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Effect of Heat Treatment on Microstructure and Mechanical Properties of Laser Additively Manufactured AISI H13 Tool Steel

The effect of heat treatment on microstructure and mechanical properties (microhardness, wear resistance and impact toughness) of laser additively manufactured AISI H13 tool steel was systemically investigated. To understand the variation of microstructure and mechanical properties under different heat treatments, the as-deposited samples were treated at 350, 450, 550, 600 and 650 °C/2 h, respectively. Microstructure and phase transformation were investigated through optical microscopy, scanning electron microscope and transmission electron microscope. The mechanical properties were characterized by nanoindentation tests, Charpy tests and high-temperature wear tests. The microstructure of as-deposited samples consisted of martensite, ultrafine carbides and retained austenite. After the tempering treatment, the martensite was converted into tempered martensite and some fine alloy carbides which precipitated in the matrix. When treated at 550 °C, the greatest hardness and nanohardness were 600 HV{sub 0.3} and 6119.4 MPa due to many needle-like carbides precipitation. The value of hardness increased firstly and then decreased when increasing the temperature. When tempered temperatures exceeded 550 °C, the carbides became coarse, and martensitic matrix recrystallized at the temperature of 650 °C. The least impact energy was 6.0 J at a temperature of 550 °C. Samples tempered at 550 °C had larger wear volume loss than that of others. Wear resistances of all samples under atmospheric condition at 400 °C showed an oxidation mechanism.

36 MATERIALS SCIENCE↗

Computational Design of a Novel Medium-Carbon, Low-Alloy Steel Microalloyed with Niobium

The design of a new steel with specific properties is always challenging owing to the complex interactions of many variables. In this work, this challenge is dealt with by combining metallurgical principles with computational thermodynamics and kinetics to design a novel steel composition suitable for thermomechanical processing and induction heat treatment to achieve a hardness level in excess of 600 HV with the potential for good fracture toughness. CALPHAD-based packages for the thermodynamics and kinetics of phase transformations and diffusion, namely Thermo-Calc{sup ®} and JMatPro{sup ®}, have been combined with an interdendritic segregation tool (IDS) to optimize the contents of chromium, molybdenum and niobium in a proposed medium-carbon low-manganese steel composition. Important factors taken into account in the modeling and optimization were hardenability and as-quenched hardness, grain refinement and alloying cost. For further investigations and verification, the designed composition, i.e., in wt.% 0.40C, 0.20Si, 0.25Mn, 0.90Cr, 0.50Mo, was cast with two nominal levels of Nb: 0 and 0.012 wt.%. The results showed that an addition of Nb decreases the austenite grain size during casting and after slab reheating prior to hot rolling. Validation experiments showed that the predicted properties, i.e., hardness, hardenability and level of segregation, for the designed composition were realistic. It is also demonstrated that the applied procedure could be useful in reducing the number of experiments required for developing compositions for other new steels.

36 MATERIALS SCIENCE↗

Hydrothermal synthesis and photocatalytic performance of hierarchical Bi{sub 2}MoO{sub 6} microspheres using BiOI microspheres as self-sacrificing templates

Bi{sub 2}MoO{sub 6} hierarchical microspheres were successfully prepared through phase transformation from BiOI microspheres with the assistance of sodium citrate under hydrothermal condition. The possible formation mechanism for the conversion of BiOI to Bi{sub 2}MoO{sub 6} is discussed here. After being annealed at 300 °C for 2 h, the obtained Bi{sub 2}MoO{sub 6} microspheres exhibited remarkably enhanced photocatalytic activity towards the degradation of rhodamine B and phenol. The superior catalytic performance can be attributed to its larger surface area and higher crystallinity. In addition, Bi{sub 2}MoO{sub 6} microspheres are stable during the degradation reaction and can be used repeatedly. - Graphical abstract: Bi{sub 2}MoO{sub 6} hierarchical microspheres were successfully prepared through a facile partial anion exchange strategy using BiOI microspheres as self-sacrificing templates. The Bi{sub 2}MoO{sub 6} microspheres show high visible light photocatalytic activity. - Highlights: • Bi{sub 2}MoO{sub 6} microspheres were prepared via self-sacrificing template anion exchange. • Sodium citrate-assisted anion exchange for preparation of Bi{sub 2}MoO{sub 6} photocatalyst. • Bi{sub 2}MoO{sub 6} catalysts show high visible light photocatalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Toughness of High-Strength Steel Weld Metals

Low-temperature phase transformation (LTPT) welding consumables are a new class of welding wires developed to mitigate hydrogen-induced cracking in the welding of high-strength steels without preheating or postweld heat treatment. LTPT weld metals have a high strength, but their toughness needs further investigation. LTPT weld metals predominately contain a martensite microstructure, which is necessary to achieve high strength; however, martensitic weld metals containing oxide inclusions have relatively poor toughness. For this study, three welding processes — gas metal arc welding (GMAW), gas tungsten arc welding (GTAW), and hot wire GTAW — were investigated. Optical microscopy, scanning electron microscopes, and transmission electron microscopes were employed for characterization. The role of the shielding gas in the formation of oxide inclusions in LTPT weld metals was investigated. The formation of oxide inclusions in the weld metals was related to the CO 2 in the shielding gas. When 100% Ar or a pure inert shielding gas mixture was used for all three welding processes, oxide inclusions were greatly reduced, and the weld metal toughness improved considerably, matching the base metal toughness. The mechanism by which inclusions promote fracture propagation in the weld metal was proposed.

36 MATERIALS SCIENCE↗

Three-dimensional sea-urchin-like hierarchical TiO{sub 2} microspheres synthesized by a one-pot hydrothermal method and their enhanced photocatalytic activity

Graphical abstract: SEM images of the samples synthesized at different hydrothermal temperatures for 8 h: (a) 75; (b) 100; (c) 120; and (d) 140°C, followed by calcination at 450 °C for 2 h. Highlights: ► Effects of calcination temperature on the phase transformation were studied. ► Effects of hydrothermal temperature and time on the morphology growth were studied. ► A two-stage reaction mechanism for the formation was presented. ► The photocatalytic activity was evaluated under sunlight irradiation. ► Effects of calcination temperature on the photocatalytic activity were studied. - Abstract: Novel three-dimensional sea-urchin-like hierarchical TiO{sub 2} superstructures were synthesized on a Ti plate in a mixture of H{sub 2}O{sub 2} and NaOH aqueous solution by a facile one-pot hydrothermal method at a low temperature, followed by protonation and calcination. The results of series of electron microscopy characterizations suggested that the hierarchical TiO{sub 2} superstructures consisted of numerous one-dimensional nanostructures. The microspheres were approximately 2–4 μm in diameter, and the one-dimensional TiO{sub 2} nanostructures were up to 600–700 nm long. A two-stage reaction mechanism, i.e., initial growth and then assembly, was proposed for the formation of these architectures. The three-dimensional sea-urchin-like hierarchical TiO{sub 2} microstructures showed excellent photocatalytic activity for the degradation of Rhodamine B aqueous solution under sunlight irradiation, which was attributed to the special three-dimensional hierarchical superstructure, and increased number of surface active sites. This novel superstructure has promising use in practical aqueous purification.

36 MATERIALS SCIENCE↗

A method for analyzing the non-stationary nucleation and overall transition kinetics: A case of water

We present the statistical method as a direct extension of the mean first-passage time concept to the analysis of molecular dynamics simulation data of a phase transformation. According to the method, the mean first-passage time trajectories for the first (i = 1) as well as for the subsequent (i = 2, 3, 4,…) nucleation events should be extracted that allows one to calculate the time-dependent nucleation rate, the critical value of the order parameter (the critical size), the waiting times for the nucleation events, and the growth law of the nuclei – i.e., all the terms, which are usually necessary to characterize the overall transition kinetics. There are no restrictions in the application of the method by the specific thermodynamic regions; and the nucleation rate parameters are extracted according to their basic definitions. The method differs from the Wedekind-Bartell scheme and its modification [A. V. Mokshin and B. N. Galimzyanov, J. Phys. Chem. B 116, 11959 (2012)], where the passage-times for the first (largest) nucleus are evaluated only and where the average waiting time for the first nucleation event is accessible instead of the true steady-state nucleation time scale. We demonstrate an efficiency of the method by its application to the analysis of the vapor-to-liquid transition kinetics in water at the different temperatures. The nucleation rate/time characteristics and the droplet growth parameters are computed on the basis of the coarse-grained molecular dynamics simulation data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Roughing on Finish Rolling Simulations in Microalloyed Strip Steels

The effects of a roughing pass in hot rolling simulations were assessed in VN and Nb-Ti steels. Continuous cooling phase transformation temperatures, flow curves, softening mechanisms (dynamic transformation DT and dynamic recrystallization DRX), and deformed microstructure morphologies were analyzed. The application of one or more roughing passes eliminates the effects of prior microstructural history and ensures that all stock material experiences equivalent hot working conditions and state of the microalloying elements. It has been shown that roughing in hot simulation has the following positive influences: (1) provide more reliable flow stress data; (2) give greater consistencies and accuracy in analysis of softening mechanisms giving three distinct regimes (DT regime at temperatures below 800 °C, DT/DRX inter-mode regime between 800 and 950 °C and DRX regime for temperatures above 950 °C for VN steel); (3) promotion of softening mechanisms as evidence by low critical strains (ε{sub c DT} was within the range 0.08-0.12, while for finishing-only pass, the ε{sub c DT} was in the range of 0.11-0.14 at ε-dot =0.1 s{sup −1}); (4) for roughing and finishing schedules, DT was verified to occur at temperatures 117 and 133 °C above Ae{sub 3} for VN steel and Nb-Ti steel, respectively, compared to the F-only schedules which showed that DT can only occur at temperatures below the Ae{sub 3}; (5) RF schedules promoted uniform microstructural morphologies compared to inhomogeneous microstructures realized in F-only schedules.

36 MATERIALS SCIENCE↗

Influence of grain size on transition temperature of thermochromic VO{sub 2}

Vanadium(IV) oxide (VO{sub 2}) is a unique material that undergoes a reversible phase transformation around 68 °C. The material could potentially be used as an energy-efficient coating for windows since its reflectance in the infrared (IR) increases significantly more than in the visible region. Currently, VO{sub 2} is limited by a transition temperature (τ{sub c}) that is too high, luminous transmittance that is too low or both. In this study, a transition temperature of 45 °C is achieved for a reactively sputtered, undoped film by restricting grain size to approximately 30 nm. It is concluded that a higher density of grain boundaries (smaller grain size) provides a greater number of nucleating defects which in turn reduces τ{sub c}. Similarly, a higher density of grain boundaries may reduce the hysteresis width (difference between transition temperatures in heating and cooling). Also in this study, a new set of optical performance metrics is proposed in which the solar spectrum is divided into the ultraviolet (UV), visible and near infrared (NIR) regions. This approach is more closely aligned with the goals of limiting UV, allowing luminous and modulating NIR transmission. Using these metrics, the optical properties of the low-τ{sub c} sample were: 2% UV transmittance, 47% luminous transmittance, and 23% NIR modulation (decrease from 43 to 33%). This study demonstrates that the grain size of VO{sub 2} should be viewed as an important parameter for controlling the transition temperature of the material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of Aqueous Fe(II) on Arsenate Sorption on Goethite and Hematite

Biogeochemical iron cycling often generates systems where aqueous Fe(II) and solid Fe(III) oxides coexist. Reactions between these species result in iron oxide surface and phase transformations, iron isotope fractionation, and redox transformations of many contaminant species. Fe(II)-induced recrystallization of goethite and hematite has recently been shown to cause the repartitioning of Ni(II) at the mineral-water interface, with adsorbed Ni incorporating into the iron oxide structure and preincorporated Ni released back into aqueous solution. However, the effect of Fe(II) on the fate and speciation of redox inactive species incompatible with iron oxide structures is unclear. Arsenate sorption to hematite and goethite in the presence of aqueous Fe(II) was studied to determine whether Fe(II) causes substantial changes in the sorption mechanisms of such incompatible species. Sorption isotherms reveal that Fe(II) minimally alters macroscopic arsenate sorption behavior except at circumneutral pH in the presence of elevated concentrations (10{sup -3} M) of Fe(II) and at high arsenate loadings, where a clear signature of precipitation is observed. Powder X-ray diffraction demonstrates that the ferrous arsenate mineral symplesite precipitates under such conditions. Extended X-ray absorption fine structure spectroscopy shows that outside this precipitation regime arsenate surface complexation mechanisms are unaffected by Fe(II). In addition, arsenate was found to suppress Fe(II) sorption through competitive adsorption processes before the onset of symplesite precipitation. This study demonstrates that the sorption of species incompatible with iron oxide structure is not substantially affected by Fe(II) but that such species may potentially interfere with Fe(II)-iron oxide reactions via competitive adsorption.

54 ENVIRONMENTAL SCIENCES↗

Stabilization of heavy metals in MSWI fly ash using silica fume

Highlights: • The stabilization of heavy metals in MSWI fly ash was investigated. • The addition of silica fume effectively reduced the leaching of Pb and Cd. • The relation of solid phase transformation and leaching behavior of heavy metals was discussed. - Abstract: The objective of this work was to investigate the feasibility and effectiveness of silica fume on stabilizing heavy metals in municipal solid waste incineration (MSWI) fly ash. In addition to compressive strength measurements, hydrated pastes were characterized by X-ray diffraction (XRD), thermal-analyses (DTA/TG), and MAS NMR ({sup 27}Al and {sup 29}Si) techniques. It was found that silica fume additions could effectively reduce the leaching of toxic heavy metals. At the addition of 20% silica fume, leaching concentrations for Cu, Pb and Zn of the hydrated paste cured for 7 days decreased from 0.32 mg/L to 0.05 mg/L, 40.99 mg/L to 4.40 mg/L, and 6.96 mg/L to 0.21 mg/L compared with the MSWI fly ash. After curing for 135 days, Cd and Pb in the leachates were not detected, while Cu and Zn concentrations decreased to 0.02 mg/L and 0.03 mg/L. The speciation of Pb and Cd by the modified version of the European Community Bureau of Reference (BCR) extractions showed that these metals converted into more stable state in hydrated pastes of MSWI fly ash in the presence of silica fume. Although exchangeable and weak-acid soluble fractions of Cu and Zn increased with hydration time, silica fume addition of 10% can satisfy the requirement of detoxification for heavy metals investigated in terms of the identification standard of hazardous waste of China.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Microstructure and oxidation behavior of NiCoCrAl/YSZ microlaminates produced by EB-PVD

Two NiCoCrAl/ZrO{sub 2}-Y{sub 2}O{sub 3} microlaminates (A and B) were fabricated by electron beam physical vapor deposition, which were different in layer number and metal-layer thickness. The layer number was 20 and 26, respectively. And the metal-layer thickness was 35 and 14 {mu}m, respectively. The microstructure and isothermal oxidation behavior were investigated. During the exposure in air at 1000 deg. C for 100 h, the t to m phase transformation occurred in the ceramic layers, and oxide scales formed at the surfaces of not only the outer metal-layers but also the internal metal-layers for the microlaminates. The oxidation rate of microlaminate B was greater than that of microlaminate A. Their overall mass gains were significantly dependent on the number and thickness of the metal-layers. The oxidation products were also influenced by metal-layer thickness. Oxide scales of the 35 {mu}m thick metal-layer microlaminate (A) consisted mainly of {alpha}-Al{sub 2}O{sub 3} and {theta}-Al{sub 2}O{sub 3}, while the oxidation products of the 14 {mu}m thick metal-layer microlaminate (B) were the mixture of {alpha}-Al{sub 2}O{sub 3}, {theta}-Al{sub 2}O{sub 3} and Cr{sub 2}O{sub 3}. It was also found that the growth of the oxide scale adjacent to the top YSZ layer was controlled by the oxygen diffusion, and that the growth of the oxide scale adjacent to the internal YSZ layer was controlled by the metal ionic diffusion. - Highlights: {yields} Effect of laminate structure on oxidation behavior of microlaminates was studied. {yields} Oxygen diffusion through YSZ layers led to the oxidation of internal metal-layers. {yields} The thinner NiCoCrAl layer was more difficult to form the stable Al{sub 2}O{sub 3} scale. {yields} Control of oxide scale growth by the oxygen diffusion in the outer metal-layers. {yields} Control of oxide scale growth by the metal ionic diffusion in internal metal-layers.

36 MATERIALS SCIENCE↗

Characterization of as-welded microstructure of heat-affected zone in modified 9Cr–1Mo–V–Nb steel weldment

Non-equilibrium microstructure of the heat-affected zone (HAZ) in the as-welded modified 9Cr–1Mo–V–Nb pipe steel (P91) weldment deposited by gas tungsten arc welding (GTAW) and flux core arc welding (FCAW) has been characterized by field-emission scanning electron microscope (FESEM) and electron backscatter diffraction (EBSD). The heterogeneous structures in the sub-layers of the as-welded HAZ are attributable to phase transformations caused by the welding thermal cycles and the local structure variations in the as-received base metal. Coarse-grained heat-affected zone (CGHAZ) has a prior austenite grain (PAG) size of 20 μm. Fine uniformly-distributed precipitates and a higher fraction of MX carbonitrides are observed in the CGHAZ. Fine-grained heat-affected zone (FGHAZ) consists of the finest grains (1.22 μm measured by EBSD, 5 μm PAG size), coarse undissolved M{sub 23}C{sub 6} carbides within the PAG boundaries and fine nucleated M{sub 23}C{sub 6} particles within the martensite laths. Inter-critical heat-affected zone (ICHAZ) consists of partially austenitized grains and over-tempered martensite laths. EBSD kernel average misorientation (KAM) map in the FGHAZ close to the ICHAZ illustrates the greatest local strain variations with a moderate normalized KAM value of 0.92°. The majority (88.1%) of the matrix grains in the CGHAZ are classified as deformed grains by EBSD grain average misorientation (GAM) evaluation. The FGHAZ close to the ICHAZ has the most recrystallized grains with an area fraction of 14.4%. The highest density variation of precipitates within grains in the FGHAZ originates from the inhomogeneous chemistry in the base metal. - Highlights: •A comprehensive characterization of the as-welded HAZ of P91 weldment is conducted. •Structural features in the each layer of the HAZ are quantified by EBSD. •Structural heterogenities in HAZ are due to welding cycle and base metal structure. •FGHAZ contains the finest grain structure and largest precipitate density variation.

36 MATERIALS SCIENCE↗

Microstructural evolution of rapidly solidified hypoeutectic Al 10Cu alloy during non-isothermal annealing transients induced by nano-second laser pulses

The evolution of characteristic nonequilibrium features presenting in morphologically distinct regions of rapid solidification (RS) microstructures in a hypoeutectic Al—10Cu (atomic %) in response to non-isothermal annealing transients has been studied by transmission electron microscopy (TEM). The capabilities of the Movie-Mode Dynamic TEM (MM-DTEM) instrument were used to expose select regions of the RS microstructure to sequences of rapid heating and cooling transients induced by nanosecond laser pulses while permitting in-situ observation. Partial melting, microstructural scale coarsening, morphological changes of the nonequilibrium features in the multi-phase RS microstructure, and solid-state phase transformation were observed. Heterogeneous nucleation of nanoscale θ-Al 2 Cu phase involved metastable supersaturated α-Al and the θ'-Al 2 Cu phases, establishing different sets of orientation relationships for the stable θ-Al 2 Cu and α-Al phases. Replacement of banded morphology grains that formed under conditions driven farthest from equilibrium by an equiaxed nanocrystalline structure comprised of α-Al phase, the primary solidification product, and an intergranular network of Al 2 Cu crystals has been attributed to local remelting. Here the experimental approach explored, permitted discovery of mechanistic details of location-specific transformation pathways activated in the multi-phase RS microstructure of hypoeutectic Al—Cu during subsequent nonisothermal transients.

36 MATERIALS SCIENCE↗

Review: mechanical behavior of metal/ceramic interfaces in nanolayered composites—experiments and modeling

In this study, recent experimental and modeling studies in nanolayered metal/ceramic composites are reviewed, with focus on the mechanical behaviors of metal/nitrides interfaces. The experimental and modeling studies of the slip systems in bulk TiN are reviewed first. Then, the experimental studies of interfaces, including co-deformation mechanism by micropillar compression tests, in situ TEM straining tests for the dynamic process of the co-deformation, thickness-dependent fracture behavior, and interrelationship among the interfacial bonding, microstructure, and mechanical response, are reviewed for the specific material systems of Al/TiN and Cu/TiN multilayers at nanoscale. The modeling studies reviewed cover first-principles density functional theory-based modeling, atomistic molecular dynamics simulations, and mesoscale modeling of nanolayered composites using discrete dislocation dynamics. The phase transformation between zinc-blende and wurtzite AlN phases in Al/AlN multilayers at nanoscale is also reviewed. Finally, a summary and perspective of possible research directions and challenges are given.

36 MATERIALS SCIENCE↗

The Beneficial Effect of Iron in Aluminum-Cerium-Based Cast Alloys

Iron (Fe) has been considered a major impurity since it is detrimental to the mechanical properties of many cast aluminum alloys due to the formation of Fe-containing brittle intermetallic phases. Fe is found naturally as an impurity in bauxite ore, resulting in Fe contamination of aluminum alloys with increasing contamination from current recycling practices. The Al–Ce–Fe system was investigated using CALPHAD (CALculation of PHAse Diagrams) modeling and experimental casting techniques. It was found that additions of Fe to the Al–Ce system are beneficial to the strength (slightly) and ductility (significantly) of the ternary alloys, which is attributed to the formation of fine metastable Al 8 CeFe 2 phase with aggregate morphology and equilibrium Al 10 CeFe 2 phase, suppressing coarse proeutectic Al 11 Ce 3 phase in near-eutectic Al–Ce alloys. Heat treatment study showed that the metastable Al 8 CeFe 2 phase transforms to predicted equilibrium Al 10 CeFe 2 phase at 500 °C, with essentially no intermetallic or grain coarsening; thus, the alloy displayed excellent property retention. The Al–Ce–Fe alloy system offers opportunities for sustainable, recyclable alloy development using low-cost Fe and low-cost cerium (a byproduct of rare-earth extraction).

42 ENGINEERING↗

Texture Evolution During Laser Direct Metal Deposition of Ti-6Al-4V

Titanium alloys are used in a wide variety of high performance applications and hence the processing of the titanium and the resulting microstructures after additive manufacturing has received significant attention. During additive manufacturing the processing route involves the transition from a liquid to solid state. The addition of successive layers results in a complex microstructure due to solid-state transformations. The current study focuses on understanding the phase transformations and relate it to the transformation texture in Ti-6Al-4V to identify conditions leading to a strong alpha transformation texture. The as deposited builds were characterized using optical microscopy and electron backscattered diffraction. The results showed columnar prior β grains with a martensitic structure after the deposition of a single layer. On subsequent depositions the martensitic microstructure decomposes to a colony and basketweave microstructure with a stronger transformation texture. The alpha texture with a colony and basketweave microstructure shows a stronger transformation texture as a result of variant selection. Thus by controlling the cooling rate of the build from the β transus it is possible to control the alpha transformation texture.

36 MATERIALS SCIENCE↗

Characterization of the effects of different tempers and aging temperatures on the precipitation behavior of Al-Mg (5.25at.%)-Mn alloys

We investigated the effects of different tempers (H131 and H116) and different aging temperatures (50 and 70 °C) on the precipitation behavior of Al-Mg (5.25 at.%)-Mn (Al 5083) alloys aged for a long time (41 and 30 months) using electron backscatter diffraction(EBSD), scanning transmission electron microscopy(STEM), energy-dispersive X-ray spectroscopy(EDS), atom probe tomography (APT), and small angle neutron scattering (SANS). Results for the GP zones and β'' phases were found in Al 5083 H116 aged at 50 °C for 24 months using APT. EDS and SANS revealed that a phase transformation process from GP zones to β'/β phases occurred for precipitates formed in both Al 5083 H131 and H116 aged at 70 °C. The effective diffusion coefficient of Mg in Al 5083 H131 is 1.8 times of that in Al 5083 H116 aged at 70 °C. The precipitation process in Al 5083 H116 aged at 50 °C is much slower than that in the sample aged at 70 °C. Finally, we identified the coarsening process in Al 5083 H131 and H116 aged at 70 °C for > 9 months.

36 MATERIALS SCIENCE↗

Pressure-induced structural changes in NH{sub 4}Br

We report angle dispersive X-ray diffraction (XRD) measurements and Raman spectroscopy on NH{sub 4}Br up to 70.0 GPa at room temperature. Three thermodynamically stable phases (phases II, IV, and V) are confirmed and a new possible phase (phase VI) of P2{sub 1}/m symmetry is proposed whose structure was established from Rietveld refinement of synchrotron XRD data for the first time. The phase sequence observed in NH{sub 4}Br is in accordance with phase II → IV → V → VI. Phase V transforms into phase VI at about 57.8 GPa with a huge volume reduction of 30%. Still, the intramolecular distances are analyzed to better understand the nature of structures. The H–H interactions become markedly more important as the N–Br distances are compacted, which is probably the reason of the kink of symmetric stretching band (ν{sub 1}) at the transition pressure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗