The Influence of Processing Parameters on Characteristics of an Aluminum Alloy Spray Deposition

In the present investigation, two nozzle configurations are used for spray deposition, convergent nozzle (nozzle-A), and convergent nozzle with 2 mm parallel portion attached at its end (nozzle-C) without changing the exit area. First, the conditions for subambient aspiration pressure, i.e., pressure at the tip of the melt delivery tube, are established by varying the protrusion length of the melt delivery tube at different applied gas pressures for both of the nozzles. Using these conditions, spray deposits in a reproducible manner are successfully obtained for 7075 Al alloy. The effect of applied gas pressure, flight distance, and nozzle configuration on various characteristics of spray deposition, viz., yield, melt flow rate, and gas-to-metal ratio, is examined. The over-spray powder is also characterized with respect to powder size distribution, shape, and microstructure. Some of the results are explained with the help of numerical analysis presented in an earlier article.

Stability of pargasite during ultrahigh-temperature metamorphism:A consequence of titanium and REE partitioning

Orthopyroxene-clinopyroxene-plagioclase needles and symplectite along the cleavage planes and grain boundaries of fluorine-bearing titanian-ferroan pargasite from the Highland Complex, Sri Lanka, are interpreted as evidence for dehydration melting at ultrahigh-temperature conditions. High Ti (up to 0.4 pfu) and F (XF up to 0.56) content in pargasite extends its stability to higher temperatures, and the composition indicates the dehydration melting reaction may take place at ultrahigh-temperatures (~950 °C) at a pressure around 10 kbar, close to peak metamorphic conditions. The increase of Ti content close to the grain boundaries and cleavage planes in pargasite indicates titanium partitioning from the melt during dehydration melting enhanced the stability of the mineral toward ultrahigh-temperature conditions. The REE content in the pargasite shows a similar behavior to that of titanium. The cores with no breakdown assemblage consist of low and flat REE concentrations with respect to the high and Eu-depleted rim. Clinopyroxene in symplectite and needle-shaped lamellae within the pargasite porphyroblasts have similar REE patterns with slightly low-concentrations relative to that of pargasite. In the breakdown assemblage, LREEs are partitioned mainly into plagioclase while the HREEs are partitioned into orthopyroxene. The REE enrichment in the pargasite rims signals their relative partitioning between pargasite rims and melt. Modeling of the partitioning of Ti and REEs associated with pargasite breakdown demonstrates that its stability is greatly enhanced at UHT conditions. This investigation implies that the stability of hydrous minerals such as amphibole can be extended to UHT conditions, and expands our knowledge of metamorphism in the lower crust.

Determination of the enthalpies of sublimation and evaporation from thermogravimetric data: Application to metalorganic complexes of Al and Cr

A series of bimetallic acetylacetonate (acac) complexes, AlxCr1-x(acac)(3), 0 <= x <= 1, have been synthesized for application as precursors for the CVD Of Substituted oxides, such as (AlxCr1-x)(2)O-3. Detailed thermal analysis has been carried out on these complexes, which are solids that begin subliming at low temperatures, followed by melting, and evaporation from the melt. By applying the Langmuir equation to differential thermogravimetry data, the vapour pressure of these complexes is estimated. From these vapour pressure data, the distinctly different enthalpies of sublimation and evaporation are calculated, using the Clausius-Clapeyron equation. Such a determination of both the enthalpies of sublimation and evaporation of complexes, which sublime and melt congruently, does not appear to have been reported in the literature to date.

Fluidity of mica particle dispersed aluminium alloy

Cast aluminium alloy-mica particle composites were made by dispersing mica particles in a vortex produced by stirring the liquid Al-4 wt% Cu-1.5 wt% Mg alloy and then casting the melt containing the suspended particles into permanent moulds. Spiral fluidity and casting fluidity of the alloy containing mica particles in suspension were determined. Both the spiral fluidity and the casting fluidity of the base alloy were found to decrease with an increase in volume or weight percent of mica particles (of a given size), and with a decrease in particle size (for a given amount of particles). The fluidities of Al-4 wt% Cu-1.5 wt% Mg alloys containing suspended mica particles were found to correlate very well with the surface area of suspended mica particles. The regression equation for spiral fluidity Y (cm) as a function of surface area of mica particles per gram of spiral X (cm2 g–1) at 700° C was found to be Y=42.62–0.42X with a correlation coefficient of 0.9634. The regression equations for casting fluidity Yprime (cm) as a functiono of surface area of mica particles per gram of fluidity test piece Xprime (cm2 g–1) at 710 and 670° C were found to be Yprime=19.71–0.17Xprime and Yprime=13.52–0.105Xprime with correlation coefficients of 0.9194 and 0.9612 respectively. The percentage decrease in casting fluidity of composite melts containing up to 2.5 wt% mica with a drop in temperature is quite similar to the corresponding decrease in the casting fluidity of base alloy melts (without mica). The change in fluidity due to mica dispersions has been discussed in terms of changes in viscosity of the composite melts. However, the fluidities of these composite alloys containing up to 2.5 wt% mica are adequate for making a variety of simple castings including bearings for which these alloys have been developed.

X-ray Topographic Assessment of Dislocations in Crystals Grown from Solution

Crystals growing from solution, the vapour phase and from supercooled melt exhibit, as a rule, planar faces. The geometry and distribution of dislocations present within the crystals thus grown are strongly related to the growth on planar faces and to the different growth sectors rather than the physical properties of the crystals and the growth methods employed. As a result, many features of generation and geometrical arrangement of defects are common to extremely different crystal species. In this paper these commoner aspects of dislocation generation and configuration which permits one to predict their nature and distribution are discussed. For the purpose of imaging the defects a very versatile and widely applicable technique viz. x-ray diffraction topography is used. Growth dislocations in solution grown crystals follow straight path with strongly defined directions. These preferred directions which in most cases lie within an angle of ±15° to the growth normal depend on the growth direction and on the Burger's vector involved. The potential configuration of dislocations in the growing crystals can be evaluated using the theory developed by Klapper which is based on linear anisotropic elastic theory. The preferred line direction of a particular dislocation corresponds to that in which the dislocation energy per unit growth length is a minimum. The line direction analysis based on this theory enables one to characterise dislocations propagating in a growing crystal. A combined theoretical analysis and experimental investigation based on the above theory is presented.

Heat-Transfer During Polymer Combustion

The nature of surface and subsurface reactions in polymer combustion is poorly underst0od.l During the burning of thermoplastic polymers a melt layer is observed on the surface, and below the melt layer there is thermal wave penetration. But the exact thickness of the melt layer and the thickness of the thermal wave penetration have not been precisely measured, although a qualitative idea has been given.

Crystallization as a Tool for Controlling and Designing Properties of Pharmaceutical Solids

The ability to deliver the drug to the patient in a safe, efficacious and cost-effective manner depends largely on the physicochemical properties of the active pharmaceutical ingredient (API) in the solid state. In this context, crystallization is of critical importance in pharmaceutical industry, as it defines physical and powder properties of crystalline APIs. An improved knowledge of the various aspects of crystallization process is therefore needed. The overall goal of this thesis was to gain better understanding of the relationships between crystallization, solid-state form and properties of pharmaceutical solids with a focus on a crystal engineering approach to design technological properties of APIs. Specifically, solid-state properties of the crystalline forms of the model APIs, erythromycin A and baclofen, and the influence of solvent on their crystallization behavior were investigated. In addition, the physical phenomena associated with wet granulation and hot-melting processing of the model APIs were examined at the molecular level. Finally, the effect of crystal habit modification of a model API on its tabletting properties was evaluated. The thesis enabled the understanding of the relationship between the crystalline forms of the model APIs, which is of practical importance for solid-state control during processing and storage. Moreover, a new crystalline form, baclofen monohydrate, was discovered and characterized. Upon polymorph screening, erythromycin A demonstrated high solvate-forming propensity thus emphasizing the need for careful control of the solvent effects during formulation. The solvent compositions that yield the desirable crystalline form of erythromycin A were defined. Furthermore, new examples on solvent-mediated phase transformations taking place during wet granulation of baclofen and hot-melt processing of erythromycin A dihydrate with PEG 6000 are reported. Since solvent-mediated phase transformations involve the crystallization of a stable phase and hence affect the dissolution kinetics and possibly absorption of the API these transformations must be well documented. Finally, a controlled-crystallization method utilizing HPMC as a crystal habit modifier was developed for erythromycin A dihydrate. The crystals with modified habit were shown to posses improved compaction properties as compared with those of unmodified crystals. This result supports the idea of morphological crystal engineering as a tool for designing technological properties of APIs and is of utmost practical interest.

Characterisation and processing of amorphous binary mixtures with low glass transition temperature

The number of drug substances in formulation development in the pharmaceutical industry is increasing. Some of these are amorphous drugs and have glass transition below ambient temperature, and thus they are usually difficult to formulate and handle. One reason for this is the reduced viscosity, related to the stickiness of the drug, that makes them complicated to handle in unit operations. Thus, the aim in this thesis was to develop a new processing method for a sticky amorphous model material. Furthermore, model materials were characterised before and after formulation, using several characterisation methods, to understand more precisely the prerequisites for physical stability of amorphous state against crystallisation. The model materials used were monoclinic paracetamol and citric acid anhydrate. Amorphous materials were prepared by melt quenching or by ethanol evaporation methods. The melt blends were found to have slightly higher viscosity than the ethanol evaporated materials. However, melt produced materials crystallised more easily upon consecutive shearing than ethanol evaporated materials. The only material that did not crystallise during shearing was a 50/50 (w/w, %) blend regardless of the preparation method and it was physically stable at least two years in dry conditions. Shearing at varying temperatures was established to measure the physical stability of amorphous materials in processing and storage conditions. The actual physical stability of the blends was better than the pure amorphous materials at ambient temperature. Molecular mobility was not related to the physical stability of the amorphous blends, observed as crystallisation. Molecular mobility of the 50/50 blend derived from a spectral linewidth as a function of temperature using solid state NMR correlated better with the molecular mobility derived from a rheometer than that of differential scanning calorimetry data. Based on the results obtained, the effect of molecular interactions, thermodynamic driving force and miscibility of the blends are discussed as the key factors to stabilise the blends. The stickiness was found to be affected glass transition and viscosity. Ultrasound extrusion and cutting were successfully tested to increase the processability of sticky material. Furthermore, it was found to be possible to process the physically stable 50/50 blend in a supercooled liquid state instead of a glassy state. The method was not found to accelerate the crystallisation. This may open up new possibilities to process amorphous materials that are otherwise impossible to manufacture into solid dosage forms.

Phase relations and dielectric properties of BaTi03 ceramics heavily substituted with neodymium

Investigations on the phase relations and dielectric properties of (1 -x)BaTiO3 + xNd2/3TiO 3 (BNT) ceramics sintered in air below 1650 K have been carried out. X-ray powder diffraction studies indicate apparent phase singularity for compositions with x < 0.3. Nd2Ti207 is detected at higher neodymium concentrations. The unit cell parameter changes continuously with neodymium content, and BaTiO3 is completely cubic at room temperature with x -- 0.0525, whereas electron diffraction studies indicate that the air-sintered BNT ceramics with x > 0.08 contain additional phases that are partly amorphous even to an electron beam. SEM observations reveal that BaTiO3 grains are mostly covered by a molten intergranular phase, and show the presence of randomly distributed Nd2Ti207 grains. Energy dispersive X-ray analysis shows the Ba-Nd-Ti ternary composition of the intergranular phase. Differential thermal analysis studies support the formation of a partial melt involving dissolution-precipitation of boundary layers of BaTiO3 grains. These complex phase relations are accounted for in terms of the phase instability of BaTiO3 with large cation-vacancy concentration as a result of heavy Nd 3+ substitution. The absence of structural intergrowth in (1 - x)BaTiO3 + xNd2/3TiO3 under oxidative conditions leads to a separation of phases wherein the new phases undergo melting and remain X-ray amorphous. BNT ceramics with 0.1 < x < 0.3 have ~eff >~ 104 with tan 6 < 0.1 and nearly flat temperature capacitance characteristics. The grain-size dependence of ee,, variations of ~eff and tan 6 with the measuring frequency, the non-ohmic resistivities, and the non-linear leakage currents at higher field-strengths which are accompanied by the decrease in eeff and rise in tan 3, are explained on the basis of an intergranular (internal boundary layer) dielectric characteristic of these ceramics.

Two-dimensional solidification in a cylindrical mold with imperfect mold contact

A two-dimensional axisymmetric problem of solidification of a superheated liquid in a long cylindrical mold has been studied in this paper by employing a new embedding technique. The mold and the melt has an imperfect contact and the heat transfer coefficient has been taken as a function of space and time. Short-time exact analytical solutions for the moving boundary and temperature distributions in the liquid, solid and mold have been obtained. The numerical results indicate that with the present solution, for some parameter values, substantial solidified thickness can be obtained. The method of solution is simple and straightforward, and consists of assuming fictitious initial temperatures for some suitable fictitious extensions of the actual regions. Sufficient conditions for the commencement of the solidification have been discussed.

Dielectric Relaxation in SrLiB9O15 Glasses

Transparent SrLiB9O15 (SLBO) glasses were fabricated via the conventional melt-quenching technique. X-ray powder diffraction and differential thermal analysis carried out on the as-quenched samples confirmed their amorphous and glassy nature, respectively. The dielectric constants in the 100 Hz to 10 MHz frequency range for SLBO glasses were measured as a function of temperature (300–1023 K). The dielectric relaxation characteristics were rationalized using the electric modulus formalism. The electrode polarization effect was subtracted from the low-frequency dielectric constant to have an insight into the intrinsic dielectric behavior of SLBO glasses. The imaginary part of electric modulus spectra was modeled using an approximate solution of Kohlrausch–Williams–Watts relation. The dielectric constant for the as-quenched glass increased with increasing temperature and exhibited anomalies in the vicinity of the glass transition and crystallization temperatures.

Influence of seeding on crystallization behaviour of BaNaB9O15 glasses

Transparent BaNaB9O15 (BNBO) glasses were fabricated via the conventional melt-quenching technique. X-ray powder diffraction (XRD) followed by differential scanning calorimetric (DSC) studies confirmed the amorphous and glassy nature of the as-quenched samples, respectively. The effect of seeding on the crystallization of BNBO glasses was studied by non-isothermal DSC method and was modeled using the Johnson-Mehl-Avrami and Ozawa equations. The activation energy for seeded glasses decreased with the increase in fraction of crystallization. The values for the onset of crystallization and Avrami exponent were found to be lower for seeded samples which were associated with the heterogeneous nucleation and epitaxial processes.

Electron and x-ray diffraction studies on Al86Fe14, Al82Fe18 and Al75Fe25 quasicrystals

Electron and x-ray diffraction experiments on the metlt-spun Al100−x Fe x (x=14, 18, 25) alloys are carried out. It is observed that all the melt-spun alloys possessing the quasi-crystalline phases have icosahedral point-group symmetry.

Crystallization studies on bulk SixTe100-x glasses

Bulk SixTe100-x (10 less-than-or-equals, slant x less-than-or-equals, slant 28) glasses have been prepared by the melt quenching technique. The crystallization of these glasses has been studied by using differential scanning calorimetry. The composition dependence of the glass transition temperature Tg, the recrystallization temperature Tcr and the melting temperature Tm show an unusual behaviour at the composition x congruent with 20. The glasses with 10 less-than-or-equals, slant x less-than-or-equals, slant 20 undergo double glass transition and double stage crystallization phenomena. On the other hand, glasses with 22 less-than-or-equals, slant x less-than-or-equals, slant 28 exhibit eutectic crystallization. The phases at different stages of crystallization have been identified by using X-ray diffraction techniques. The unusual behaviour at x congruent with 20 can be explained on the basis of the changes in the network topologies of IV-VI chalcogenide glasses.

Crystallization kinetics of poly(l-lactic acid)

The morphology and crystal growth of poly(l-lactic acid), PLLA have been studied from the melt as a function of undercooling and molecular weight using hot stage microscopy. Attention has been given to the application of growth rate equation on the growth rate data of PLLA and thus various nucleation parameters have been calculated. The criteria of Regime I and Regime II types of crystallization has been applied for the evaluation of substrate lengths.