In-situ and ex-situ study of crystallization behaviour of magnetron sputtered Ni63Zr37 amorphous thin film

ABSTRACT

The stages of crystallization of magnetron sputter-deposited Ni₆₃Zr₃₇ film with mostly amorphous structure have been investigated by differential scanning calorimetry (DSC) and in-situ annealing at 300°C by use of heating stage on a high-resolution transmission electron microscope (HRTEM). These results have been further confirmed by grazing incidence X-ray diffraction analyses of thin film specimens annealed ex-situ at 300°C for various durations. The temperature for crystallization found by DSC has been found to increase from 371°C to 434°C with an increase in heating rate from 3°C/min to 10°C/min, and the apparent activation energy for amorphous to crystalline transformation has been found as ～260.2?kJ/mol from the Kissinger plot. Studies on HRTEM using in-situ heating stage have shown the crystallization to occur on annealing at 300°C for ～10?min. Crystallization at a temperature lower than that found by DSC is attributed to structural relaxation with reduction of free volume due to thermal activation. It has been observed that Ni₃Zr forms first due to its large negative enthalpy of formation, and is followed by the formation of Ni-rich solid solution (Ni_ss) grains. HRTEM studies have shown grain rotation with the formation of partial dislocations at Ni₃Zr-Ni_ss interfaces as well as twinning followed by detwinning with dislocation formation in the Ni_ss matrix possibly to reduce the interfacial energy.     

De-vitrification of nanoscale phase-separated amorphous thin films in the immiscible copper–niobium system

Copper and niobium are mutually immiscible in the solid state and exhibit a large positive enthalpy of mixing in the liquid state. Using vapour quenching via magnetron co-sputter deposition, far-from equilibrium amorphous Cu–Nb films have been deposited which exhibit a nanoscale phase separation. Annealing these amorphous films at low temperatures (~200?°C) initiates crystallization via the nucleation and growth of primary nanocrystals of a face-centred cubic Cu-rich phase separated by the amorphous matrix. Interestingly, subsequent annealing at a higher temperature (>300?°C) leads to the polymorphic nucleation and growth of large spherulitic grains of a body-centred cubic Nb-rich phase within the retained amorphous matrix of the partially crystallized film. This sequential two-stage crystallization process has been investigated in detail by combining transmission electron microscopy [TEM] (including high-resolution TEM) and atom probe tomography studies. These results provide new insights into the crystallization behaviour of such unusual far-from equilibrium phase-separated metallic glasses in immiscible systems.     

Austenite grain growth kinetics and mechanism of grain growth in 12Cr ultra-super-critical rotor steel

ABSTRACT

In this paper, the austenite grain growth behaviour of 12Cr ultra-super-critical (USC) rotor steel was investigated by a series of heat treatments. The heat treatments at heating temperatures of 900°C–1250°C and holding time of 1?h–20?h were conducted in an electric box-type heating furnace. Experimental results showed that the sizes of austenite grain were affected by heating temperatures and holding time, and heating temperature was the dominant factor. In addition, the grain growth rate changed significantly before and after the turning points of 1050°C and 1250°C. Meanwhile, an austenite grain growth mathematical model was established at different heating temperature stages, and possession of the capability to accurately predict austenite grain size was confirmed. Furthermore, the microstructure of austenite grain in the heating process was observed by optical microscope (OM) and transmission electron microscopy (TEM), which revealed the mechanism of austenite grain growth. Analysis indicated that the change of quantity of precipitate particles with increasing heating temperature was the main reason for the difference in austenite grain growth.     

Reactive Compatibilization of Poly(trimethylene terephthalate)/Polypropylene Blends by Polypropylene‐graft‐Maleic Anhydride. Part 2. Crystallization Behavior

The crystallization behavior of uncompatibilized and reactive compatibilized poly(trimethylene terephthalate)/polypropylene (PTT/PP) blends was investigated. In both blends, PTT and PP crystallization rates were accelerated by the presence of each other, especially at low concentrations. When PP content in the uncompatibilized blends was increased to 50–60 wt%, PTT showed fractionated crystallization; a small PTT crystallization exotherm appeared at ～135°C besides the normal ～175°C exotherm. Above 70 wt% PP, PTT crystallization exotherms disappeared. In contrast, PP in the blends showed crystallization exotherms at 113–121°C for all compositions. When a maleic anhydride‐grafted PP (PP‐g‐MAH) was added as a reactive compatibilizer, the crystallization temperatures (T _c ) of PTT and PP shifted significantly to lower temperatures. The shift of PTT's T _c was larger than that of the PP, suggesting that addition of the PP‐g‐MAH had a larger effect on PTT's crystallization than on PP due to reaction between maleic anhydride and PTT.

The nonisothermal crystallization kinetics was analyzed by a modified Avrami equation. The results confirmed that PTT's and PP's crystallization was accelerated by the presence of each other and the effect varied with blend compositions. When the PP content increased from 0 to 60 wt%, PTT's Avrami exponent n decreased from 4.35 to 3.01; nucleation changed from a thermal to an athermal mode with three‐dimensional growths. In contrast, when the PTT content increased from 0 to 90 wt% in the blends, changes in PP's n values indicated that nucleation changed from a thermal (0–50 wt% PTT) to athermal (60–70 wt% PTT) mode, and then back to a thermal (80–90 wt% PTT) mode. When PP‐g‐MAH was added as a compatibilizer, the crystallization process shifted considerably to lower temperatures and it took a longer crystallization time to reach a given crystallinity compared to the uncompatibilized blends.     

Mechanism of Bi2Sr2CaCu2Ox crystallization and superconducting properties for Bi2Sr2CaCu2Ox/Ag tapes prepared using isothermal partial melting method

The mechanism of Bi₂Sr₂CaCu₂O_x (Bi-2212) crystallization from a partially molten state has been studied by means of thermal analysis, X-ray diffraction (XRD) measurement, and microstructural observation in Bi-2212/Ag tapes. Tapes have been prepared using the isothermal partial melting (IPM) method, under which partial melting and solidification are carried out at the same temperature in an nitrogen atmosphere and 20% oxygen partial pressure (p(O₂)), respectively. The Bi-2212 phase crystallizes by peritectic reaction between (Sr, Ca)CuO₂ (1:1 phase) and the liquid phase at processing temperatures (T_p)≥855°C. At the beginning of Bi-2212 crystallization, only the 1:1 and the liquid phases are present in tapes. The Bi-2212 nucleation occurs in the vicinity of 1:1 grains (homogeneous nucleation). This peritectic reaction progresses by recovery of oxygen in the liquid phase. In contrast, the nucleation of the Bi-2212 phase occurs heterogeneously at T_p≤850°C. The Bi-2212 phase co-exists with four Bi-free phases ((Sr, Ca)₁₄Cu₂₄O₄₁ (14:24 phase), (Sr, Ca)₂CuO₃ (2:1 phase), (Sr, Ca)O (1:0 phase), and the 1:1 phase) and the liquid phase in the early stage of the Bi-2212 crystallization step. Since the precipitation temperature of the Bi-2212 phase is higher than 850°C, the Bi-2212 crystallization progresses by direct precipitation. The crystallization paths affect microstructure and transport critical current density (J_c) of Bi-2212 tapes.     

Correlation of dielectric properties,Raman spectra and calorimetric measurements of β-cyclodextrin-polyiodide complexes (β-cyclodextrin)2 ·BaI7 ·11H2O and (β-cyclodextrin)2 ·CdI7·15H2O

The frequency and temperature dependence of real and imaginary parts of the dielectric constant (ε′,?ε″), the phase shift (?) and the ac-conductivity (σ) of polycrystalline complexes (β-CD)₂·BaI₇·11H₂O and (β-CD)₂·CdI₇·15H₂O (β-CD?=?β-cyclodextrin) has been investigated over the frequency and temperature ranges 0–100?kHz and 140–420?K in combination with their Raman spectra, DSC traces and XRD patterns. The ε′(T), ε″(T) and ?(T) values at frequency 300?Hz in the range T<330?K show two sigmoids, two bell-shaped curves and two minima respectively revealing the existence of two kinds of water molecule, the tightly bound and the easily movable. Both complexes show the transition of normal hydrogen bonds to flip-flop type at 201?K. In the β-Ba complex most of the eleven water molecules remain tightly bound and only a small number of them are easily movable. On the contrary, in the β-Cd case the tightly bound water molecules are transformed gradually to easily movable. Their DSC traces show endothermic peaks with onset temperatures 118°C, 128°C for β-Ba and 106°C, 123°C, 131°C for β-Cd. The peaks 118°C, 106°C, 123°C are related to the easily movable and the tightly bound water molecules, while the peaks at 128°C, 131°C are caused by the sublimation of iodine. The activation energy of Ba²⁺ ions is 0.52?eV when all the water molecules exist in the sample and 0.99?eV when the easily movable water molecules have been removed. In the case of β-Cd the corresponding activation energies are 0.57?eV and 0.33?eV. The Raman peaks at 179?cm^?1, 170?cm^?1 and 165–166?cm^?1 are due to the charge transfer interactions in the polyiodide chains.     

Isothermal Crystallization Kinetics and Melting Behavior of a Luminescent Conjugated Polymer,Poly(9,9-Dihexylfluorene-Alt-2,5-Didodecyloxybenzene)

A study of the isothermal crystallization behaviors of poly(9,9-dihexylfluorene-alt-2,5-didodecyloxybenzene) (PF6OC12) was carried out using differential scanning calorimetry (DSC). The crystallization kinetics under isothermal conditions could be described by the Avrami equation. The Avrami exponent n ranges from 3.43 to 3.71 for PF6OC12 at crystallization temperatures between 100.0°C and 90.0°C, indicating a three-dimensional spherical crystal growth with homogeneous nucleation in the primary crystallization stage for the isothermal melt crystallization process. In the DSC scan, after the isothermal crystallization, multiple melting behavior was found. The multiple endotherms could be attributed to melting of recrystallized materials produced originally during different crystallization processes. According to the Arrhenius equation, the activation energy was determined to be 211.29 kJmol^?1 for the isothermal melt crystallization of PF6OC12.     

Reactivity and diffusion between La0.8Sr0.2MnO3 and ZrO2 at interfaces in SOFC cores by TEM analyses on FIB samples

In this paper, we investigate the diffusion and reactivity at the interface between the electrolyte (YSZ) and the cathode (LSM) of planar SOFC single cells by Analytical and High Resolution Transmission Microscopy. Cells were obtained via an aqueous tape-casting process allowing casting the three layers (cathode, electrolyte, anode [Ni-YSZ]) in a single operation. To allow the cell to function at intermediate temperatures (750–850 °C), the final electrolyte thickness after co-sintering at 1350 °C must range between 40 μm and 50 μm. As-sintered cells as well as cells that have been operated at 850 °C have been considered here; it is shown that the electrical performances were one order of magnitude less than expected and that they deteriorated quickly under operating conditions.In order to explain this behavior, we carried out analytical transmission electron microcopy. To obtain precisely located chemical and structural information, we used the “H-Shape” as well as the Lift Out FIB (Focused Ion Beam) techniques to extract 5 × 10 × 0.1 μm TEM samples; additional High Resolution characterization was carried out at interfaces between LSM and YSZ grains on standard ion-milled samples. We showed that the co-sintering temperature (1350 °C) was responsible for some diffusion of manganese through the electrolyte and the cathode, leading then to the rise of a significant electronic conduction and to the drop off of the ionic conductivity, and accounts for the germination and growth of the resistive pyrochlore phase La₂Zr₂O₇. Operating the cell at 850 °C do not aggravate these phenomena, but rather alters the anode microstructure.     

A thermo-chemical study of the defect structure of barium oxide

A study of BaO has been made by use of thermogravimetric analysis, oxygen concentration analysis, and X-ray lattice parameter measurements in the temperature range 850°C ? T ? 1420°C and oxygen pressure range 7 × 10^-6 atm ? p_O2 ? 0·820 atm. Both the weight gain by the BaO samples and subsequently determined excess oxygen concentration were found to be directly proportional to . The enthalpy of incorporation oxygen in the lattice

$\text{1}\text{2}\text{O}{}_2\text{(g)=O(excess)}$

was determined to be ?0·395 ± 0·034 eV. Creation of vacancies on cation sites or of oxygen interstitials are consistent with the experimental results. As an alternative, the formation of O₂^2? ions, (as in BaO₂) as a result of incorporation of excess oxygen in the lattice, has been suggested.     

Non-isothermal crystallization kinetics of alkyl-functionalized graphene oxide/high-density polyethylene nanocomposites

Dodecyl amine-functionalized graphene oxide (DA-GO) was obtained via an amidation reaction. The results of X-ray diffraction and Fourier-transform infrared spectroscopy verified that long alkyl chains of DA were successfully grafted on the GO sheets. Transmission electron microscope and scanning electron microscope techniques illustrated that homogeneously dispersed DA-GO/high-density polyethylene (HDPE) nanocomposites were obtained. The effects of DA-GO on the non-isothermal crystallization of HDPE were then investigated by differential scanning calorimetry (DSC) at various cooling rates (2, 5, 10, and 20?°C/min). Significant increase in the onset crystalline temperature (T_o) and the peak crystallization temperature (T_p) of HDPE incorporating DA-GO indicated the strong nucleating ability of DA-GO. The investigation of half-time crystallization time (t_1/2) demonstrated that crystallization rate of HDPE consisting of DA-GO is faster than that of pure HDPE at a given cooling rate. Ozawa, Avrami, and the combined Avrami–Ozawa methods (Mo) were used for analyzing experimental data. The Mo approach was successful in describing the non-isothermal crystallization process of DA-GO/HDPE nanocomposites. The results indicated that low DA-GO content accelerates the crystallization of HDPE, while higher content hinders the crystallization of HDPE.     

Nonisothermal Crystallization Kinetics of Miscible Blends of Polycaprolactone and Crosslinked Carboxylated Polyester Resin

The nonisothermal crystallization process of polycaprolactone (PCL)/crosslinked carboxylated polyester resin (CPER) blends has been investigated for different blend concentrations by differential scanning calorimetry (DSC). The DSC measurements were carried out under different cooling rates namely: 1, 3, 5, 10, and 20°C/min. Thermally induced crosslinking of CPER in the blends was accomplished using triglycidyl isocyanurate as a crosslinking agent at 200°C for 10 min. The cured PCL/CPER blends were transparent above the melting temperature of PCL and only one glass transition temperature, T_g, located in the temperature range between the two T_gs of the pure polymer components, was observed, indicating that PCL and crosslinked CPER are miscible over the entire range of concentration. The nonisothermal crystallization kinetics was analyzed based on different theoretical approaches, including modified Avrami, Ozawa, and combined Avrami–Ozawa methods. All of the different theoretical approaches successfully described the kinetic behavior of the nonisothermal crystallization process of PCL in the blends. In addition, the spherulitic growth rate was evaluated nonisothermally from the spherulitic morphologies at different temperatures using polarized optical microscope during cooling the molten sample. Only one master curve of temperature dependence of crystal growth rate could be constructed for PCL/CPER blends, regardless of different blend concentrations. Furthermore, the activation energy of nonisothermal crystallization process (ΔE_a) was calculated as a function of blend concentration based on the Kissinger equation. The value of ΔE_a was found to be concentration dependent, i.e., increasing from 83 kJ/mol for pure PCL to 115 and 119 kJ/mol for 75 and 50 wt% PCL, respectively. This finding suggested that CPER could significantly restrict the dynamics of the PCL chain segments, thereby inhibit the crystallization process and consequently elevate the ΔE_a.     

Preparation and properties of semiconductor CuO nanoparticles via a simple precipitation method at different reaction temperatures

Preparation and properties of CuO nanoparticles as an important p-type semiconductor via a simple precipitation method at different reaction temperatures varying from 10 to 115°C using copper acetate as a starting material have been reported. In addition, we investigated the influence of the ultrasonic irradiation through synthesizing the nanosized CuO at 60°C. Samples were characterized by XRD, FT-IR, SEM, TEM and UV-Vis techniques. XRD patterns of samples were identical to the single-phase pure CuO with a monoclinic structure. FT-IR spectra exhibited sharp peaks at around 519 and 598?cm^?1 which can be assigned to vibrations of the Cu-O bond. Results indicated that properties of samples had great dependence on the temperature and ultrasonic irradiation. The crystallite size and crystallization increased with increasing the temperature from 10 to 115°C. The band gap of samples was estimated to be in the range of 1.9–2.9?eV that is larger than the reported value for the bulk CuO (1.85?eV). This study provides a simple method for the preparation of nanosized CuO with a better surface uniformity and a narrow size distribution. Synthesized CuO samples with adjustable and controllable optical properties make the applicability of copper oxide even more versatile.     

Isothermal Crystallization and Melting Behavior of Composites Composed of Poly(L-lactic Acid) and Poly(glycolic Acid) Fibers

Several composites of poly (L-lactic acid) (PLLA) with poly (glycolic acid) (PGA) fibers were prepared. The isothermal crystallization kinetics and melting behavior of PLLA and all of the composites were characterized by using differential scanning calorimetry. The experimental data were processed by using the Avrami equation. The relative parameters, such as the Avrami exponent and half-time crystallization, revealed that PGA fibers had positive effects on the crystallization of PLLA, but these effects had only a minimal dependence on the PGA fiber content. Moreover, at low isothermal crystallization temperatures (85°C～110°C), recrystallization during the heating scan was observed, which could lower the melting point of the samples to a certain extent.     

Use of thermal annealing for radiation hardening of germanium to γ-rays

Thermal annealing for extended periods (20-1000 hours) at moderately low temperatures (500–675°C) is shown to produce significant hardening to the γ-radiation induced E_V + 0.23 eV and E_V + 0.38 eV levels in Ge crystals grown by the Czochralski technique from silica crucibles. Annealed samples showed concentrations of these levels between 33–58% of those in untreated control samples, as measured by deep level transient spectroscopy. In some samples, heating to 500°C for 1 hour produced the same effect.     

Strong interaction of an Al2Cu intermetallic precipitate with its boundary

NMR, X-ray diffraction (XRD) and transmission electron microscopy (TEM) experiments have been undertaken to establish the nature of Ω-platelets which form during heat treatment of aluminium alloys containing Cu, Mg (Mg lean) and Ag of the order of 0.1 at. % [1]. The platelets lie on (111) planes of the Al host lattice, separated from the Al on either face by a thin layer, one or two atoms thick, of Mg and Ag atoms. At temperatures between 185°C and 250°C the platelets have been previously shown to coarsen (thicken) slowly with time but more rapidly at 300°C [2,3]. TEM observations are described which confirm that the platelets remain on (111)_α for heat treatments up until at least 5?h at 300°C. The NMR and XRD results indicate that for thick platelets the bulk of the platelet material, sufficiently distant from the two bounding interfaces, is exactly tetragonal Al₂Cu θ-phase, but that platelets of the order of 2–4?nm thick (e.g. 100?h at 185°C) have a structure strongly influenced by interaction with the platelet boundary, which removes the axial symmetry of the Cu atom. Both NMR and XRD observations have shown a gradual transition between these two limits.     

Die einwirkung der struktur auf die kristallisationskinetik des glasigen selens

By means of a calorimetric method the rate of crystallization of vitreous selenium samples remelted at various temperatures t_U (225–3502C) was studied at a temperature of 90.0°C. To describe the kinetics the Avrami equation was used. The samples remelted at t_U < 260°C crystallized in one stage, A. For the samples remelted at t_U ? 260°C two stages, A and B, were observed. The rate constants k_Kr = z(L · c_Kr)$\text{1}\text{2}$ and the coefficients z were calculated from the Avrami equation. For the samples remelted at t_U = 225, 250 and 330°C, the activation energy e_kr was determined.The values of z, k_Kr and z · E_Kr were found to decrease as the temperature t_U increased. The kinetics of crystallization probably depend upon the structure of vitreous selenium (i.e. on the number of crystalline regions and on content of the small rings), which in turn is dependent on the temperature _U. This supposition was confirmed mathematically.     

Phase transformations in calcite from electrical impedance measurements

The phase transformation in calcite I-IV-V and calcite ? aragonite have been characterized by electrical impedance measurements at temperatures 600–1200°C and pressures 0.5–2.5?GPa in a piston cylinder apparatus. The bulk conductivity σ has been measured from Argand plots in the frequency range 10⁵–10^?2?Hz in an electric cell representing a coaxial cylindrical capacitor. The synthetic polycrystalline powder of CaCO₃ and natural crystals of calcite were used as starting materials. The transformation temperature T_c was identified from resistivity-temperature curves as a kink point of the activation energy. At pressure above 2?GPa in ordered phase calcite I, the activation energy E _σ is c. 1.05?eV, and in disordered phase calcite V E _σ is c. 0.75?eV. The pressure dependence of T_c for the rotational order–disorder transformation in calcite is positive for pressures <1?GPa and negative for pressures >1?GPa. The transformation boundary of calcite 1–IV is observed only during first heating in samples after a long annealing at low temperatures. The activation energy of calcite I???IV decreases gradually from 1.8 to 1.05?eV with the pressure increase from 0.5 to 2?GPa. The kinetics of calcite ? aragonite transformation has been monitored by measuring a time-variation of the electrical resistance of a calcite sample at 10³?Hz in the stability P-T field of aragonite. The variation of the impedance correlates with the degree of phase transformation, estimated from X-ray powder diffraction studies on quenched products of experiments. The kinetics of calcite ? aragonite transformation may be fitted to the Avrami kinetics with the exponent m???1–1.5.     

Studies on the synthesis and characterization of Zn1− x Cd x S and Zn1− x Cd x S:Mn2+ semiconductor quantum dots

Quantum dots (3–4?nm) of Zn_{1? x} Cd _x S (both free of Mn²⁺ and with Mn²⁺ incorporated) were synthesized through a novel solvothermal-microwave irradiation technique. Detailed structural analysis of the Zn_{1? x} Cd _x S and Zn_{1? x} Cd _x S:Mn²⁺ (x?=?0, 0.25, 0.5, 0.75 and 1) materials was carried out using powder X-ray diffraction technique. For all the compositions, the crystallite size was controlled to less than 1.5?nm. The optical energy gap for Zn_{1? x} Cd _x S was found to vary from 3.878 to 2.519?eV and for Zn_1?x Cd _x S:Mn²⁺ it varies from 3.830 to 2.442?eV when x is increased from 0 to 1. Overall, the optical energy gap could be tuned from a minimum of 2.442?eV to a maximum of 3.878?eV. DC conductivity analysis (from 40°C to 150°C) and electrical energy gap analysis for all the compositions were also performed. The dc conductivity for Zn_{1? x} Cd _x S solid solutions varies from 0.3840?×?10^?10 to 8.7782?×?10^?10?mho/m at 150°C and for Zn_{1? x} Cd _x S:Mn²⁺ it varies from 0.5751?×?10^?10 to 9.8078?×?10^?10 mho /m at 150°C (for x?=?0 to x?=?1). The method of synthesis and the results observed in this investigation may assist in the fabrication of optical devices when the required operational performance falls under the range observed in the study.     

Effects of Montmorillonite on the Nonisothermal Crystallization Behavior of the Poly(trimethylene terephthalate)/Polypropylene/Montmorillonite Nanocomposites

Organic montmorillonite (MMT) reinforced poly(trimethylene terephthalate) (PTT)/ polypropylene (PP) nanocomposites were prepared by melt blending. The effects of MMT on the nonisothermal crystallization of the matrix polymers were investigated using differential scanning colorimetry (DSC) and analyzed by the Avrami equation. The DSC results indicated that the effects of MMT on the crystallization processes of the two polymers exhibited great disparity. The PTT's crystallization was accelerated significantly by MMT no matter whether PTT was the continuous phase or not, but the thermal nucleation mode and three-dimensional growth mechanism remained unchanged. However, in the presence of MMT, the PP's crystallization was slightly retarded with PP as the dispersed phase, and was influenced little with PTT as the dispersed phase. When the MMT content was increased from 2_wt% to 7_wt%, the crystallization of the PTT phase was slightly accelerated, whereas the crystallization of the PP phase was severely retarded, especially at lower temperatures. Moreover, the nucleation mechanism for the PP's crystallization changed from a thermal mode to an athermal one. In the polypropylene-graft-maleic anhydride (PP-g-MAH) compatibilized PTT/PP blends, with the addition of 2_wt% MMT during melt blending, the T _c (PTT) shifted 7.8°C to lower temperature and had a broadened exotherm, whereas the T _c (PP) shifted 17.1°C to higher temperature, with a narrowed exotherm. TEM analysis confirmed that part of the PP-g-MAH was combined with MMT during blending.