Flexural strength reduction of cement pastes exposed to CaCl2 solutions

Calcium chloride (CaCl₂) can react with calcium hydroxide (Ca(OH)₂) to form calcium oxychloride which can reduce flexural strength and damage concrete. This paper aims to characterize the reduction in flexural strength of cement pastes exposed to CaCl₂ solutions using the ball-on-three-balls test. The amounts of Ca(OH)₂ and calcium oxychloride in the cement paste are measured using thermogravimetric analysis and low-temperature differential scanning calorimetry, respectively. The volume change that occurs as a result of the reactions between the cement paste and CaCl₂ is also measured. The reduction in flexural strength increases as the concentration of the CaCl₂ solution increases and the exposure temperature decreases. The flexural strength reduction can be mitigated by increasing the amount of supplementary cementitious materials (fly ash) in the cement pastes. Lowering the water-cementitious materials ratio also reduces the flexural strength reduction. The flexural strength reduction is correlated with the amount of calcium oxychloride and the volume change in the cement pastes exposed to the CaCl₂ solution. While the flexural strength reduction is believed to be primarily due to the formation of calcium oxychloride, the formation of Friedel's salt and Kuzel's salt also contributes to the flexural strength reduction.     

Solid solutions in the Ag<Subscript>2</Subscript>Se-PbSe-Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> system

The phase equilibria in the pseudoternary system Ag₂Se-PbSe-Bi₂Se₃ have been studied using differential thermal analysis, x-ray diffraction, and microhardness measurements. The results have been used to construct the T-x phase diagram along the AgBiSe₂-PbSe join and the 900-K section of the ternary phase diagram. The AgBiSe₂-PbSe system contains a continuous series of cubic solid solutions with the NaCl structure. Their lattice parameter is an almost linear function of composition (a = 5.822–6.125 Å). The formation of the solid solutions stabilizes the high-temperature phase of AgBiSe₂: PbSe dissolution in this compound markedly reduces its polymorphic transformation temperature (590 K), down to room temperature at ? 10 mol % PbSe. In the Ag₂Se-PbSe-Bi₂Se₃ system, the γ-phase exists in a broad region around the AgBiSe₂-PbSe pseudobinary join.     

Electrical conductivity of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Tm<Subscript>2</Subscript>O<Subscript>3</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> solid solutions

New solid solutions, Bi_2?x?y Tm _x Nb _y O_3+δ, with tetragonal and cubic structures have been synthesized in the Bi₂O₃-Tm₂O₃-Nb₂O₅ system, and their electrical conductivity has been measured at temperatures from 670 to 1020 K. The 1020-K conductivity of the tetragonal solid solution Bi_1.8Tm_0.15Nb_0.05O_3+δ is comparable to that of Bi_1.75Tm_0.25O₃, the best conductor in the Bi₂O₃-Tm₂O₃ system.     

Thermal conductivity of Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Gd<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> solid solutions

We have measured the thermal conductivity of Bi₂Te₃-Sb₂Te₃-Gd₂Te₃ solid solutions at temperatures from ～80 to 300 K and have determined the electronic and lattice components of their total thermal conductivity and the contributions of Sb₂Te₃ and Gd₂Te₃ to their thermal resistance. The results indicate that heat in these materials is transported largely by phonons and that three-phonon processes play a key role in determining the lattice thermal conductivity of the solid solutions.     

Crystallization from high-temperature solutions in the K<Subscript>2</Subscript>O-P<Subscript>2</Subscript>O<Subscript>5</Subscript>-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> system

We have studied general trends of crystallization from high-temperature solutions in the K₂O-P₂O₅-V₂O₅-Bi₂O₃ system at P/V = 0.5?2.0, K/(P + V) = 0.7?1.4, and Bi₂O₃ contents from 25 to 50 wt % and identified the stability regions of BiPO₄, K₃Bi₅(PO₄)₆, K₂Bi₃O(PO₄)₃, and K₃Bi₂(PO₄)_{3 ? x} (VO₄) _x (x = 0?3) solid solutions. The synthesized compounds have been characterized by X-ray powder diffraction and IR spectroscopy, and the structure of two solid solutions has been determined by single-crystal X-ray diffraction (sp. gr. C ₂/c): K₃Bi₂(PO₄)₂(VO₄), a = 13.8857(8), b = 13.5432(5), c = 6.8679(4) Å, β = 114.031(7)°; K₃Bi₂(PO₄)_1.25(VO₄)_1.75, a = 13.907(4), b = 13.615(2), c = 6.956(2) Å, β = 113.52(4)°.     

Mitigation of ammonia-induced SCC in a cupronickel alloy by additions of MgCl<Subscript>2</Subscript>

The authors carried out failure analysis of bent and branched copper-nickel alloy pipelines that had failed in marine environments. These failures were almost always dominated by a brittle stress-corrosion cracking (SCC) mode and could often be attributed to the presence of ammoniacal byproducts in the operating environment. Attempts were made to reproduce the marine-type field failures in the laboratory by testing a Cu-5.37%Ni alloy, similar to the material used in failed pipelines. The tests were performed under slow strain rate test (SSRT) conditions in aqueous ammonia and ammoniacal seawater. Results revealed that the ammonia-induced brittle SCC failures were predominant and reduced the load-bearing capacity of the alloy. The real-life failures are not simple SSRT-type failures. The operating conditions, in addition to the induced residual stresses from manufacturing/processing, subject the system pipes to external forces and widely varying pressures and fluid flow rates. This combination of stresses can produce both static and cyclic stress conditions, similar to a static load coupled with a low-amplitude cyclic load. Tests conducted under superimposed cyclic stresses on prestressed specimens were found to accelerate the stress-corrosion failures in the present copper-nickel alloy in an ammoniacal environment. During the testing process, it was established that chlorides of sodium and magnesium also had a role to play on the ammonia-induced SCC. Further tests were therefore designed, and this paper summarizes test results, which point to the possible mitigation of ammonia-induced SCC in cupronickels by the addition of MgCl₂.     

Mitigation of ammonia-induced SCC in a cupronickel alloy by additions of MgCl<Subscript>2</Subscript>

The work presented in Part 1 of this article showed that additions of magnesium chloride (MgCl₂) to ammonia solutions reduced the tendency of ammonia-induced stress-corrosion cracking (SCC) initiation in a Cu-5%Ni alloy. The present work was undertaken to study the SCC behavior of the test alloy exposed to ammonia in the presence of varying concentrations of MgCl₂. The exposure to MgCl₂ additions reduced the severity of the ammonia-induced SCC.     

Superprotonic CsH<Subscript>2</Subscript>PO<Subscript>4</Subscript>-CsHSO<Subscript>4</Subscript> solid solutions

We have performed partial HSO₄⁻ substitution in CsH₂PO₄ and studied the associated structural changes and the proton conductivity of the resultant (CsH₂PO₄)_{1 − x} (CsHSO₄) _x solid solutions in the range x = 0.01–0.3. The results indicate that, at room temperature, the solid solutions are disordered. In the range x = 0.01–0.1, they are isostructural with the low-temperature phase of CsH₂PO₄ (sp. gr. P2₁/m), and their unit-cell parameters increase with x, whereas in the range x = 0.15–0.3 the solid solutions are isostructural with the high-temperature, cubic phase of CsH₂PO₄ (Pm3m), and their unit-cell parameter decreases. The conductivity of the (CsH₂PO₄)_{1 − x} (CsHSO₄) _x solid solutions with x ≤ 0.3 depends significantly on their composition and increases at low temperatures by up to four orders of magnitude, approaching that of the superionic phase of CsH₂PO₄ in the range x = 0.15–0.3 because of the hydrogen bond weakening and increased proton mobility. The conductivity of the superionic phase decreases with increasing x by no more than a factor of 1.5–2, and the superionic phase transition, which occurs at 231°C in CsH₂PO₄, shifts to lower temperatures and disappears for x ≥ 0.15. The activation energy for low-temperature conduction decreases with increasing x: from 0.9 eV in CsH₂PO₄ to 0.48 eV at x = 0.1.     

Formation of solid solutions in the TiO<Subscript>2</Subscript>-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The phase formation and reaction kinetics in the TiO₂-Cr₂O₃ system have been studied by x-ray diffraction and electron microscopy. The Cr₂O₃ solubility in TiO₂ has been accurately determined, and the rate parameters of the formation of solid solutions in this system have been evaluated. The results demonstrate that Cr₂O₃ dissolves in rutile and not in anatase. Cr₂O₃ markedly reduces the temperature of the anatase-rutile phase transition.     

Extruded thermoelectric materials based on Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> solid solutions

Extruded n-type materials based on Bi₂Te₃-Bi₂Se₃ alloys containing 6 to 40 mol % Bi₂Se₃ have been investigated using microstructural analysis and thermoelectric measurements at room temperature and in the range 100–400 K. Their electrical properties have been compared to those of single-crystal analogs. Compositions have been found at which the extruded materials offer the highest thermoelectric performance in different temperature ranges.     

Lithium ion conductivity of LiLaO<Subscript>2</Subscript>-Li<Subscript>2</Subscript>ZrO<Subscript>3</Subscript> solid solutions

The limits of the LiLaO₂-and Li₂ZrO₃-based solid solutions in the LiLaO₂-Li₂ZrO₃ system have been determined: 0–10 mol % Li₂ZrO₃ and 0–5 mol % LiLaO₂, respectively. We have studied the transport properties (electronic conductivity, temperature and composition dependences of conductivity and activation energy) of lithium lanthanate and the solid solutions in the LiLaO₂-Li₂ZrO₃ system. Conduction in LiLaO₂ is likely due to lithium ion transport through a polyhedral network.     

Na<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-CaMoO<Subscript>4</Subscript>-Ce<Subscript>2/3</Subscript>MoO<Subscript>4</Subscript> scheelite-like solid solutions

We have studied tetragonal scheelite-like solid solutions in the ternary system Na₂MoO₄-CaMoO₄-Ce_2/3MoO₄: Na _0.7Ca_y Ce_{1.1 ? 2y/3} (MoO₄)₂ (0 ≤ y ≤ 0.6) and Na_0.3 Ca_zCe_{1.23? 2z/3} (MoO₄)₂ (0 ≤ z ≤ 1.4). The solid solutions melt congruently at temperatures from 1100 to 1200°C. Their lattice parameters have been determined. Using reflection spectra, we evaluated the color parameters of all the samples studied.     

Etching behavior of CdTe in aqueous H<Subscript>2</Subscript>O<Subscript>2</Subscript>-HI-C<Subscript>6</Subscript>H<Subscript>8</Subscript>O<Subscript>7</Subscript> solutions

This paper examines the dissolution behavior of the (111)A, (111)B, (110), and (100) surfaces of CdTe single crystals in aqueous H₂O₂-HI-C₆H₈O₇ (citric acid) solutions. We have determined the dissolution rate of the crystals as a function of temperature and solution concentration, located the composition regions of polishing and selective etchants, and studied the microstructure and roughness of surfaces polished with optimized etchants. The etching behavior of CdTe is shown to depend on its crystallographic orientation.     

Synthesis and x-ray diffraction study of solid solutions in the Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript>-Zn<Subscript>2</Subscript>TiO<Subscript>4</Subscript>-Zn<Subscript>2</Subscript>ZrO<Subscript>4</Subscript> system

The multicomponent refractory oxide system Zn₂(Ti_aSn_b)_{1 ? x} Zr_xO₄ (a + b = 1; a: b = 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 1: 0, 2: 1, 3: 1, 4: 1; x = 0?1.0; Δx = 0.05) has been studied by x-ray diffraction, using samples prepared by melting appropriate oxide mixtures in a low-temperature hydrogen-oxygen plasma. Two phases, both with wide homogeneity ranges, have been identified: α-phase, with a cubic inverse spinel structure, and β-phase, with a tetragonal spinel structure. The phase boundaries in the system have been determined. Structural data are presented for about 100 solid solutions of different compositions.     

Crystal-chemical aspect of formation of CdAs<Subscript>2</Subscript>-ZnAs<Subscript>2</Subscript> solid solutions

The initial stages of the formation of CdAs₂-ZnAs₂ solid solutions are analyzed in terms of crystalchemical energetics. Given that the bond enthalpies decrease in the order H (Zn-As)< H (Cd-As)< H (As-As), it is concluded that, most likely, CdAs₂-based solid solutions are substitutional and ZnAs₂-based solid solutions are interstitial, and that the thermochemical stability of the substitutional solid solutions is higher than that of CdAs₂ . The conclusions drawn from crystal-chemical analysis correlate with the reported x-ray diffraction, chemical analysis, resistivity, and Hall data for the solid solutions.Translated from Neorganicheskie Materialy, Vol. 41, No. 1, 2005, pp. 7–10. Original Russian Text Copyright © 2005 by Sanygin, Mikhailov, Palkina, Steblevskii, Kvardakov, Marenkin.     

Synthesis and crystal structure of [UO<Subscript>2</Subscript>(OH)(CO(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>)<Subscript>3</Subscript>]<Subscript>2</Subscript>(ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The complex [UO₂(OH)(CO(NH₂)₂)₃]₂(ClO₄)₂ (I) was synthesized. A single crystal X-ray diffraction study showed that compound I crystallizes in the triclinic system with the unit cell parameters a = 7.1410(2), b = 10.1097(2), c = 11.0240(4) Å, α = 104.648(1)°, β = 103.088(1)°, γ = 108.549(1)°, space group \(P\bar 1\), Z = 1, R = 0.0193. The uranium-containing structural units of the crystals are binuclear groups [UO₂(OH)· (CO(NH₂)₂)₃] ₂ ²⁺ belonging to crystal-chemical group AM²M ₃ ¹ [A = UO ₂ ²⁺ , M² = OH^?, M¹ = CO(NH₂)₂] of uranyl complexes. The crystal-chemical analysis of nonvalent interactions using the method of molecular Voronoi-Dirichlet polyhedra was performed, and the IR spectra of crystals of I were analyzed.     

Properties of nanocrystalline ZrO<Subscript>2</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>-CoO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powders

We have studied the properties of nanocrystalline ZrO₂-Y₂O₃-CeO₂-CoO-Al₂O₃ powders prepared via hydrothermal treatment of a mixture of coprecipitated hydroxides at 210°C. A number of general trends are identified in the variation of the properties of the synthesized powders during heat treatment at temperatures from 500 to 1200°C. Our results demonstrate that the addition of 0.3 mol % CoO to nanocrystalline ZrO₂-based powders containing 1 to 5 mol % Al₂O₃ allows one to obtain composites with good sinterability at a reduced temperature (1200°C).     

Distillation recovery of AsCl<Subscript>3</Subscript> from AsCl<Subscript>3</Subscript>-HCl-H<Subscript>2</Subscript>O solutions

The distillation recovery of arsenic trichloride from saturated solutions in concentrated hydrochloric acid has been studied experimentally at a pressure of 1.013 × 10⁵ Pa and temperatures from 60 to 75°C, and the optimal process temperature has been determined.     

Solid-state reactions in the system Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>

The formation mechanisms of Li _x Na_{1 ?x} Ta _y Nb_{1 ? y} O₃ perovskite solid solutions in the Li₂CO₃-Na₂CO₃-Nb₂O₅-Ta₂O₅ system have been studied by x-ray diffraction, differential thermal analysis, thermogravimetry, IR spectroscopy, and mass spectrometry at temperatures from 300 to 1100°C. The results indicate that the synthesis of Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions involves a complex sequence of consecutive and parallel solid-state reactions. An optimized synthesis procedure for Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions is proposed.     

Growth and properties of LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript>-NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> crystals

Platelike Li_{1 ? x} Na _x Cu₂O₂ single crystals up to 2 × 10 × 10 mm in dimensions have been grown by slowly cooling (1 ? x)Li₂CO₃·xNa₂O₂·4CuO melts in alundum crucibles in air. Li_{1 ? x} Na _x Cu₂O₂ solid solutions in the LiCu₂O₂-NaCu₂O₂ system have been shown to exist in the composition range 0.78 < x < 1. The temperature stability ranges of NaCu₂O₂ and LiCu₂O₂ are 780–930 and 890–1050°C, respectively. The Mössbauer spectra and electrical conductivity of the crystals have been measured.