Effect of cooling rate and Al content on solidification characteristics of AZ magnesium alloys using cooling curve thermal analysis

The solidification behavior of AZ Magnesium alloys in various cooling conditions was investigated using a computer-aided cooling curve thermal analysis method. In each case, the cooling curve and its first and second derivative curves have been plotted using accurate thermal analysis equipment and solidification characteristics were recognized from these curves. The cooling rates used in the present study range from 0.22 to 8.13 °C s^?1. The results of thermal analysis show that the solidification parameters of AZ alloys such as nucleation temperature (T _N,α), nucleation undercooling (?T _N,α), recalescence undercooling (?T _R,α), range of solidification temperature (?T _S) and total solidification time (t _f) are influenced by variation of cooling rate. Also, the effect of Al content on these parameters was studied. Microstructural evaluation was carried out to determine the correlation between the cooling rate and secondary dendrite arm spacing.     

Influence of variation in the silicon content on the silicon precipitation in the Al–Si binary system

Ti-based amorphous alloys produced by ultra-rapid melt cooling represent an excellent option as biomaterials because of their mechanical properties and corrosion resistance. However, complete elimination of toxic elements is affecting the glass-forming ability and amorphous structure could be obtained only for thin ribbons or powders that are subsequently processed by powder metallurgy. Amorphous ribbons of special Ti₄₂Zr₄₀Ta₃Si₁₅ alloy, which is completely free of any toxic element, were produced by melt spinning, and the thermostability of resulting material was investigated in order to estimate its ability for further heat processing. Isochronal differential scanning calorimetry (DSC) was used to determine transformation points such as glass transition temperature T _g or crystallization temperature T _x. The activation energy for crystallization of amorphous phase was calculated based on Kissinger method, using heating rates ranging between 5 and 20 °C min^?1. Amorphous structure of resulting ribbon was evidenced by means of X-rays diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM). It was determined that amorphous Ti₄₂Zr₄₀Ta₃Si₁₅ alloy has a high activation energy for crystallization, similar to other Ti-based amorphous alloys, which provides good thermal stability for subsequent processing, especially by means of powder metallurgy techniques.     

Thermal analysis study on the simultaneous grain refinement and modification of 380.3 aluminum alloy

In this research, effect of integrated Al–10Sr–1Ti–2B master alloy has been studied on the microstructure and solidification characteristics of 380.3 aluminum alloy. Thermal Analysis has been used as a technique to study the cooling curves and first derivative curves during solidification of the alloy. Effect of integrated grain refiner and modifier on solidification parameters such as α-Al dendrite growth temperature (T _G,α), α-Al dendrite recalescence undercooling (?T _R,α), aluminum–silicon eutectic growth temperature (T _G,E), and eutectic recalescence undercooling (?T _R,E) has been determined. By increasing master alloy content, T _G,α and ?T _R,E have been increased, but, ?T _R,E has been decreased, and T _G,E increases first and then decreases. Aluminum–silicon eutectic depression temperature ( $ \Updelta T_{\text{G,E}}^{{{\text{Al}} - {\text{Si}}}} $ ) can be used as a parameter to control the modification of eutectic silicon. The results of this research indicate that the optimum level of Al–10Sr–1Ti–2B master alloy for the simultaneous grain refinement and modification of 380.3 alloy is about 0.5 mass%.     

Melting and crystallization DSC profiles of milk fat depending on selected factors

The aim of this study was to test selected factors, such as sample preparation and measurement procedure, potentially influencing repeatability of DSC analysis of milk fat melting and crystallization. The study investigated the effect of such factors as scanning rate, type of sample pans, method of butter dehydration, and final temperature in the cooling experiment. Based on recorded results, it was observed that cooling rate has a considerable effect on temperature, enthalpy, and height of peaks in the process of milk fat crystallization, as well as peak height and enthalpy in the melting process. By contrast, in the melting process no significant differences were observed in all measured temperatures in the range of heating rate of 2–20 °C min^?1 (p > 0.05). No statistically significant effect on thermodynamic parameters was found for sample pan type, the applied butter dehydration method and various final cooling temperatures (?60, ?50, and ?40 °C) either in the melting or crystallization processes. Only temperature of the second peak (T _c2) in the crystallization process constituted an exception in this respect, with significant differences (p ≤ 0.05) being recorded depending on the applied pan and dehydration method. With regard to the dehydration method, for the extraction and centrifugation methods the first peak forming during crystallization was characterized by high instability, manifested by various peak shape. Generally, it was found that the analysis of the melting and crystallization processes in milk fat, despite its complex composition, is characterized by high repeatability. Mean values of RSD calculated from all the experiments were very low, i.e., 1.8 % for the temperature in the melting process and 1.5 % in crystallization, 0.9 % for melting enthalpy, and 3.2 % for crystallization enthalpy, whereas for peak heights in melting it was 2.9 % and for crystallization it was 9.3 %, respectively.     

Thermal analysis study on the grain refinement of Al–15Zn–2.5Mg–2.5Cu alloy

Computer-aided cooling curve analysis is a reliable method to characterize the solidification behavior of an alloy. In this study, the effect of Al–5Ti–1B grain refiner on the solidification path, microstructure and macrostructure of a new Al–Zn–Mg–Cu super high-strength aluminum alloy containing high amounts of zinc was investigated using thermal analysis technique. The grain size measurement showed that Al–5Ti–1B reduces the grain size from 1402 to 405 μm. Solidification parameters in the liquidus region were in a good accordance with microstructural results. The addition of 1 mass% of Al–5Ti–1B grain refiner decreased ΔT _N from 9.1 to 7.7 °C. It also diminished recalescence undercooling from 1.42 to 0.32 °C. The grain refinement also altered dendritic structure of the alloy from a coarse, elongated and non-uniform to a rosette and more uniform shape. Moreover, the grain refiner resulted in a more uniform distribution of eutectic structure between dendrite arms. Furthermore, the grain refinement enhanced fraction of solid at dendrite coherency point from 21 % for unrefined alloy to 25 % for the alloy containing 1 mass% Al–5Ti–1B. In the same trend, the addition of 1 mass% Al–5Ti–1B reduced the amounts of porosity from 2.3 to 1.8 %.     

Shear-induced nonisothermal crystallization of two grades of PLA

Shear-induced nonisothermal crystallization of two commercial polylactides (PLAs) differing in optical purity was studied. The molten polymers were sheared at selected temperatures (T_s) and subsequently cooled. The crystallization was followed by a light depolarization method, whereas the specimens were analysed ex-situ by DSC, 2D-WAXS and SEM after etching. It was found that the effect of shear, especially on the crystallinity developed during post-shearing cooling, intensified with a decrease of T_s from 160 to 146 ^°C, and with increasing shear rate and strain. Moreover, the effect of shear on PLA1.5 with d-lactide content of 1.5% was stronger than PLA2.8 with 2.8% of d-lactide, although maximum crystallinity of both polymers was practically the same. A decrease of cooling rate from 30 to 10 ^°C/min increased crystallinity of both PLAs, except for those shearing conditions which induced high crystallinity even during faster cooling. Although SEM examination revealed some row-nucleated forms, no significant crystal orientation was detected by 2D-WAXS, indicating that, under the experimental conditions, the shear induced predominantly point-like nuclei.     

Microcalorimetric study of the effect of manganese on the growth and metabolism in a heterogeneously expressing manganese-dependent superoxide dismutase (Mn-SOD) strain

DSC, SEM–EDS, XRD and high-temperature XRD analysis was used to study thermal and crystallization behaviour of yttrium aluminate glasses prepared in the form of microspheres. The glasses YA-E (eutectic composition from the pseudo-binary system Al₂O₃–Y₃Al₅O₁₂) and YA-G (a composition identical to the stoichiometric Y₃Al₅O₁₂ (YAG) phase) were prepared by combination of the Pechini method with flame synthesis. The resulting microspheres were largely amorphous, but contained traces of yttrium–aluminium garnet as the main crystalline phase embedded in the yttrium aluminate glass matrix. Crystallization of the YAG phase was observed as the dominant exothermic process on DSC curves. From the DSC records, the basic thermal characteristics of the matrix glass, i.e. T _g (glass transition temperature), T _x (onset of crystallization peak temperature), T _f (temperature of the inflection point of the crystallization peak) and T _p (maximum of crystallization peak temperature), were determined. HT XRD experiments in the temperature interval 750–1200 °C and isothermal HT XRD experiments at 932, 998 and 1200 °C with 6-h holding time were also performed. Crystallization experiments at lower temperatures 932 °C (YA-E) and 915 °C (YA-G) were conducted to study phase development in a low-temperature region. Crystallization experiments at higher temperatures (1000, 1300 and 1500 °C) with maximum holding time of 6 h were performed to study crystallization of α-Al₂O₃ in the eutectic system. The SEM and SEM–EDS examination of polished cross sections of crystallized microspheres revealed slow volume crystallization of the YAG phase in the AY-E glass. Eventually, polycrystalline microspheres with fine-grained microstructure were prepared after 6-h treatment at 1500 °C.     

Polymorphism and melt crystallisation of racemic betaxolol, a β-adrenergic antagonist drug

We report the polymorphic behaviour, in melt cooling experiments, of racemic betaxolol, a low aqueous solubility selective β₁-adrenergic antagonist drug with a flexible molecular structure. A multidisciplinary approach is employed, using thermal analysis (differential scanning calorimetry, polarised light thermomicroscopy), spectroscopic methods (infrared spectroscopy, magic angle spinning ¹H NMR) and X-ray powder diffraction. A glass phase is obtained, T _g ~ ?10 °C, on cooling the melt, unless the cooling rate is ≤0.5 °C min^?1, while a new metastable form, polymorph II, T _fus = 33 °C, is generated in subsequent heating runs in a two step process. Although either partial crystallisation from the melt in the first step or the formation of an intermediate, metastable, low ordered phase may explain these observations, our results favour the second hypothesis. The stable polymorph I, T _fus = 69 °C, which crystallizes on further heating after form II melting, has also been obtained either from polymorph II or from the molten phase, on standing at 25 °C. The racemic betaxolol crystalline phases are found to exhibit some degree of disorder.     

Influence of annealing temperature on microstructural and electrochemical properties of rf-sputtered LiMn2O4 film cathodes

The microstructural and electrochemical properties of rf-sputtered LiMn₂O₄ films were investigated as a function of post-deposition process. The degree of crystallization in the films gradually increased with the increase of annealing temperature (T _a). The films annealed at T _a?=?973 K exhibited characteristic peaks with predominant (111) orientation representing the cubic spinel structure of Fd3m symmetry. The estimated Mn–Mn and Mn–O distances obtained from the X-ray diffraction data were observed to be increased slightly with T _a. Characteristic changes in surface morphological features were observed as a function of T _a as evidenced from scanning electron microscopy. The estimated root mean square (RMS) roughness of the films increased from 97 to 161 nm with augmentation of T _a. The electrochemical studies, viz. cyclic voltammetry (CV), specific discharge capacity and Li ion diffusion coefficient were carried out for annealed LiMn₂O₄ films in saturated aqueous electrolyte (Li₂SO₄) in the potential window of 0–1.2 V and correlated with surface morphology and grain size. The LiMn₂O₄ films annealed at T _a?=?973 K exhibited better electrochemical performance and demonstrated a discharge capacity of about 53.5 μA h cm^?2 μm^?1 with diffusion coefficient of 1.2?×?10^?13 cm² s^?1.     

Effect of cooling rate on the microstructure and solidification characteristics of Al2024 alloy using computer-aided thermal analysis technique

The aim of this work was to investigate the effect of different cooling rates on the microstructure and solidification parameters of 2024 aluminum alloy. Solidification characteristics are recognized from the cooling curve and its first and second derivative curves which have been plotted using thermal analysis technique. In this study, a mold having high cooling rate was designed and used to simulate the direct-chill casting process. The results of thermal analysis show that the characteristic parameters of Al2024 alloy are influenced by cooling rate. The cooling rates used in the present study range from 0.4 to 17.5 °C s^?1. Increasing the cooling rate affects the undercooling parameters both in liquidus and eutectic solidification regions. Investigations showed that solidification parameters such as nucleation temperature, recalescence undercooling temperature, and range of solidification temperature are influenced by variation of cooling rates. Microstructural evaluation was carried out to present the correlation between the cooling rate and dendrite arm spacing.     

Glass transition and crystallization kinetics analysis of Sb–Se–Ge chalcogenide glasses

Differential thermal analysis (DTA) has been employed to investigate the effect of Ge addition on the glass transition behavior and crystallization kinetics of Sb₁₀Se_90?xGe_x (x = 0, 19, 21, 23, 25, 27) alloys. The three characteristic temperatures viz. glass transition (T _g), crystallization (T _c), and melting (T _m) have been determined and found to vary with the heating rates and Ge content. Thermal stability and glass forming tendency have been evaluated in terms of ΔT (= T _c ? T _g) and reduced glass transition temperature. The activation energies for glass transition and crystallization have been used to analyze the nucleation and growth process. The activation energy analysis also determines the suitability of alloys to be used in switching applications. Results have been interpreted in terms of bond energies and structural transformations in the investigated alloys.     

Nonequilibrium crystallization of alloys in the naphthalene-dibenzyl system

Precrystallization supercooling states ΔT _L ^? in the naphthalene-dibenzyl system are investigated via thermal analysis to determine the metastable area of the supercooling state under normal conditions of crystallization. Autonomous supercooling is observed and the enthalpy of crystallization relative to the liquidus and solidus temperature is found. It is established that ΔT _L ^? falls smoothly as the concentration of the second component rises and reaches its lowest point with an eutectic alloy. The data on supercooling states and enthalpy are used to calculate different parameters of alloy crystallization in the system under study.     

Phase transition temperatures of Sn–Zn–Al system and their comparison with calculated phase diagrams

The Sn?CZn?CAl system was studied in connection with the possible substitution of lead-based solders for temperatures up to 350?°C. Ternary alloys with up to 3?wt% of aluminium were prepared. The investigated alloys lie close to the monovariant line (eutectic valley) of the Sn?CZn?CAl system. The temperatures of phase transitions of six binary Sn?CZn reference alloys and fourteen ternary Sn?CZn?CAl alloys using DTA method were investigated in this paper. DTA experiments were performed at the heating/cooling rate of?4?°C?min^?1 using Setaram SETSYS 18_TM experimental equipment. The temperatures of phase transitions in the ternary Sn?CZn?CAl system were obtained, namely, the temperature of ternary eutectic reaction T _E1 (197.7?±?0.7?°C), temperature of ternary transition reaction T _U1 (278.6?±?0.7?°C), temperatures of liquidus and other transition temperatures for studied alloys. Temperatures obtained during DTA heating runs were used as authoritative. DTA curves obtained during cooling enabled realising better differentiation of the obtained overlapped heat effects (peaks) during heating. Theoretical isopleths of the Sn?CZn?CAl phase diagram were calculated using the Thermocalc software and MP0602 thermodynamic database. Experimental data were compared with the calculated temperatures, and a good agreement was obtained.     

Study of phase transformation temperatures of alloys based on Fe–C–Cr in high-temperature area

Three alloys based on Fe–C–Cr were studied. These alloys contained carbon in a range of 0.308–0.380 mass% and chromium 1.058–4.990 mass%. Temperatures of solidus (onward used as T_S), liquidus (onward used as T_L) and peritectic transformation (onward used as T_P) were studied in the high-temperature region. These temperatures were obtained using two thermal analysis methods: differential thermal analysis (onward used as DTA) and simple thermal analysis (onward used as TA). The Setaram Setsys 18_TM was used for experiments with employment of the DTA method. All measurements were taken in an inert atmosphere of pure argon at heating rate of 10 °C min^?1, and simple TA method was used for the experiments with the use of the Netzsch STA 449 F3 Jupiter. Measurements were taken in inert atmosphere of pure argon at a heating and cooling rate of 5 °C min^?1. Phase transformation temperatures were obtained by heating and cooling process and were approximated to “equilibrium conditions” (DTA method: zero heating rate and sample mass, standard, TA method: only standard) (?aludová et al. in J Therm Anal Calorim 112:465–471, 2013a. doi: https://doi.org/10.1007/s10973-012-2847-8; J Therm Anal Calorim 111:1203–1210, 2013b. doi: https://doi.org/10.1007/s10973-012-2346-y). The experimental data were compared and discussed with the calculation results using IDS (solidification analysis package) software (onward used as SW) Thermo-Calc and the TCFE8 (Thermo-Calc Fe-based alloys) database. The results of the two alloys were compared with those published for similar steels. The experimentally obtained transition temperatures were close to the calculated values. The solidus, liquidus and peritectic transformation temperatures were lowered with increasing carbon (range 0.308–0.380 mass%) and chromium content (range 1.058–4.990 mass%). The smallest difference between the experimental results and theoretical calculations was observed at the liquidus temperature for all alloys. Nonetheless, the difference measured for the solidus temperatures was much greater.     

Study of thermo-oxidative chemical pre-treatment of isotactic polypropylene

A thermo-oxidative pre-treatment with chemical solutions is required in order to provide the adherence of inorganic semiconductor to the isotactic polypropylene (iPP) surface. A few thin films of iPP were treated with oxidizing solution at 90 °C. The crystalline properties were analyzed using XRD, and it had shown the presence of the α-monoclinic phases. The ATR-FTIR spectra had indicated that characteristic iPP peaks after thermo-oxidative chemical pre-treatment diminished sharply. Moreover, the new carbonyl groups (C = O) were observed, which signified oxidation. The UV–Vis spectra had showed a blue shift in the absorption edge, which corresponded to decrease in the optical band gap. The non-isothermal decomposition and crystallization kinetics of iPP films were studied and compared by means of thermogravimetric analysis and differential scanning calorimetric measurement. The values of the melting temperature T _m and the crystallization temperature T _c were found to be iPP surface structure and heating/cooling rate dependent. The activation energy of crystallization E _c was determined.     

Phase equilibria in the ZnGeAs<Subscript>2</Subscript>–MnAs system

The ZnGeAs₂–MnAs system is a eutectic-type system as determined by X-ray powder diffraction, DTA, and microstructure observation, with the eutectic coordinates: 61 mol % ZnGeAs₂ mol %, 39 mol % MnAs, and T_m = 816°C. The eutectic is a lamellar eutectic as shown by microstructure examination. A characteristic feature of the system is a small mutual solubility of the components. Precision analysis of diffraction patterns enabled us to refine unit cell parameters for cubic and tetragonal ZnGeAs₂ phases. MnAs in alloys is shown to consist of a hexagonal phase and a orthorhombic phase. ZnGeAs₂ and MnAs alloys are ferromagnets (T_C ~ 320 K). Their magnetization increases in response to increasing MnAs content.     

Annealing effects in commercial aluminium hot-rolled 7075(–Sc–Zr) alloys

In the present work, the effect of hot rolling (at temperature 300 °C/60 min) on mechanical, thermal properties, microstructure and recrystallization behaviour of the commercial AlZnMgCuFe(ScZr) (7075-Sc,Zr) alloys was investigated. Microhardness together with differential scanning calorimetry measurements was compared to microstructure development that was observed by transmission and scanning electron microscopy and electron backscatter diffraction. Microstructure observation proved two types of eutectic phase (T-phase and Mn,Fe,Si-containing phase) at (sub)grain boundaries in hot-rolled alloys. The grain size was?~?20 μm in the AlZnMgCuFeScZr and?~?1000 μm in the AlZnMgCuFe alloy. Sc,Zr-addition in hot-rolled AlZnMgCuFe(ScZr) alloys significantly refined the grains. Primary multilayer Al₃(Sc,Zr) particles precipitated during casting and subsequent cooling in the alloy with Sc,Zr-addition. These particles were stable up to 450 °C. No changes of microhardness values (in accuracy of measurement) from room temperature up to 450 °C in the alloys were observed there. Thus, the probable presence of these secondary Al₃(Sc,Zr) particles is most likely the reason of hardening (ΔHV?≈?20) of the AlZnMgCuFeScZr alloy. A little higher electrochemical potential was measured for AlZnMgCuFeScZr alloy (??1144 mV) than for AlZnMgCuFe alloy (??1171 mV). One exothermic process was observed in hot-rolled alloys; apparent activation energy of this process was calculated as?~?100 kJ mol^?1. Additional precipitation and/or coarsening of S-phase together with precipitation of T-phase are probably connected with the exothermic process. Sc,Zr-addition has a significant antirecrystallization effect. No recrystallization was observed in the hot-rolled AlZnMgCuFeScZr alloy, neither after annealing at 350 °C/10 h nor after annealing at 450 °C/10 h. A partial recrystallization effect of the hot-rolled AlZnMgCuFe alloy is clearly registered after annealing at 350 °C/10 h and occurs very strongly after annealing at 450 °C/10 h.

     

Non-isothermal crystallization kinetics of a Si–Ca–P–Mg bioactive glass

In this work, the crystallization process of a SiO₂–3CaO·P₂O₅–MgO glass was studied by non-isothermal measurements using differential thermal analysis carried out at various heating rates. X-ray diffraction at room and high temperature was used to identify and follow the evolution of crystalline phases with temperature. The activation energy associated with glass transition, (E _g), the activation energy for the crystallization of the primary crystalline phase (E _c), and the Avrami exponent (n) were determined under non-isothermal conditions using different equations, namely from Kissinger, Matusita & Sakka, and Osawa. A complex crystallization process was observed with associated activation energies reflecting the change of behavior during in situ crystal precipitation. It was found that the crystallization process was affected by the fraction of crystallization, (x), giving rise to decreasing activation energy values, E _c(x), with the increase of x. Values ranging from about 580 kJ mol^?1 for the lower crystallized volume fraction to about 480 kJ mol^?1 for volume fractions higher than 80 % were found. The Avrami exponents, calculated for the crystallization process at a constant heating rate of 10 °C min^?1, increased with the crystallized fraction, from 1.6 to 2, indicating that the number of nucleant sites is temperature dependent and that crystals grow as near needle-like structures.     

Dilatometric study of phase transformations in advanced high-strength bainitic steel

The work deals with dilatometric studies of a new-developed advanced high-strength bainitic 3Mn–1.5Al steel. Ferritic, bainitic and martensitic phase transformations are investigated in detail in respect of their temperature range forming and microstructures produced under various conditions of both continuous and isothermal cooling. The equilibrium temperatures of A _e1 and A _e3 and phase composition of the investigated steel were initially calculated whereas critical temperatures of A _c1 and A _c3 as well as the decomposition of retained austenite were determined upon heating. The major tests consisted of controlled cooling of undeformed or plastically deformed austenite using the dilatometer within the cooling rate range of 2–0.5 °C s^?1. The effects of the cooling rate and deformation at temperatures of 900 and 1,050 °C on the phase transformation behaviour and microstructure were explained. The final experiment was carried out using a thermo-mechanical simulator under conditions of multi-step deformation and isothermal holding of the steel at 400 °C. Microstructural features were revealed using light microscopy and scanning electron microscopy techniques.     

Investigation of solid solubility and metastable phase in dilute Th-Co alloys

The solubility of cobalt in α thorium is described by the equation c_s(at.% Co) = 10970 exp(−13844/T). The heat of solution is −115.2 kJ mol⁻ Co and the terminal solubility at the eutectic temperature 1100 °C is 0.46 at.% Co. A newly identified metastable phase with a plate morphology is present in thorium-rich alloys on quenching from the high (αTh) region. Upon aging for different times at 500 °C and above, this phase transforms to rod-like particles of Th₇Co₃.