from the study of molecular weights of obtained polystyrenes prepared simply by varying monomer to initiator ratio. A possible mechanistic pathway for this polymerization was suggested based on the results of the ¹H NMR spectroscopic analysis of the model reactions as well as the end group analysis of the obtained polymer.     

Single-crystal elastic constants of natural ettringite

The single-crystal elastic constants of natural ettringite were determined by Brillouin spectroscopy at ambient conditions. The six non-zero elastic constants of this trigonal mineral are: C₁₁ = 35.1 ± 0.1 GPa, C₁₂ = 21.9 ±0.1 GPa, C₁₃ = 20.0 ± 0.5 GPa, C₁₄ = 0.6 ± 0.2 GPa, C₃₃ = 55 ± 1 GPa, C₄₄ = 11.0 ± 0.2 GPa. The Hill average of the aggregate bulk, shear modulus and the polycrystal Young's modulus and Poisson's ratio are 27.3 ± 0.9 GPa, 9.5 ± 0.8 GPa, 25 ± 2 GPa and 0.34 ± 0.02 respectively. The longitudinal and shear elastic anisotropy are C₃₃/C₁₁ = 0.64 ± 0.01 and C₆₆/C₄₄ =0.60 ± 0.01. The elastic anisotropy in ettringite is connected to its crystallographic structure. Stiff chains of [Al(OH)₆]³⁻ octahedra alternating with triplets of Ca²⁺ in eight-fold coordination run parallel to the c-axis leading to higher stiffness along this direction. The determination of the elastic stiffness tensor can help in the prediction of the early age properties of cement paste when ettringite crystals precipitate and in the modeling of both internal and external sulfate attack when secondary ettringite formation leads to expansion of concrete.