Unravelling the metal borides evolution in the transient liquid phase bonding of Ni-based alloys via high-throughput transmission electron microscopy and first-principles thermo-kinetic calculations

The understanding of temperature and time-dependent metal borides precipitation/dissolution is cru-cial for the design of the transient liquid phase(TLP)bonding process of Ni-based alloys.It however remains elusive despite substantial research efforts for many years mainly owing to the uncertainty on the precipitated metal borides and the complex thermo-kinetics in the process.In this paper,we have unambiguously constructed the micro/nanoscale map of the precipitated metal borides in the TLP bonded Ni-based Inconel 718 superalloy via a high-throughput transmission electron microscopy(TEM)analy-sis.Five types of metal borides were found to precipitate in the diffusion affected zone(DAZ)when the isothermal solidification is completed.They are the M5B3 with stacking faults,Ti-rich M3B4,and Nb-rich M3B4 at the grain boundaries as well as single-crystalline M5B3 and M3B2 inside the grains.Notably,the crystal structure of the faulted M5B3 was rationalized by a hybrid modelling approach integrating first-principles calculation and TEM experiments.The sublattice model,with the optimized thermodynamic model parameters,was used to reproduce the metal borides precipitation map in the TLP process using DICTRA software.Coupling with multiscale simulation and experimental data,the present work built a modified thermo-kinetic model,which enables the design of the TLP bonding process of Ni-based alloys that often involves complicated time-temperature schedules and the precipitation/dissolution of a vari-ety of different phases.The strategy can be applied to the design of the brazing process of other alloys or hvbrid materials such as ceramics and metal.     

Processing of nimesulide-PEG 400-PG-PVP solid dispersions: preparation,characterization, and in vitro dissolution

The objective of this investigation was to study the influence of dissolution enhancers such as polyethylene glycol 400, propylene glycol, polyvinylpyrrolidone K30, sodium lauryl sulfate, and Tween 80 on in vitro dissolution of a model active pharmaceutical material--nimesulide. Preliminary studies were conducted using a physical blend of nimesulide, and the adjuvants and solid dispersions were prepared using solvent evaporation and cogrinding methods. Aqueous solution of adjuvants was first triturated with nimesulide, followed by mixing with lactose and microcrystalline cellulose, and finally water was evaporated under vacuum in a cogrinding method. A 33 factorial design was adopted in a cogrinding method using the concentration of polyethylene glycol 400, propylene glycol, and polyvinylpyrrolidone K30 as independent variables. Tween 80 and sodium lauryl sulfate were added in all the batches. Full and reduced models were evolved for different dependent variables. The reduced models were validated using two checkpoints. Angle of repose < 35 degrees, percentage of drug released in 30 min (Q30) > 40%, 45 min (Q45) > 50%, and 120 min (Q12) > 60% were used as constraints for the selection of an optimized batch. Contour plots are presented for the selected dependent variables. Polyvinylpyrrolidone was found to be more effective in increasing the drug dissolution, compared with polyethylene glycol 400 and propylene glycol. The granule flow was adversely affected when high levels of liquid adjuvants were used in formulations. Wettability study was conducted to measure wetting time for pure drug and the optimized batch. Improved drug dissolution was attributed to improved wetting and the solubilizing effect of adjuvants from the pseudosolid dispersions of nimesulide. Significant improvement in drug dissolution was observed (Q120 = 70%), compared with pure drug powder (Q120 = 15%). In conclusion, dissolution of nimesulide can be modulated using an appropriate blend of pharmaceutical adjuvants.     

Laser beam melting of aluminum alloys with hull-core build strategy by using an initial meso-scale simulation

Laser beam melting (LBM) of aluminum alloys is gaining a wide popularity in different industrial applications as an alternative technology for the production of individual and complex parts. A long build time and the high amount of experimental work for optimizing or finding new process parameters are two of the current challenges for reaching an industrial maturity. This paper proposes an efficient way to determine new process parameters for aluminum alloy aluminum-silicon10-magnesium with highest build-up rates by using a 3D finite element model on the mesoscopic level. High laser power in combination with the hull-core build strategy was used to increase the build-up rate without impairing the part accuracy. The influences of high laser power, laser diameter and scan speed on the melt pool were studied by using a thermal simulation of single laser tracks. Based on the simulation results the process window could be derived and was tested on a laser beam melting (LBM) system. The achieved reduction of the build time of up to 31 % without loss in part accuracy proved the novel approach for the prediction of the required process window as an efficient method to reduce costly and time-consuming experimental work.     

Insights into the dissolution mechanisms of detergent agglomerates: An approach to assess dissolution heterogeneity

In this work, the dissolution mechanisms of detergent agglomerates with different binders were investigated in aqueous solution. The dissolution processes of detergent agglomerates were online monitored by using in situ UV–VIS spectrophotometer and electric conductivity probe. Dissolution profiles were correlated by Weibull model to evaluate the time-dependent dissolution rate coefficient and to classify the type of dissolution rate function k_t(t). The Kullback-Leibler information distance d_K-L was proposed to assess the degree of dissolution heterogeneity. The results indicate that the sodium linear alkylbenzene sulfonates (NaLAS) and sodium carbonates (Na₂CO₃) in detergent agglomerates have different dissolution behaviors, and their dissolution rates are influenced by the type and content of binders. Moreover, detergent agglomerates using semi-solid NaLAS paste or liquid linear alkylbenzene sulfonic acid (HLAS) as binders in granulation processes follow different dissolution mechanisms in water.     

Sustained release microspheres of diclofenac sodium using PEGylated rosin derivatives

The PEGylated derivatives of rosin-PD-1 and PD-2 synthesized and characterized earlier (Nande et al., 2006) were investigated as potential materials for sustained release microsphere prepared by emulsion solvent evaporation method using diclofenac sodium (DCS) as model drug. All the microspheres exhibited smooth surfaces intercepted by pores; their sizes (d(90)) ranged between 11-24 microm. The entrapment efficiency (< 80%) of the microspheres increased proportionally with derivative concentration. Presence of solvent like isopropyl alcohol or dichloromethane rendered the microspheres with large sizes but with reduced drug entrapment. Microspheres with small size were obtained at an optimum viscosity of liquid paraffin; any change lead to increase in the particle size. Magnesium stearate was found to be most suitable detackifier in the present system. The drug release was directly related to the particle size--small sized microspheres released drug at a faster rate. The dissolution data complied with Higuchi equation while the mechanism of drug release was Fickian diffusion (n approximately 0.5). Controlled inhibition of edema, as tested by hind paw edema method, was observed for 10 h when the microspheres were administered intraperitoneally. The present study found the derivatives as promising materials for preparing microspheres for sustained delivery of DCS.     

Using volatile solvents for ion formation in liquid molecular beam expansion mass spectrometry

Cocrystallization between analyte and matrix is required by matrix-assisted laser desorption/ionization and can represent a significant limitation of the technique. A molecular beam expansion, mass spectrometric method has been developed to explore the possibility of using pure solvents as matrix to avoid cocrystallization. Two kinds of solvent, liquid CS2 and liquid or supercritical CO2, have been studied with 266-nm UV laser irradiation. We successfully ionized a number of compounds, including caffeine, guanine, cholesterol, and mixed fullerenes. Under some conditions, the mass spectra reflect parent radical cations formed by photoionization. Under other conditions, protonated, sodiated (and with CS2 even sulfated) ions are seen reflecting a nonunimolecular ionization process. When UV-transparent CO2 is used as a solvent, only analyte molecules with a UV chromophore are detected. However, with UV-absorbing CS2, we demonstrate ionization of molecules lacking a UV chromophore. This work provides strong evidence that one can form solvent clusters containing analyte, that laser photoionization of the solvent precedes ionization of the analyte, and that solvent evaporation along with the indirect ionization leads to reduced parent ion fragmentation. The exploration of this now demonstrated concept with other solvents would appear fruitful for future work.     

Effect of Formulation and Process Variables on the Dissolution Profile of Naproxen Sodium from Tablets

Results of this investigation revealed some important formulation characteristics of naproxen sodium. Tablets made from the granules, prepared by wet granulation method using water, showed a significant decrease in solution as compared to those made by dry blending method. During wet granulation, heat was evolved due to the hydration of naproxen sodium resulting in the retardation of dissolution. The pseudo-polymorphism and hydration is being investigated by Bansal et. al. (1). In addition, when polyvinyl pyrolidone (PVP K-90) was used instead of PVP K-30, the dissolution was further retarted. Addition of cross carmellose sodium (Ac-Di-Sol) did not change the dissolution behavior of these tablets. When naproxen sodium was granulated with water, a decrease in dissolution rate was observed as mixing time was increased from 5 minutes to 15 minutes. The increase in hardness of the tablet from 10 Kp to 18Kp did not alter the dissolution profile of naproxen sodium. When granulation was prepared using a low shear mixer (Planetary mixer) versus a high shear mixer (T.K. Fielder), the resultant tablets exhibited similar dissolution and physical chemical properties.     

Dispersion and reaction of TiB2 in liquid iron alloys

Abstract

The degree of reaction and dispersion achieved when TiB₂ powders are melted in contact with liquid iron based alloys has been assessed via a levitation dispersion test which had been developed earlier. Both Fe₂B and TiC were observed to form as a result of dissolution and reaction of TiB₂. The formation of TiC occurs during the reaction of commercial grade TiB₂ with liquid iron alloys containing as little as 0·08 wt-%C. The reaction of high purity TiB₂ with liquid iron alloys containing 0·24 wt-%C does not however lead to TiC formation. The formation of Fe₂B was observed for all conditions tested, owing to the effectively zero solubility of boron in solid iron. The TiB₂ remaining after dissolution and reaction was found to produce relatively good dispersions in the iron matrix and therefore additions of TiB₂ to liquid iron alloys may provide a means of producing Fe–TiB₂ composite materials. However, the brittle properties of Fe₂B will mean that, whereas such materials may be very hard, they are likely to lack toughness.

MST/1477     

Shaped inorganic, organic and inorganic-organic composite shells from surface engineering of crystal templates

The fabrication of inorganic (silica), organic (polymer) and inorganic-organic (silica-polymer composite) shaped shells through surface coating of crystal templates is the subject of the present work. The fabrication process comprises controlled coating of cubic sodium chloride and truncated rhombohedral sugar crystallites with sol-gel derived silica and/or polymeric compounds in order to frame the crystallites surfaces with a thick enough shell such that the geometric shape persist after removal of the encapsulated crystal-templates by aqueous dissolution. The presence of inorganic and/or organic matter in the wrapped crystals was evidenced by IR spectroscopy, while, the dissolution process as well as the morphology of the derived 3D-shaped shells was observed by optical microscopy.     

Investigation of Dissolution Enhancement of Nifedipine by Deposition on Superdisintegrants

In this study we aimed to investigate the dissolution enhancement of nifedipine by the solvent deposition technique using superdisintegrants including Ac-Di-Sol, Kollldon CL, and Explotab as excipients. The relative significance of action of solvent deposition (deposition of small drug particles on the excipient after solvent is evaporated) and action of superdislntegrant was investigated. The effect of solvent on dissolution of nifedipine in the solvent deposition system was also Investigated. Differential scanning calorlmetry (DSC) was used to study the interaction between nifedipine and superdisintegrants. Capsules and tablets of a physical mixture and a solvent deposition system of nifedipine were prepared. The dissolution rate of nifedipine of these capsules and tablets was studied. The results of this study show that solvent deposition system with lactose and super dlslntegrants in capsule and tablet dosage forms can significantly enhance dissolution rate of nifedipine. Both the action of superdislntegrant and solvent deposition contribute to the enhancement of the dissolution, but the solvent deposition is mainly responsible for this enhancement. The solvent and disintegrants used can influence the dissolution rate also. The solvent deposition system using both Kollldon CL as excipient and dichloromethane as solvent has the highest dissolution rate. DSC study indicated Kollldon CL has the strongest interaction with nifedipine also.     

Sustained Release Microspheres of Diclofenac Sodium Using PEGylated Rosin Derivatives

The PEGylated derivatives of rosin-PD-1 and PD-2 synthesized and characterized earlier () were investigated as potential materials for sustained release microsphere prepared by emulsion solvent evaporation method using diclofenac sodium (DCS) as model drug. All the microspheres exhibited smooth surfaces intercepted by pores; their sizes (d₉₀) ranged between 11–24 μm. The entrapment efficiency (< 80%) of the microspheres increased proportionally with derivative concentration. Presence of solvent like isopropyl alcohol or dichloromethane rendered the microspheres with large sizes but with reduced drug entrapment. Microspheres with small size were obtained at an optimum viscosity of liquid paraffin; any change lead to increase in the particle size. Magnesium stearate was found to be most suitable detackifier in the present system. The drug release was directly related to the particle size—small sized microspheres released drug at a faster rate. The dissolution data complied with Higuchi equation while the mechanism of drug release was Fickian diffusion (n ～ 0.5). Controlled inhibition of edema, as tested by hind paw edema method, was observed for 10 h when the microspheres were administered intraperitoneally. The present study found the derivatives as promising materials for preparing microspheres for sustained delivery of DCS.     

Effect of Formulation and Process Variables on the Dissolution Profile of Naproxen Sodium from Tablets

Abstract

Results of this investigation revealed some important formulation characteristics of naproxen sodium. Tablets made from the granules, prepared by wet granulation method using water, showed a significant decrease in solution as compared to those made by dry blending method. During wet granulation, heat was evolved due to the hydration of naproxen sodium resulting in the retardation of dissolution. The pseudo-polymorphism and hydration is being investigated by Bansal et. al. (1). In addition, when polyvinyl pyrolidone (PVP K-90) was used instead of PVP K-30, the dissolution was further retarted. Addition of cross carmellose sodium (Ac-Di-Sol) did not change the dissolution behavior of these tablets. When naproxen sodium was granulated with water, a decrease in dissolution rate was observed as mixing time was increased from 5 minutes to 15 minutes. The increase in hardness of the tablet from 10 Kp to 18Kp did not alter the dissolution profile of naproxen sodium. When granulation was prepared using a low shear mixer (Planetary mixer) versus a high shear mixer (T.K. Fielder), the resultant tablets exhibited similar dissolution and physical chemical properties.     

A Ternary Hybrid-Cation Room-Temperature Liquid Metal Battery and Interfacial Selection Mechanism Study

The dendrite-free sodium–potassium (Na–K) liquid alloy composed of two alkali metals is one of the ideal alternatives for Li metal as an anode material while maintaining large capacity, low potential, and high abundance. However, Na- or K-ion batteries have limited cathode materials that can deliver stably large capacity. Combining advantages of both, a hybrid-cation liquid metal battery is designed for a Li-ion-insertion-based cathode to deliver stable high capacity using a Na–K liquid anode to avoid dendrites. The mechanical property of the Na–K alloy is confirmed by simulation and experimental characterization, which leads to stable cycling performance. The charge carrier selection principle in this ternary hybrid-cation system is investigated, showing consistency with the proposed interfacial layer formation and ion distribution mechanism for the electrochemical process as well as the good stability. With Li ions contributing stable cycling as the cathode charge carrier, the K ion working as charge carrier on the anode, and Na as the medium to liquefy K metal, such a ternary hybrid battery system not only inherits the rich battery chemistry of Li-insertion cathodes but also broadens the understanding of alkali metal alloys and hybrid-ion battery chemistry.     

All-cellulose composites by partial dissolution in the ionic liquid 1-butyl-3-methylimidazolium chloride

Fully bio-based and biodegradable all-cellulose composites were prepared in the form of films by partial dissolution of two cellulose sources: a commercially available microfibrillated cellulose (MFC) and filter paper (FP). The solvent selected for this work was the ionic liquid 1-butyl-3-methylimidazolium chloride ([C₄mim]Cl). Both cellulose sources were partially dissolved at 80 °C and consolidated by partial dissolution, resulting in excellent mechanical properties. X-ray diffraction and electron microscopy demonstrated that partial dissolution was a viable path to transform FP into a continuous paracrystalline matrix reinforced with cellulose I crystallites. In contrast, partially dissolved MFC was not as thoroughly dissolved and large amounts of undissolved material were still visible along the centre line of the films after the longest dissolution times. Consequently, partially dissolved MFC retained its initially high crystallinity. The degree of polymerization of the materials after dissolution was significantly reduced.     

Fast release of liquid antisolvent precipitated fenofibrate at high drug loading from biocompatible thin films

Motivated by recent papers on nano and micro-particle slurry casting of poorly water-soluble drugs forming biocompatible films with enhanced properties, this work explores incorporation of liquid antisolvent (LAS) precipitated suspensions of fenofibrate, a model poorly soluble drug using both semi-synthetic (HPMC E15 LV) and natural (sodium alginate, SA) polymer as film formers. Centrifugation and subsequent resuspension were employed to minimize residual solvent and increase drug loading (～20%) in the LAS suspensions and in the film. Film’s critical quality attributes (CQAs), including drug distribution and uniformity, mechanical properties, and dissolution were assessed. Crystalline nature of FNB was largely preserved in the film without any polymorphic changes confirmed by XRD, DSC, and Raman. The NIR chemical imaging, corroborated by SEM imaging and drug content relative standard deviation (RSD) indicates that the drug is uniformly distributed without any observable large agglomerates. The films with SA showed lower mechanical strength as compared to HPMC due to SA’s low molecular weight. All films exhibited immediate drug release as has been the case using FNB nano particles in previous papers. Interestingly, although addition of plasticizer improved film dissolution, HPMC-based films had a faster dissolution compared to SA-based films in spite of higher mechanical strength of the former.     

Wettability of SiC and graphite by Co–Ta alloys: evaluation of the reactivity supported by thermodynamic calculations

Within the context of the design of high-temperature brazing process for C and SiC-based composites, a basic study is presented here about the wetting and interfacial reactivity of Co–Ta alloys in contact with graphite or SiC. Wetting results are presented for the first time showing that Co–Ta alloys wet C or SiC fairly or excellently depending on the relative amount of Ta. The final interfacial microchemistry and microstructures are the result of the interplay between the typical interfacial phenomena of the pure elements. Specifically, depending on the alloy composition, dissolution of the ceramic phase by Co or formation of a continuous interfacial layer of TaC that prevents dissolution prevails. The discussion about the interfacial reactivity between liquid Co–Ta alloys and graphite or SiC, as well as the interpretation of solidification phenomena and the formation of interfacial phases, is supported by making reference to new multi-component phase diagrams calculated by CALPHAD method.     

Processing of Nimesulide-PEG 400-PG-PVP Solid Dispersions: Preparation,Characterization, and In Vitro Dissolution

Abstract

The objective of this investigation was to study the influence of dissolution enhancers such as polyethylene glycol 400, propylene glycol, polyvinylpyrrolidone K30, sodium lauryl sulfate, and Tween 80 on in vitro dissolution of a model active pharmaceutical material—nimesulide. Preliminary studies were conducted using a physical blend of nimesulide, and the adjuvants and solid dispersions were prepared using solvent evaporation and cogrinding methods. Aqueous solution of adjuvants was first triturated with nimesulide, followed by mixing with lactose and microcrystalline cellulose, and finally water was evaporated under vacuum in a cogrinding method. A 3³ factorial design was adopted in a cogrinding method using the concentration of polyethylene glycol 400, propylene glycol, and polyvinylpyrrolidone K30 as independent variables. Tween 80 and sodium lauryl sulfate were added in all the batches. Full and reduced models were evolved for different dependent variables. The reduced models were validated using two checkpoints. Angle of repose <35°, percentage of drug released in 30 min (Q₃₀)>40%, 45 min (Q₄₅)>50%, and 120 min (Q₁₂₀)>60% were used as constraints for the selection of an optimized batch. Contour plots are presented for the selected dependent variables. Polyvinylpyrrolidone was found to be more effective in increasing the drug dissolution, compared with polyethylene glycol 400 and propylene glycol. The granule flow was adversely affected when high levels of liquid adjuvants were used in formulations. Wettability study was conducted to measure wetting time for pure drug and the optimized batch. Improved drug dissolution was attributed to improved wetting and the solubilizing effect of adjuvants from the pseudosolid dispersions of nimesulide. Significant improvement in drug dissolution was observed (Q₁₂₀ = 70%), compared with pure drug powder (Q₁₂₀ = 15%). In conclusion, dissolution of nimesulide can be modulated using an appropriate blend of pharmaceutical adjuvants.     

铝合金表面碱性化学抛光液组分的最佳浓度

铝合金碱性化学抛光效果较酸性抛光的差,为此,研究了低温下铝合金碱性化学抛光基础液及添加剂的最佳浓度。结果表明:以250g/L氢氧化钠、150g/L硝酸钠、15g/L硅酸钠、13g/L氟化钾为基础组分,分别加入30g/L硫脲、2g/L十二烷基硫酸钠、1.0g/L硫酸铜都可以使抛光效果得到提升,但加入30g/L硫脲效果更好,可以使铝合金抛光后的光泽度达到274 Gs,单位面积消耗量达0.01643kg/m~2。该工艺具有无污染、抛光光泽度高、操作简便等特点。     

A Systematic Approach to Design and Prepare Poly(meth)acrylate Based Solid Dispersions of Poorly Water-soluble Drug by Spray Drying

Objective of present study was to develop formulation which improves solubility of furosemide and stability of spray dried solid dispersion. Various processing parameters were optimized by applying DoE. In first step, screening of poly(meth)acrylates were carried out using solvent casting methods to select appropriate polymer. In second step, solid dispersion was prepared using optimized poly(meth)acrylate via spray drying process and trials were conducted as per DoE. Characterization of spray dried microparticles was carried out using SEM, DSC, XRD, in-vitro dissolution, and stability study. EUDRAGIT® E PO was screened as a suitable polymeric carrier in solvent casting method. In-vitro dissolution showed 100% releases within 20 min for spray dried powder as compared to 9% release for pure drug after 60 min in 0.1 N HCl. SEM analysis revealed conversion of crystalline shape to spherical shape. DSC and XRD confirmed that crystalline form was converted into amorphous form which was stable even after 3 months of storage. Outcome of DoE revealed that, feed rate has significant effect on %LOD while solid content has major effect on the process yield. So, present work indicates that EUDRAGIT® E PO formed a stable spray dried solid dispersion and it has ability to enhance dissolution of furosemide.     

Two step coating of a hypereutectic PM Al-Si alloy

The aim of the present work was to combine the high strength of Al-Si alloys produced via Rapid Solidification (RS) and Spray Forming (SF) with a wear resistant surface coating, designed for high temperature use. The surface coating, composed mainly of nickel and chromium, was applied in a two step process: plasma spray followed by laser surface alloying using a diode laser. The microstructure and hardness of the surface coating were analysed. In the Al-Si alloys produced via Rapid Solidification, gas bubble formation was observed during the laser alloying process. In the Spray Formed alloys, globules of the coating material and a needle-like microstructure formed, in detriment to the mechanical properties of the alloyed layer.