Crystallographic aspects related to the high pressure–high temperature phase transformation of boron nitride

Crystallographic relations between different forms of boron nitride (BN) appearing at the high pressure–high temperature structural phase transformation have been revealed by high-resolution transmission electron microscopy (HRTEM). As starting materials, crystalline hexagonal BN (hBN) with different degrees of crystallinity, or with defects intentionally introduced, were used. Cubic BN (cBN) is formed only as a minor component, the rest consisting of different forms of sp ² bonded BN: hBN, compressed, monoclinic deformed hBN, or turbostratic BN (tBN). The small cBN crystallites (300–400?nm) contain many defects such as twins, stacking faults and nanoinclusions of other BN forms: tBN, rhombohedral BN (rBN) and wurtzite BN (wBN). The cBN phase grows epitaxially on the basal plane of hBN. The nucleation sites for cBN are revealed by HRTEM. They consist of nanoarches (sp ³ hybridized, highly curved nanostructures), frequently observed at the edges of the hBN crystallites in the starting materials. Based on HRTEM observations of specimens not fully transformed, a nucleation and growth model for cBN is proposed which is consistent with existing theoretical and experimental models.     

Synthesis of nanocrystalline magnesium nitride (Mg3N2) powder using thermal plasma

Nanocrystalline magnesium nitride (Mg₃N₂) powder was synthesized from bulk magnesium by thermal plasma at atmospheric pressure. Magnesium vapor was generated through heating the bulk magnesium by DC plasma jet and reacted with ammonia gas. Injecting position and flow rates of ammonia gas were controlled to investigate an ideal condition for Mg₃N₂ synthesis. The synthesized Mg₃N₂ was cooled and collected on the chamber wall. Characteristics of the synthesized powders for each experimental condition were analyzed by X-ray diffractometer (XRD), scanning electron microscopy (SEM) and thermogravity analysis (TGA). In absence of NH₃, magnesium metal powder was formed. The synthesis with NH₃ injection in low temperature region resulted in a formation of crystalline magnesium nitride with trigonal morphology, whereas the mixture of magnesium metal and amorphous Mg₃N₂ was formed when NH₃ was injected in high temperature region. Also, vaporization process of magnesium was discussed.     

硅在cBN单晶合成中的行为

 实验制备了复合氮化物Li₈SiN₄，并对合成温度、合成时间、气流量等因素的影响以及产物的稳定性进行了讨论。研究了Li₈SiN₄作为触媒添加剂时硅在cBN单晶合成中的作用。结果表明：cBN晶体多为截角八面体，晶面致密光滑；硅参与cBN的合成反应，并以SiO₂的形式沉积在cBN表面。     

Kinetics of phase transformation from hBN to cBN in the presence of Mg3BN3 catalyst

Abstract

Transformation kinetics from hBN to cBN has been studied at 6 GPa with changing reaction temperature and content of catalyst mixed with hBN powder. At lower catalyst content (3–10 wt %), rate of transformation was extraordinary rapid between 1300 and 1350 C. At higher catalyst content (30–50 wt %), rate of transformation was decreased. Normal nucleation kinetics was observed at about 1500 C. The rapid transformation temperature region correlates characteristic behavior of the sintering process.     

Crystallisation kinetics of amorphous Si–C–N ceramics: Dependence on nitrogen partial pressure

The crystallisation kinetics of amorphous precursor-derived ceramics of composition Si₂₆C₄₁N₃₃ is investigated as a function of temperature and nitrogen partial pressure using X-ray diffractometry. Isothermal annealing at a pressure of 1 bar leads to simultaneous crystallisation of Si₃N₄ and SiC, while only crystalline SiC is formed with annealing at a reduced pressure of 1 mbar. Rate constants of crystallisation are determined using the Johnson–Mehl–Avrami–Kolmogorov (JMAK) formalism. For temperatures below 1700°C, crystallisation rates are significantly higher for annealing at 1 mbar compared to 1 bar. For an explanation of the results, a model is proposed, which is based on diffusion-controlled nucleation and growth of crystalline Si₃N₄ and SiC in an amorphous matrix combined with thermal decomposition of Si₃N₄ at high temperatures.     

等离子体增强化学气相沉积法制备立方氮化硼薄膜过程中的表面生长机理

利用感应耦合等离子体增强化学气相沉积法以Ar，He，N₂和B₂H₆为反应气体制备了高纯立方氮化硼薄膜.用四极质谱仪对等离子体状况进行了系统的分析，发现B₂H₆完全被电离而N₂只是部分被电离.H₂和过量的N₂在等离子体中生成大量中性的H原子和活化的N^*₂，它们与表面的相互作用严重地阻碍了立方 关键词： 立方氮化硼薄膜 等离子体 质谱     

Reaction kinetics of α-CuInSe2 formation from an In2Se3/CuSe bilayer precursor film

The reaction pathway and kinetics of α-CuInSe₂ formation from a glass/In₂Se₃/CuSe polycrystalline bilayer precursor film were investigated using time-resolved, in situ high-temperature X-ray diffraction. Bilayer glass/In₂Se₃/CuSe precursor films were deposited on thin glass substrates in a migration enhanced molecular beam epitaxial deposition system. These films were then temperature ramp annealed or isothermally soaked while monitoring the phase evolution. The initial In₂Se₃ and CuSe reactant phases were directly transformed to α-CuInSe₂ without any detectable intermediate phase. Kinetic parameters were estimated using the Avrami and parabolic diffusion controlled reaction models. The parabolic reaction model fitted the experimental data better than the Avrami model over the entire temperature range (230-290 °C) of the set of isothermal experiments, with an estimated activation energy of 162 (±5) kJ/mol.     

Peculiarities of spontaneous crystallization of cubic boron nitride single crystal powders in the Li-B-N (H,Be) system

Abstract

We have investigated the effect of beryllium additions on the kinetics of conversion of hexagonal graphite-like BN to cubic BN (hBN → cBN) as well as on the linear rate of cBN crystal growth in a Li-B-N (H, Be) system. Experiments were performed in the temperature range 1940-2080K at a pressure of 4.3GPa. With the addition of 0.25 and 0.50wt.% beryllium the activation energy of the cBN formation process is found to be 45.8 and 42.0kJ/mol, respectively. The resulting crystals showed p-type conductivity. The activation energy of the impurity carriers for the samples with 0.25 and 0.50 wt.% beryllium additions equalled 0.22 and 0.17eV, respectively.     

Confined Crystallization in Polymer Blends: DSC Studies of the Behavior and Kinetics of Isothermal Crystallization of Polypropylene in Poly(cis-butadiene) Rubber Blends

Thermal properties of polypropylene with poly(cis-butadiene) rubber (iPP/PcBR) blends have been measured by differential scanning calorimetry (DSC), and the melting point T_m, crystallization temperature T_c, enthalpy Δ H (melting enthalpies and crystalline enthalpies), and equilibrium melting point T⁰ _m have been measured and calculated. The variation of T_m, T_c, Δ H and T⁰ _m with composition in the blends was discussed, showing that an interaction between phases is present in iPP/PcBR blends. The degree of supercooling characterizing the interaction between two phases in the blends and the crystallizability of the blends which bears a relationship to the composition of the blends was discussed. The kinetics of isothermal crystallization of the crystalline phase in iPP/PcBR blends was studied in terms of the Avrami equation, and the Avrami exponent n and velocity constant K were obtained. The Avrami exponent n is between 3 and 2, meaning that iPP has a thermal nucleation with two dimensional growths. The variation of the Avrami exponent n, velocity constant K, and crystallization rate G bear a relation to the composition of the blends, n increases with increasing content ofPcBR. K also increased with increasing content of PcBR. All of the K for the blends are greater than for pure iPP. The crystallization rate G (t_1/2) depends on the compositions in the blends; all G of the blends are greater than for iPP.     

On phase diagrams and on cBN formation in the system BN-Ca3B2N4

Abstract

The phase diagrams of Ca₃B₂N₄ and of the system BN-Ca₃B₂N₄ has been studied by high pressure differential thermal analysis Ca₃B₂N₄ has 3 structural phases and melts at higher temperature. The system BN-Ca₃B₂N₄ formes an eutectic melt and cBN is synthesized by nucleation and crystal growth.     

Precipitation kinetics of W2B5 in (Ti0.4W0.5Cr0.1)B2 solid solutions

The isothermal precipitation kinetics of W₂B₅ secondary phase from supersaturated polycrystalline (Ti_0.4W_0.5Cr_0.1)B₂ solid solutions were investigated with X-ray diffractometry and scanning electron microscopy in the temperature range between 1500 and 1700°C. The precipitate formation is described by a modified Johnson–Mehl–Avrami–Kolmogorov (JMAK) model, where W₂B₅ particles nucleate preferentially at grain boundaries and subsequently grow into the volume by a two-dimensional process controlled by volume diffusion of the transition metals. Numerical calculations are used to describe quantitatively the time dependence of the precipitated fraction and to determine a differential JMAK exponent n _diff which gives information on the nucleation and growth modes. n _diff decreases during the precipitation process from 2 to about 0.8 for all temperatures investigated. The first limit corresponds to the classical JMAK model (two-dimensional diffusional growth and constant nucleation rate) and the decrease in n _diff is the consequence of an impingement of the nucleating and growing particles in the late stages of the process. Nucleation and growth rates are determined as functions of reciprocal temperature, where the first quantity shows a non-monotonic behaviour with a maximum at about 1650°C and the second quantity exhibits an Arrhenius behaviour with an activation enthalpy of 3.6?eV. From this it can be concluded that the overall precipitate formation is dominated by the kinetics of atomic motion at low temperatures and by the thermodynamics of nucleation at high temperatures.     

Hydrothermal Synthesis of Metal Oxide Nanoparticles at Supercritical Conditions

Hydrothermal synthesis of CeO₂ and AlO(OH) were conducted using a flow type apparatus over the range of temperature from 523 to 673 K at 30 MPa. Nanosize crystals were formed at supercritical conditions. The mechanism of nanoparticle formation at supercritical conditions was discussed based on the metal oxide solubility and kinetics of the hydrothermal synthesis reaction. The reaction rate of Ce(NO₃)₃ and Al(NO₃)₃ was evaluated using a flow type reactor. The Arrhenius plot of the first order rate constant fell on a straight line in the subcritical region, while it deviated from the straight line to the higher values above the critical point. The solubility of Ce(OH)₃ and AlO(OH) was estimated by using a modified HKF model in a wide range of pH and temperature. In acidic conditions, where hydrothermal synthesis reaction is concerned, solubility gradually decreased with increasing temperature and then drastically dropped above the critical point. The trend of the solubility and the kinetics around the critical point could be explained by taking account of the dielectric constant effect on the reactions. There are two reasons why nanoparticle are formed at supercritical conditions. Larger particles are produced at subcritical conditions due to Ostwald ripening; that could not be observed in supercritical water because of the extremely low solubility. Second reason is the faster nucleation rate in supercritical water because of the lower solubility and the extremely fast reaction rate.     

Crystallization Kinetics of Nucleated Polypropylene with Organic Phosphates

The crystallization kinetics of isotactic polypropylene (iPP) and nucleated iPP with two organic phosphates, sodium salt (NA7) and triglyceride ester (NA8) of 2,2'-methylene-bis(4,6-di-tert-butylphenyl) phosphoric acid, were investigated by means of a differential scanning calorimeter under isothermal and nonisothermal conditions. During isothermal crystallization, a modified Avrami equation was used to describe the crystallization kinetics. Moreover, kinetics parameters, such as the Avrami exponent, n, the crystallization rate constant, k, and the half-time of crystallization, τ_1/2, are compared. The results showed that a dramatic decrease of the half-time of crystallization, as well as a significant increase of the overall crystallization rate, were observed in the presence of the organic phosphates. During nonisothermal crystallization, the primary crystallization was analyzed using the Ozawa model, leading to similar Avrami exponents for iPP and iPP/NA7, which means simultaneous nucleation with three-dimensional spherulitic growth. However, for iPP/NA8, the Avrami exponent in nonisothermal crystallization is evidently different from that in isothermal crystallization, which would indicate a different mechanism of crystal growth. Adding the nucleating agent to iPP makes the overall crystallization activation energy increase.     

Kinetics of Isothermal and Nonisothermal Crystallization of Poly(ethylene oxide) (PEO) in PEO/Fatty Acid Blends

In this work, isothermal and nonisothermal crystallization kinetics of poly(ethylene oxide) (PEO) and PEO in PEO/fatty acid (lauric and stearic acid) blends, that are used as thermal energy storage materials, was studied using differential scanning calorimetry (DSC) data. The Avrami equation was adopted to describe isothermal crystallization of PEO and nonisothermal crystallization was analyzed using both the modified Avrami approach and Ozawa method. Avrami exponent (n) for PEO crystallization was in the range 1.08–1.32 (10–90% relative crystallinity), despite of spherulites formation, while for PEO in PEO/fatty acid blends n was between 1.61 and 2.13. Hoffman and Lauritzen theory was applied to calculate the activation energy of nucleation (K_g) – the lowest value of K_g was observed for pure PEO, despite of heterogeneous nucleation of fatty acid crystals in PEO/fatty acid blends. For nonisothermal crystallization of PEO in PEO/lauric acid (1:1 w/w) and PEO/stearic acid (1:3 w/w) blends, secondary crystallization occurred and values of the Avrami exponent were 2.8 and 2.0, respectively. The crystallization activation energies of PEO were determined to be ?260 kJ/mol for pure PEO, ?538 kJ/mol for PEO/lauric acid blend, and ?387 kJ/mol for PEO/stearic acid blend for isothermal crystallization and ?135,6 kJ/mol, ?114,5 kJ/mol, and ?92,8 kJ/mol, respectively, for nonisothermal crystallization.     

Surface and bulk crystallization of amorphous alloys Ni-Si-B probed by electrical resistivity

Electrical resistivity measurements are tested as a sensitive probe of the crystallization processes in amorphous metallic alloys of Ni₇₈Si₇B₁₅, rendering the determination of nucleation rates at the surface and in bulk. It is shown that the increase in the electrical resistivity just below the crystallization temperature is mainly due to nucleation phenomena. Moreover, the Avrami coefficient, calculated from resistivity data, provides information about types of crystallization mechanisms, dimensionality of the crystallite growth and the sequence of crystallization stages.     

A room-temperature approach to boron nitride hollow spheres

Boron nitride hollow spheres were synthesized by the reaction of BBr₃ and NaNH₂ at room temperature; X-ray powder diffraction pattern could be indexed as hexagonal BN with the lattice constants of a=2.482 and c=6.701 Å; high-resolution transmission electron microscopy image showed the hollow spheres consisted of BN nanoparticles, with diameter between 80 and 300 nm; a possible formation mechanism of BN hollow spheres was discussed.     

In situ synchrotron diffraction studies on the formation kinetics of jarosites

This paper reports the results of time‐resolved synchrotron powder diffraction experiments where jarosites with different K/H₃O, K/Na and Na/H₃O ratios were synthesized in situ at temperatures of 353, 368 and 393 K in order to observe the effect on kinetics and species produced. The Na/H₃O sample formed monoclinic jarosite at all three temperatures, whereas the K/H₃O and K/Na samples formed as rhombohedral jarosites at 353 K, and as mixtures of rhombohedral and monoclinic jarosites at the higher temperatures. The relative amount of the monoclinic phase increased with increase in temperature. Unit‐cell parameter changes with reaction time could be explained by changes in iron stoichiometry (samples become more stoichiometric with time) together with changes in K/H₃O and Na/H₃O ratios. The reaction kinetics have been fitted using a two‐stage Avrami model, with two different Avrami exponents corresponding to initial two‐dimensional growth followed by one‐dimensional diffusion‐controlled growth. Activation energies for the initial growth stage were calculated to be in the range 90–126 kJ mol^?1.     

Thermal conductivity and heat capacity of Si3N4/BN fiber monoliths

This paper reports on measurements within the 5–300-K temperature interval of the thermal conductivity of Si₃N₄ and BN polycrystalline ceramic samples and Si₃N₄/BN fiber monoliths (FM) with different fiber arrangement architecture, [0], [90], and [0/90], with fibers arranged, accordingly, along and across the sample axis and the [0] and [90] layers stacked alternately. In the 3.5–300-K interval, the heat capacity at constant pressure, and at 77 K, the sound velocity have been measured in polycrystalline Si₃N₄ and BN samples and in Si₃N₄/BN [0] fiber monoliths. Our studies suggest that, with a high enough degree of confidence, but for some compositions—with minor assumptions, it can be maintained that, in the case of the Si₃N₄/BN fiber monoliths, one can use for calculation of their thermal conductivities and heat capacities within certain temperature intervals simple models considering mixtures of the Si₃N₄ and BN components with due account of their contributions to formation of the Si₃N₄/BN FM. It has been established that in the low-temperature domain (5–25 K), phonons in Si₃N₄/BN [0], [90], and [0/90] fiber monoliths scatter primarily from dislocations. This effect is not observed in ceramic Si₃N₄ and BN samples. The experimental data obtained on the thermal conductivity, heat capacity, and sound velocity have been used to calculate phonon mean free path lengths in polycrystalline Si₃N₄ and BN samples and the effective mean free path length in the Si₃N₄/BN [0] FM.     

The effects of dc bias voltage on the crystal size and crystal quality. of cBN films

For the deposition of cubic boron nitride thin films in Ar–N₂–BF₃–H₂ system by dc jet plasma chemical vapor deposition, the role of dc substrate bias ranging from -70 V to -150 V was investigated. A critical bias voltage was observed for the formation of cBN phase. The cBN content in the film increased with bias voltage and reached a maximum at the bias voltage of -85 V. Increasing the bias voltage further caused a decrease in cBN content and peeling of the films from the substrate. By combining the results of infrared spectroscopy, Raman spectroscopy and X-ray diffraction, the bias voltage was also found to strongly affect the crystal size, crystal quality and residual stress of the deposited films. A bias voltage a little higher than the critical value was demonstrated to be favorable for the deposition of a high-quality cBN film with large crystal size and low residual stress. Received: 13 June 2000 / Accepted: 21 June 2000 / Published online: 23 August 2000     

Correlation between stress profiles of cubic boron nitride thin films and the phase sequence revealed from infrared data

Cubic boron nitride thin films have been ion-beam-assisted deposited on silicon cantilever structures and subsequently back-etched in order to study the stress evolution and finally the growth mechanisms. After each sputtering step, the film stress, the remaining thickness, and the IR data were examined. In this way, the layered sequence of cBN on top of a hBN base layer, influencing the development of the intrinsic film stress, could be studied in detail. The observed stress distribution can be divided into three regions. First, a non-cubic base layer with a constant stress value is formed, followed by a linear increase in the stress after cBN nucleation as a result of the coalescence of cBN nanocrystals. Finally, the stress reaches a second plateau characteristic of the cBN top layer. In addition, the layered sequence was verified by the evolution of the FTIR spectra. Furthermore, the fraction of the sp²-bonded material of the cBN top layer was determined from the IR data. For various deposition conditions, a linear relationship between the stress of the nanocrystalline cBN top layer and the amount of sp³-bonded material was observed. From this, it can be concluded that stress relaxation occurs at the sp²-bonded grain boundary material. No evidence for stress relaxation after cBN nucleation was found. Received: 27 August 1999 / Accepted: 31 August 1999 / Published online: 3 November 1999