The rates of dehydroxylation of smectites intercalated with the decomposition products of Ni(phen)3SO4 are from 2 to 4 times greater than those of clays without the heat-stable intercalate. These results suggest that the intercalated material, in keeping the clay sheets separated, provides a more ready avenue for water loss during the dehydroxylation process.

The kinetics of the thermal decomposition of the kaolin: dimethylsulfoxide (kaolin: DMSO) and the kaolin: N-methylformarnide (kaolin: NMF) intercalates have been reexamined. Two different sample sizes (2 mg and 8 mg) and grain-size distributions (<45 μm and 45–63 μm were investigated using isothermal and dynamic gravimetry in the temperature range 100°–200oC. All sample configurations for the kaolin: DMSO intercalate (2 mg, <45 μm; 2 mg, 45–63 μm; 8 mg, <45 μm; 8 mg, 45–63 μm) followed the rate law -ln(1 - α) = kt to a value for α, the reaction fraction complete, of.6, yielding activation energies and standard deviations at the 99% confidence level of 85.5 ± 3.79 and 71.75 ± 8.75 kJ/mole for the isothermal and dynamic runs, respectively. The kaolin: NMF intercalate (2 mg, <45 μm) also followed the same rate law for α <.8, with activation energies and standard deviations at the 99% confidence level of 89 ± 5.05 and 79.25 ± 6.47 kj/mole for the isothermal and dynamic studies, respectively. In solution the rate law -ln(1 - α) = kt is known as first-order kinetics, but here it appears to represent the non-instantaneous nucleation of uniformly sized particles, followed by the inward movement of a reaction interface.

The dissolution in 1 M HC1 of Al-, Mn-, and Ni-substituted hematites and the influence of metal substitution on dissolution rate and kinetics of dissolution were investigated. The inhomogeneous dissolution of most of the hematites investigated was well described by the Avrami-Erofe'ev rate equation, kt = √[-ln(l − α)], where k is the dissolution rate in time, t, and α is the Fe dissolved. Dissolution of Al-substituted hematite occurred mostly by edge attack and hole formation normal to (001), with the rate of dissolution, k, directly related to surface area (SA). Dissolution of rhombohedral Mn- and Ni-bearing hematites occurred at domain boundaries, crystal edges, and corners with k unrelated to SA. The morphology of Mn- and Ni-substituted hematites changed during dissolution with clover-leaf-like forms developing as dissolution proceeded, whereas the original plate-like morphology of Al-bearing hematite was generally retained. Acid attack of platy and rhomboidal hematite is influenced by the direct (e.g., metaloxygen bond energy, hematite crystallinity) and indirect (e.g., crystal size and shape) affects associated with incorporation of foreign ions within hematite.

Smectites are a group of minerals traditionally analyzed by thermal methods due to their exceptionally large adsorbed-water contents and the presence of OH groups, which makes them unique among all common soil- and rock-forming minerals. The dehydration reaction of smectite is a low-temperature endothermic effect that ends typically below 200°C. Although the removal of bulk interlayer water requires activation energy (Ea) of just above 30 kJ/mol, the removal of the last few H2O molecules attached strongly to interlayer cations requires Ea > 100 kJ/mol. Dehydroxylation is the loss of structural OH groups that proceeds as evolution of H2O molecules out of the smectite structure and occurs in the 300–900°C range. In trioctahedral species, dehydroxylation is combined with recrystallization and proceeds usually at > 700°C. In dioctahedral species, the temperature of dehydroxylation is controlled by the type of octahedral vacancy, having trans-vacant and cis-vacant distinguished by the boundary at ~ 600°C, and by the octahedral cation–OH bond strength, following the order Mg > Al > Fe. The Ea of dehydroxylation correlates linearly with the temperature of maximum dehydroxylation; from > 170 kJ/mol for Cs+-exchanged beidellite and nontronite, through ~ 300 kJ/mol in Mg-rich montmorillonite, to > 500 kJ/mol in trioctahedral saponite. Dehydration and dehydroxylation of smectites can be accompanied by a number of other phenomena, such as dehydrogenation or defluorination. At high temperatures, smectite amorphization and recrystallization occurs. Unless amorphized and/or recrystallized, smectites can undergo rehydration and rehydroxylation, which are opposite reactions to dehydration and dehydroxylation, respectively. This review discusses the details of the above-mentioned thermal reactions of smectites, focusing on thermogravimetric methods, evolved gas analysis, and structural alterations. Factors affecting the accuracy and precision of thermal analysis of smectite are discussed along with examples of best laboratory practices. The paper also provides the most recent description and critical evaluation of smectite reaction kinetics.

Different changes in the structural and thermal properties of various types of talc have been reported in the literature which have made comparison of analytical results difficult. The objective of the present study was to obtain some fundamental insights into the effects of the thermal behavior of talc and to carry out kinetic analyses of the decomposition of talc under high temperature. X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetry-differential scanning calorimetry (TG-DSC) were used to study the thermal decomposition mechanism. The Coats-Redfern decomposition model was used to determine the decomposition mechanism of talc samples. The results showed that the decomposition of talc commenced at ~800°C, peaking at ~895°C, with the formation of enstatite and amorphous silica. An isothermal treatment at 1000°C caused the complete dehydroxylation of talc. The XRD and FTIR results indicated that the enstatite and amorphous silica phases were transformed into clinoenstatite and paracrystalline opal phases, respectively, after the decomposition stage at 1200°C. Good linearity in the Coats-Redfern model was observed from room temperature to 1300°C and the activation energy was calculated to be 69 kcal/mol.

The mechanism of decolorization of crude maize and sunflower oils was studied by means of adsorption of β-carotene by a low-grade bentonite, containing mixed-layered illite-smectite. Decolorization depends on temperature and the time required for equilibrium decreases with increasing temperature. The study of the kinetics of adsorption showed that decolorization of maize oil is a first-order process which occurs in two steps: a first fast step with higher activation energy (25.6 kJ mol−1), indicating the influence of a chemical interaction between the pigment and the clay surface, followed by a second slow step with low activation energy (12.3 kJ mol−1), characteristic of physical adsorption on the previously adsorbed molecules. Decolorization of sunflower oil is also a first-order process, described by a single mechanism with intermediate activation energy (19.0 kJ mol−1). Adsorption isotherms of decolorization of maize oil follow the Freundlich equation, indicating the existence of heterogeneous adsorption sites on the solid's surface. Heterogeneity is attributed both to different active centers on the smectite surface (Brönsted and Lewis centers) and to the different phases present in bentonite, such as illitic layers and clinoptilolite, which also have active centers on their surfaces.

Limpets (Patella spp.) are marine gastropods that inhabit rocky shores along the coasts of Europe, the Mediterranean, Macaronesia and the north-west coast of Africa. Being considered key species, limpets have an important role regulating algal assemblages in coastal communities. The goal of this work was to evaluate the influence of sea temperature on the respiration rate of four limpet species occurring in mainland Portugal, in line with predictions from the metabolic theory of ecology. The individuals were collected from rocky shores in Portugal and exposed to sea temperatures ranging from 6–28°C for respiration rate assessments. Following the estimation of the relationship between oxygen consumption and temperature the activation energy was calculated. In parallel, low and high thermal thresholds were determined for three of the species. The results indicated that P. ulyssiponensis oxygen consumption increased linearly with sea temperature and the remaining species presented the same tendency. The values of activation energy ranged between 0.33–0.76 eV. For P. ulyssiponensis, the highest activation energy indicated that this species is more sensitive to temperature variations while for the tested temperatures it presented a higher thermal tolerance limit than the other species. Such findings indicate that P. ulyssiponensis is the most susceptible of these species to climate change, in line with the tolerance–plasticity trade-off hypothesis. This work provides a good starting point for understanding the effect of sea temperature on oxygen consumption in Patella spp. and for comprehending sensitivity of limpets to temperature increases under future climate change scenarios.

Clays are raw materials with properties that are necessary for the manufacture of ceramic tiles. The characteristics of clay ceramic raw materials may vary within the same mineral deposit. Clay blending promotes better use of clay reserves, thereby increasing the applicability and life cycle of raw materials. Therefore, it is important to understand the mechanisms controlling the firing of ceramic tiles. In this study, three different clays from a clay deposit were assessed and ten formulations were prepared using the mixture design method. The formulations were analysed using differential thermal and thermogravimetric analyses and dilatometric analysis. Subsequently, the most refractory and fluxing formulations were subjected to thermal tests under various heating rates, similar to the process used for the calculation of apparent sintering activation energy for the densification of clays and for pyroplasticity tests. It is suggested that a mineral deposit can be assessed based on activation energy and thermal kinetics, expanding the alternatives available to the miner through the planning of mixtures with various clays and thus reducing the energy costs of the industrial process.

The hot deformation behavior of Ti–6Al–4V alloy with starting fully lamellar microstructure was investigated by conducting isothermal hot compression tests at the temperature of 700–1000 °C and strain rate of 0.001–10 s−1. The deformation activation energy is calculated to be 342 kJ/mol at temperatures from 750 to 850 °C, whereas the higher apparent activation energy of 610 kJ/mol is obtained at a high temperature regime of 900–1000 °C. The relationship between the dynamic softening behavior and deformation parameters was analyzed by power dissipation efficiency η, which shows an increasing trend as the deformation temperature increases and strain rate decreases, respectively. Processing maps were constructed. The instability flow is dominated by the presence of adiabatic shear bands, and the dynamic softening is mainly caused by a combination effect of dynamic recrystallization and dynamic recovery. Moreover, straining is found to have a positive effect on lowering the phase transformation temperature.

The temperature (T) and pressure (P) dependence of dielectric and conductivity properties of natural leucite were determined using complex impedance spectroscopy at frequencies from 103 to 106 Hz. Experiments were carried out in a Walker multi-anvil cell at 1 atm and P from 2.5 to 6 GPa and at T from 350 to 800°C. At pressure >6 GPa and temperature >790°C the leucite broke down to kalsilite+sanidine and dielectric properties for this phase assemblage are given at 6.0–7.0 GPa and T to 1050°C.

Leucite conductivity increases with increasing T and decreases with increasing P reflecting their different effects on migration of K cations within the channels in the leucite aluminosilicate framework. Activation energies for K+ migration in leucite increase with increasing pressure (0.74–0.97 eV; 70.0–93.2 kJ/mol) and activation volumes for leucite increase with increasing T (6.42–9.51 cm3/mol; 400–700°C). The latter data provide model K+ cation diameters increasing from 2.7 Å at 400°C to 3.2 Å at 700°C. These values are consistent with the earlier suggestion of Palmer and Salje that the ionic mobility mechanism consists of diffusion along <110> rather than along the main channels parallel to <111>.

In this work, differential scanning calorimetry (DSC) was used to characterize and analyze the precipitation/dissolution kinetics of second phase particles during the cooling/reheating process in a vanadium microalloyed steel. The results indicated that three obvious exothermic peaks were detected on the cooling DSC curve. Furthermore, three corresponding endothermic peaks were also detected on the heating DSC curve. Combined with thermodynamic calculation and transmission electron microscopy analysis, these three exothermic peaks along cooling DSC curve were defined as the precipitation reaction of V(CN), the reaction of austenite transformation into ferrite and the precipitation reaction of VC, respectively. Meanwhile, three corresponding reverse reactions for cooling were also defined along the reheating DSC curve. The linear regression result revealed that the precipitation activation energies for V(CN) and VC were identified as 311.2 kJ/mol and 167.6 kJ/mol, respectively. The dissolution activation energies for VC and V(CN) were identified as 255.4 kJ/mol and 592.6 kJ/mol, respectively.

Previous work on the structural and thermal properties of various types of kaolinite have led to different conclusions, rendering comparison of analytical results difficult. The objectives of the present study were to investigate the thermal behaviour of kaolinite and to carry out a kinetic analysis of the decomposition of kaolinite at high temperatures. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetry-differential scanning calorimetry (TG-DSC) were used to study the mechanism of the thermal decomposition. The modified Coats–Redfern, Friedman, Flynn–Wall–Ozawa and Kissinger decomposition models were used to determine the decomposition mechanism of the kaolinite sample. The dehydroxylation of kaolinite occurred at ∼600°C with the formation of metakaolin, which then transformed into either γ-alumina or aluminium-silicon spinel together with amorphous silica. The results of the XRD and FTIR analyses indicated that the γ-alumina, or aluminium-silicon spinel and amorphous silica phases, transformed into mullite and α-cristobalite, respectively, after decomposition at 900°C. Good linearity was observed with the modified Coats–Redfern, Flynn–Wall–Ozawa and Kissinger models from room temperature to 1400°C and the range of the activation energy determined was 120–180 kJ/mol.

The hot deformation behavior of as-cast AZ91 magnesium alloy reinforced by SiC nanoparticles (SiCp/AZ91 nanocomposite) was investigated using hot compression test. Compared with unreinforced AZ91 alloy, peak stress of the SiCp/AZ91 nanocomposite achieved faster and high temperature deformation ability which was enhanced by the addition of SiC nanoparticles. The values of n for the AZ91 alloy and nanocomposite were 6.9 and 4.6, while the values of Q were 207.96 kJ/mol and 184.6 kJ/mol, respectively. The processing map showed the optimum processing conditions for the nanocomposite mainly concentrated at 523–673 K/0.018–0.001 s−1 and the maximum power dissipation efficiency was found to be 36% at a temperature of 673 K and the strain rate of 0.001 s−1. Based on the constitutive equation and processing map, the deformation mechanism for the present nanocomposite should be dominated by the mechanism of dynamic recrystalization.

In this paper we have reported analysis on activation energy and humidity sensing studies of Cu-doped ZnO thin films. Thin Films of undoped and Cu-doped ZnO nanomaterials were prepared. Undoped and Cu-doped ZnO thin films annealed at 600 °C showed the best results with sensitivity of 20.63 MΩ/%RH and 39.14 MΩ/%RH respectively in the 15–95% RH range. Low value of activation energy indicated that this sensing element had low operating temperature and could be used at room temperature. Other parameters like response time, recovery time, hysteresis, and aging effects were also studied. The crystallite size for the sensing element of pure ZnO annealed at 600 °C calculated from Scherrer's formula is in the 24–38 nm range. For the sensing element of 7% Cu doped ZnO the range of crystallite size is 25–41 nm. The average grain size as measured from SEM micrograph for 7% Cu doped ZnO and pure ZnO sensing elements were 36 and 42 nm, respectively.

Activation energies for the intermixing reaction of textured metal-metal multilayer thin films have been determined using X-ray diffraction analysis. Kinetic data were collected utilizing an area detector so as to reduce intensity bias from changes in out-of-plane texture during the intermixing reaction. Activation energies for Al/Pt, Ni/Ti, and Co/Al metal-metal multilayer thin films have been determined as 95.4(2) kJ/mol, 201(13) kJ/mol, and 247(19) kJ/mol, respectively.

Thermal degradation of graphene based mineral oil lubricants was studied using thermogravimetric analysis (TGA). As-synthesized graphene sheets of 8, 12, and 60 nm thick and engine oil formulations 20W50 SN/CF and 20W50 SJ/CF were used for synthesizing various test samples. UV-Vis spectrophotometry, zeta potential, field emission scanning electron microscopy, and energy-dispersive x-ray spectroscopy were used to characterize the graphene sheets and the nanolubricants. TGA revealed that the onset temperature of oxidation for the SN/CF oil could be delayed by 13–17 °C in the presence of graphene. Moreover the rate of oxidation when the weight loss of oil in the presence of graphene reaches 40–20% could be delayed by more than 30 °C. Resistance to oil degradation depends strongly on the graphene nanoparticle size and concentration. TGA kinetics studies show that the base oils have higher activation energy (Ea) and the addition of graphene significantly reduces Ea.

The present work is concerned with the determination of boron activation energy in theC35 steel and an estimation of the mass gain generated by the boriding treatment. Theboride layers are produced by the pack-boriding method on the C35 steel in the temperaturerange of 800−1000 °C for atreatment time ranging from 0.5 to 8 h. The presence of both FeB and Fe2B phases was confirmed by theX-ray diffraction technique and by a microscopic examination of the cross-sections ofborided samples. The boron activation energy was evaluated as 153.1 kJ mol-1 in the temperature range of800−1000 °C. This value ofenergy is in agreement with the literature data. The mass gain was measured by weighingthe samples before and after the boriding treatment by the weighing technique. Theevolution of mass gain as a function of temperature and time can be described by aparabolic law. Finally, an iso-thickness diagram was established to be used as a tool tooptimize the boride layers thicknesses according to the industrial application.

Effects of temperature on the spectral properties of visual pigments were measured in the physiological range (5–28°C) in photoreceptor cells of bullfrog (Rana catesbeiana) and crucian carp (Carassius carassius). Absorbance spectra recorded by microspectrophotometry (MSP) in single cells and sensitivity spectra recorded by electroretinography (ERG) across the isolated retina were combined to yield accurate composite spectra from ca. 400 nm to 800 nm. The four photoreceptor types selected for study allowed three comparisons illuminating the properties of pigments using the dehydroretinal (A2) chromophore: (1) the two members of an A1/A2 pigment pair with the same opsin (porphyropsin vs. rhodopsin in bullfrog “red” rods); (2) two A2 pigments with similar spectra (porphyropsin rods of bullfrog and crucian carp); and (3) two A2 pigments with different spectra (rods vs. long-wavelength-sensitive (L-) cones of crucian carp). Qualitatively, the temperature effects on A2 pigments were similar to those described previously for the A1 pigment of toad “red” rods. Warming caused an increase in relative sensitivities at very long wavelengths but additionally a small shift of λmax toward shorter wavelengths. The former effect was used for estimating the minimum energy required for photoactivation (Ea) of the pigment. Bullfrog rod opsin with A2 chromophore had Ea = 44.2 ± 0.9 kcal/mol, significantly lower (one-tailed P < 0.05) than the value Ea = 46.5 ± 0.8 kcal/mol for the same opsin coupled to A1. The A2 rod pigment of crucian carp had Ea = 42.3 ± 0.6 kcal/mol, which is significantly higher (one-tailed P < 0.01) than that of the L-cones in the same retina (Ea = 38.3 ± 0.4 kcal/mol), whereas the difference compared with the bullfrog A2 rod pigment is not statistically significant (two-tailed P = 0.13). No strict connection between λmax and Ea appears to exist among A2 pigments any more than among A1 pigments. Still, the A1 → A2 chromophore substitution in bullfrog opsin causes three changes correlated as originally hypothesized by Barlow (1957): a red-shift of λmax, a decrease in Ea, and an increase in thermal noise.

An objective method for determining the coagulum cutting time is needed to improve consistency and processing efficiency of goats' cheese. A fibre optic sensor was used to measure the backscatter of near-infrared radiation at 880 nm during the coagulation of skimmed goats' milk for the purpose of predicting coagulum cutting time. A randomised block design, replicated three times, was used to test the effect of three protein concentrations (3, 5 and 7% (w/w)) on diffuse reflectance parameters for cutting time prediction of milk coagulated at five different temperatures (20, 25, 30, 35 and 40°C) to assure a wide range of coagulation rates. The inclusion of a protein term in the existing algorithms was essential to reduce the standard error of prediction to under 6·2 min. An algorithm including a time-based parameter and a protein term, Tcut=β0T2 min (1+γ% Protein) was found to predict cutting time with a SEP of 2·42 min and an R2 of 0·98. γ was considered constant (γ=−0·0674, goats' milk) representing the protein effect on β0. Algorithms using response-based parameters (such as change in reflectance ratio) and the composition parameter protein required additional regression parameters such as temperature and an intercept term to predict the cutting time with the same precision as algorithms using only time-based parameters. Time-based parameters were found to decrease proportionally with increasing temperature and decreasing protein concentration. Response-based and mixed-based parameters were found to decrease with decreasing temperature. Reflectance ratio at cutting time did not significantly change with protein concentration for skimmed goats' milk. The activation energy of κ-casein hydrolysis was calculated based on changes in reflectance profile parameters and was found to be in the range 63–72 kJ mol−1.

Temperature effects on spectral properties of the two types of rod photoreceptors in toad retina, “red” and “green” rods, were studied in the range 0–38°C. Absorbance spectra of the visual pigments were recorded by single-cell microspectrophotometry (MSP) and spectral sensitivities of red rods were measured by electroretinogram (ERG) recording across the isolated retina. The red-rod visual pigment is a usual rhodopsin (λmax = 503.6 nm and 502.3 nm at room temperature (21°C) in, respectively, Bufo marinus and Bufo bufo), that of green rods (λmax = 432.6 nm in Bufo marinus) belongs to the “blue” cone pigment family. In red rods, λmax depended inversely and monotonically on temperature, shifting by −2.3 nm when temperature was raised from 0°C to 38°C. Green-rod λmax showed no measurable dependence on temperature. In red rods, warming caused a relative increase of sensitivity in the long-wavelength range. This effect can be used for estimating the energy needed for photoexcitation, giving Ea = 44.3 ± 0.6 kcal/mol for Bufo marinus rhodopsin and 48.8 ± 0.5 kcal/mol for Bufo bufo rhodopsin. The values are significantly different (P < 0.001), although the two rhodopsins have very similar absorption spectra and thermal isomerization rates. Our recording techniques did not allow measurement of the corresponding effect at long wavelengths in green rods. Although spectral effects of temperature changes in the physiological range are small and of little significance for visual function, they reveal information about the energy states and different spectral tuning mechanisms of the visual pigments.