Mechanism and Kinetics of Thermal Decomposition of MgCl<Subscript>2</Subscript> × 6H<Subscript>2</Subscript>O

The reaction mechanism and kinetic behavior of thermal decomposition of MgCl₂ × 6H₂O were studied by thermal gravimetric analysis. The results showed that the thermal decomposition process of MgCl₂ × 6H₂O could be divided into six stages. In the first two stages, four crystalline waters were lost. The dehydration and hydrolysis coexisted during the third and fourth stages. The fifth stage corresponded to the evaporation of 0.3 crystalline waters, and one molecular hydrogen chloride was eliminated in the last stage. The kinetic analysis of the thermal decomposition process was performed using the Doyle, Coats–Redfern, and Malek methods. The results suggested that the mechanisms of six stages were two-dimensional phase boundary mechanism, three-dimensional phase boundary mechanism, nucleation and nuclei growth mechanism (Avrami–Erofeev equation n = 3), two-dimensional phase boundary mechanism, three-dimensional diffusion mechanism (cylinder and G-B equation), and nucleation and nuclei growth mechanism (Avrami–Erofeev equation n = 1), respectively. The apparent active energies of six stages were 66.8 kJ × mol⁻¹, 138.0 kJ × mol⁻¹, 77.2 kJ × mol⁻¹, 135.6 kJ × mol⁻¹, 77.4 kJ × mol⁻¹, and 92.2 kJ × mol⁻¹, respectively. The frequency factors were 3.6 × 10⁹ s⁻¹, 8.8 × 10¹⁷ s⁻¹, 4.6 × 10⁹ s⁻¹, 3.0 × 10¹⁴ s⁻¹, 78.6 s⁻¹, and 1.2 × 10³ s⁻¹, respectively.     

Deformation and failure of Zr<Subscript>57</Subscript>Nb<Subscript>5</Subscript>Al<Subscript>10</Subscript>Cu<Subscript>15.4</Subscript>Ni<Subscript>12.6</Subscript>/W particle composites under quasi-static and dynamic compression

We have investigated the mechanical behavior of a composite material consisting of a Zr₅₇Nb₅Al₁₀Cu_15.4Ni_12.6 metallic glass matrix with 60 vol pct tungsten particles under uniaxial compression over a range of strain rates from 10⁻⁴ to 10⁴ s⁻¹. In contrast to the behavior of single-phase metallic glasses, the failure strength of the composite increases with increasing strain rate. The composite shows substantially greater plastic deformation than the unreinforced glass under both quasi-static and dynamic loading. Under quasi-static loading, the composite specimens do not fail even at nominal plastic strains in excess of 30 pct. Under dynamic loading, fracture of the composite specimens is induced by shear bands at plastic strains of approximately 20 to 30 pct. We observed evidence of shear localization in the composite on two distinct length scales. Multiple shear bands with thicknesses less than 1 μm form under both quasi-static and dynamic loading. The large plastic deformation developed in the composite specimens is due to the ability of the tungsten particles both to initiate these shear bands and to restrict their propagation. In addition, the dynamic specimens also show shear bands with thicknesses on the order of 50 μm; the tungsten particles inside these shear bands are extensively deformed. We propose that thermal softening of the tungsten particles results in a lowered constraint for shear band development, leading to earlier failure under dynamic loading.     

High-temperature deformation behavior of coarse- and fine-grained MoSi<Subscript>2</Subscript> with different silica contents

The elevated-temperature deformation behavior of polycrystalline molybdenum disilicide (MoSi₂), in the range of 1000 °C to 1350 °C at the strain rates of 10⁻³, 5×10⁻⁴, or 10⁻⁴ s⁻¹, has been studied. The yield strength, post-yield flow behavior comprising strain hardening and serrations, as well as some of the deformation microstructures of reaction-hot-pressed (RHP) MoSi₂ samples, processed by hot pressing an elemental Mo + Si powder mixture and having a grain size of 5 μm and oxygen content of 0.06 wt pct, have been compared with those of samples prepared by hot pressing of commercial-grade Starck MoSi₂ powder, with a grain size of 27 μm and oxygen content of 0.89 wt pct. While the fine-grained RHP MoSi₂ samples have shown higher yield strength at relatively lower temperatures and higher strain rates, the coarse-grained Starck MoSi₂ has a higher yield at decreasing strain rates and higher temperatures. The work-hardening or softening characteristics are dependent on grain size, temperature, and strain rate. Enhanced dislocation activity and dynamic recovery, accomplished by arrangement of dislocations in low-angle boundaries, characterize the deformation behavior of fine-grained RHP MoSi₂ at a temperature of 1200 °C and above and are responsible for increased uniform plastic strain with increasing temperature. The silica content appears to be less effective in degrading the high-temperature yield strength if the grain size is coarse, but leads to plastic-flow localization and strain softening in Starck MoSi₂. Serrated plastic flow has also been observed in a large number of samples, mostly when deformed at specific combinations of strain rates and temperatures.     

Dynamic phase transformation during superplastic deformation of Nb/Nb<Subscript>3</Subscript>Al <Emphasis Type="Italic">in-situ</Emphasis> composite

Nb_ss/Nb₃Al in-situ composite with the nominal composition of Nb-16 mol pct Al-1 mol pct B, consisting of bcc niobium solid solution (Nb_ss) and A15 ordered Nb₃Al, was synthesized by arc melting, homogenization annealing, and isothermal forging, and their superplastic deformation behavior was investigated by tensile tests and microstructure observations. Maximum superplastic elongation over 750 pct was obtained at 1573 K and at a strain rate of 1.6 × 10⁻⁴ s⁻¹ for as-forged specimens. Phase transformation from Nb_ss to Nb₃Al was observed to occur during superplastic deformation. Dynamic phase transformation during superplastic deformation progresses more quickly than static phase transformation during annealing without applied stress. Dynamic phase transformation is accompanied by phase-boundary migration, which operates as an accommodation process of grain-boundary sliding. Dislocation creep dominates deformation and grain-boundary sliding is inhibited at a high strain rate, while grain-boundary sliding and cavity formation are promoted at a low strain rate because of insufficient accommodation of grain-boundary sliding arising from sluggish dynamic phase transformation. It is concluded that there exists an optimum strain rate that guarantees the grain-boundary sliding and the rapid dynamic phase transformation to achieve maximum superplastic elongation.     

Thermodynamics of Arsenic in FeOx-CaO-SiO<Subscript>2</Subscript> Slags

The distribution of arsenic between calcium ferrite slag and liquid silver (wt pct As in slag/ wt pct As in liquid silver) with 22 wt pct CaO and between iron silicate slag with 24 wt pct SiO₂ and calcium iron silicate slags was measured at 1573 K (1300 °C) under a controlled CO-CO₂-Ar atmosphere. For the calcium ferrite slags, a broad range of oxygen partial pressure (10^–11 to 0.21 atm) was covered, whereas for the silicate slags, the oxygen partial pressure was varied from 10^–9 to 3.1 × 10^–7 atm. The measured relations between the distribution ratio of As and the oxygen partial pressure indicates that the oxidation state of arsenic in these slags is predominantly As³⁺ or AsO_1.5. The measured distribution ratio of arsenic between the calcium ferrite slag and the liquid silver was about an order of magnitude higher than that of the iron silicate slag. In addition, an increasing concentration of SiO₂ in the calcium-ferrite-based melts resulted in decreases in the distribution of arsenic into the slag. Through the use of measured equilibrium data on the arsenic content of the metal and slag in conjunction with the composition dependent on the activity of arsenic in the metal, the activity of AsO_1.5 in the slags was deduced. These activity data on AsO_1.5 show a negative deviation from the ideal behavior in these slags.     

Evaluating the Diffusion Coefficient of Sulfur in Low-Silica CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag

The chemical diffusion coefficient of sulfur in the ternary slag of composition 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was measured at 1680 K, 1700 K, and 1723 K (1403 °C, 1427 °C, and 1450 °C) using the experimental method proposed earlier by the authors. The P_\textS2 P_{{{\text{S}}_{2} }} and P_\textO2 P_{{{\text{O}}_{2} }} pressures were calculated from the Gibbs energy of the equilibrium reaction between CaO in the slag and solid CaS. The density of the slag was obtained from earlier experiments. Initially, the order of magnitude for the diffusion coefficient was taken from the works of Saito and Kawai but later was modified so that the concentration curve for sulfur obtained from the program was in good fit with the experimental results. The diffusion coefficient of sulfur in 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was estimated to be in the range 3.98 to 4.14 × 10⁻⁶ cm²/s for the temperature range 1680 K to 1723 K (1403 °C to 1450 °C), which is in good agreement with the results available in literature     

Influence of Strain Rate on Compressive Deformation Behavior of a Zr-Cu-Ni-Al Bulk Metallic Glass at Room Temperature

The compressive-deformation behavior of the Zr_50.7Cu₂₈Ni₉Al_12.3 bulk metallic glass (BMG) was investigated over a wide strain-rate range at room temperature. The yield strength of the BMG studied is independent of the strain rates applied upon quasi-static loading; however, it decreases remarkably upon dynamic loading. Serrated flows and shear bands appear at low quasi-static strain rates; nevertheless, they vanish as the strain rate increases to 1.0 × 10⁻¹ s⁻¹. Cracks appearing on the side surface of the fractured sample after dynamic compression yield a strain-accommodation deformation mechanism upon dynamic loading. Scanning electron microscopy observations reveal that molten liquids increase on the fractured surfaces with increasing strain rate, indicating that adiabatic heating in the shear bands is enhanced as the strain rate increases.     

Effect of strain rate on the strain-induced <Emphasis Type="Italic">γ</Emphasis> → <Emphasis Type="Italic">α</Emphasis>′-martensite transformation and mechanical properties of austenitic stainless steels

The effect of strain rate on strain-induced γ → α′-martensite transformation and mechanical behavior of austenitic stainless steel grades EN 1.4318 (AISI 301LN) and EN 1.4301 (AISI 304) was studied at strain rates ranging between 3×10⁻⁴ and 200 s⁻¹. The most important effect of the strain rate was found to be the adiabatic heating that suppresses the strain-induced γ → α′ transformation. A correlation between the work-hardening rate and the rate of γ → α′ transformation was found. Therefore, the changes in the extent of the α′-martensite formation strongly affected the work-hardening rate and the ultimate tensile strength of the materials. Changes in the martensite formation and work-hardening rate affected also the ductility of the studied steels. Furthermore, it was shown that the square root of the α′-martensite fraction is a linear function of flow stress. This indicates that the formation of α′-martensite affects the stress by influencing the dislocation density of the austenite phase. Olson-Cohen analysis of the martensite measurement results did not indicate any effect of strain rate on shear band formation, which was contrary to the transmission electron microscopy (TEM) examinations. The β parameter decreased with increasing strain rate, which indicates a decrease in the chemical driving force of the α → α′ transformation.     

Preparation and Properties of Ti<Subscript>50</Subscript>Cu<Subscript>28</Subscript>Ni<Subscript>15</Subscript>Sn<Subscript>7</Subscript> Bulk Metallic Glass by Vacuum Hot Pressing

Amorphous Ti₅₀Cu₂₈Ni₁₅Sn₇ alloy powders were synthesized by a mechanical alloying (MA) technique. Differential scanning calorimetry (DSC) results showed that, after 7 hours of exposure to the milling process, amorphous Ti₅₀Cu₂₈Ni₁₅Sn₇ alloy powders exhibit a wide supercooled liquid region of 61 K. Consolidation of amorphous powders were performed at a temperature slightly higher than the glass transition temperature under a pressure of ∼1.2 GPa, and bulk metallic glass (BMG) discs can be prepared successfully. However, we noticed partial crystallization during the hot pressing process and were not able to achieve full densification of BMG. The Vickers microhardness of Ti₅₀Cu₂₈Ni₁₅Sn₇ BMG was 634 kg/mm², and the trace of the indentation revealed that pre-existing particle boundaries or interfaces between nanocrystals and amorphous matrix may serve as the crack initiation sites. Thus, typical brittle failure of Ti₅₀Cu₂₈Ni₁₅Sn₇ BMG was observed and resulted in relatively low fracture stress compared to that estimated by the microhardness. This article is based on a presentation given in the symposium entitled “Bulk Metallic Glasses IV,” which occurred February 25–March 1, 2007 during the TMS Annual Meeting in Orlando, Florida under the auspices of the TMS/ASM Mechanical Behavior of Materials Committee.     

Deformation and fracture behavior of 316L sintered stainless steel under various strain rate and relative sintered density conditions

This study investigates the effects of the strain rate and the relative sintered density on the mechanical response and fracture behavior of 316L sintered stainless steel. Low strain rate compression tests are conducted on an MTS 810 servohydraulic machine at strain rates of 10⁻³ to 10⁻¹ s⁻¹, while dynamic impact tests are performed using a split-Hopkinson bar at strain, rates of 3×10³ to 9×10³ s⁻¹. The Taguchi method with an L₉ orthogonal array is used to characterize and optimize the sintering process control factors such that the specimens have three different relative sintered densities, i.e., 83, 88, and 93 pct. It is found that the strain rate and relative sintered density have significant effects on the flow stress, fracture strain, strain rate sensitivity, and activation volume. The significant differences observed in the strain rate sensitivity and activation volume in the high and low strain rate tests indicate that the corresponding deformation is dominated by different rate controlling mechanisms. Furthermore, the changes in strain rate sensitivity and thermal activation volume observed at different levels of the relative sintered density are related to the work hardening stress. At high strain rate and relative sintered densities slip deformation in the form of slip bands is frequently observed within the grains. Therefore, it appears that higher strain rates and relative sintered densities represent favorable conditions for the formation of shear bands and cracking, and hence lead to premature specimen fracture. The fracture surfaces contain dimplelike structures, which are indicative of a ductile fracture mode. The depth and the density of these dimples decrease as the strain rate and relative sintered density increase, indicating a loss of ductility.     

Synthesis and Characterization of Microwave Absorbing SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript>/ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> Nanocomposite

Zinc ferrite and strontium hexaferrite; SrFe₁₂O₁₉/ZnFe₂O₄ (SrFe_11.6Zn_0.4O₁₉) nanoparticles having super paramagnetic nature were synthesized by simultaneous co-precipitation of iron, zinc and strontium chloride salts using 5 M sodium hydroxide solution. The resulting precursors were heat treated (HT) at 850, 950 and 1150°C for 4 h in nitrogen atmosphere. The hysteresis loops showed an increase in saturation magnetization from 1.040 to 58.938 emu/g with increasing HT temperatures. The ‘as-synthesized’ particles have size in the range of 20–25 nm with spherical and needle shapes. Further, these spherical and needle shaped nanoparticles tend to change their morphology to hexagonal plate shape with increase in HT temperatures. The effect of such a systematic morphological transformation of nanoparticles on dielectric (complex permittivity and permeability) and microwave absorption properties were estimated in X band (8.2–12.2 GHz). The maximum reflection loss of the composite reaches −26.51 dB (more than 99% power attenuation) at 10.636 GHz which suits its application in RADAR absorbing materials.     

Standard gibbs energy of formation of Mg<Subscript>48</Subscript>Zn<Subscript>52</Subscript> determined by solution calorimetry and measurement of heat capacity from near absolute zero kelvin

The thermodynamic properties of Mg₄₈Zn₅₂ were investigated by calorimetry. The standard entropy of formation at 298 K, Δ_f S ₂₉₈ ^o , was determined from measuring the heat capacity, C _p , from near absolute zero (2 K) to 300 K by the relaxation method. The standard enthalpy of formation at 298 K, Δ_f H ₂₉₈ ^o , was determined by solution calorimetry in hydrochloric acid solution. The standard Gibbs energy of formation at 298 K, Δ_f G ₂₉₈ ^o , was determined from these data. The obtained results were as follows: Δ_f H ₂₉₈ ^o (Mg₄₈Zn₅₂)=(−1214±(300) kJ · mol⁻¹;Δ_fS ₂₉₈ ^o (Mg₄₈Zn₅₂)=(−123±0.36) J · K⁻¹ · mol⁻¹; and Δ_f G ₂₉₈ ^o (Mg₄₈Zn₅₂)=(−1177±(300) kJ · mol⁻¹. The electronic contribution to the heat capacity of Mg₄₈Zn₅₂ was found to be approximately equal to pure magnesium, indicating that the density of states in the vicinity of the Fermi level follows the free electron parabolic law.     

The influence of crystallographic orientation and strain rate on the high-temperature low-cyclic fatigue property of a nickel-base single-crystal superalloy

Fully reversed low-cyclic fatigue (LCF) tests were conducted on [001], [012], [-112], [011], and [-114] oriented single crystals of nickel-based superalloy DD3 with different cyclic strain rates at 950°C. The cyclic strain rates were chosen as 1.0×10⁻², 1.33×10⁻³ and 0.33×10⁻³ s⁻¹. The octahedral slip systems were confirmed to be activated on all the specimens. The experimental result shows that the fatigue behavior depends on the crystallographic orientation and cyclic strain rate. Except [001] orientation specimens, it is found from the scanning electron microscopy (SEM) examination that there are typical fatigue striations on the fracture surfaces. These fatigue striations are made up of cracks. The width of the fatigue striations depends on the crystallographic orientation and varies with the total strain range. A simple linear relationship exists between the width and total shear strain range modified by an orientation and strain rate parameter. The nonconformity to the Schmid law of tensile/compressive flow stress and plastic behavior existed at 950°C, and an orientation and strain rate modified Lall-Chin-Pope (LCP) model was derived for the nonconformity. The influence of crystallographic orientation and cyclic strain rate on the LCF behavior can be predicted satisfactorily by the model. In terms of an orientation and strain rate modified total strain range, a model for fatigue life was proposed and used successfully to correlate the fatigue lives studied in this article.     

Coarsening of Al<Subscript>3</Subscript>Sc precipitates in an Al-0.28 wt pct Sc alloy

The Ostwald ripening of Al₃Sc precipitates in an Al-0.28 wt pct Sc alloy during aging at 673, 698, and 723 K has been examined by measuring the average size of precipitates by transmission electron microscopy (TEM) and the reduction in Sc concentration in the Al matrix with aging time, t, by electrical resistivity. The coarsening kinetics of Al₃Sc precipitates obey the t ^1/3 time law, as predicted by the Lifshitz-Slyozov-Wagner (LSW) theory. The kinetics of the reduction of Sc concentration with t are consistent with the predicted t ^−1/3 time law. Application of the LSW theory has enabled independent calculation of the Al/Al₃Sc interface energy, γ, and volume diffusion coefficient, D, of Sc in Al during coarsening of precipitates. The Gibbs-Thompson equation has been used to give a value of γ using coarsening data obtained from TEM and electrical resistivity measurements. The value of γ estimated from the LSW theory is 218 mJ m⁻², which is nearly identical to 230 mJ m⁻² from the Gibbs-Thompson equation. The pre-exponential factor and activation energy for diffusion of Sc in Al are determined to be (7.2±6.0)×10⁻⁴ m² s⁻¹ and 176±9 kJ mol⁻¹, respectively. The values are in agreement with those for diffusion of Sc in Al obtained from tracer diffusion measurements.