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At least 19 records

Determination of the succinonitrile-benzene and succinonitrile-cyclohexanol phase diagrams by thermal and UV spectroscopic analysis

Equilibrium temperature-composition diagrams were determined for the two organic systems, succinonitrile-benzene and succinonitrile-cyclohexanol. Measurements were made using the common thermal analysis methods and UV spectrophotometry. Succinonitrile-benzene monotectic was chosen for its low affinity for water and because UV analysis would be simplified. Succinonitrile-cyclohexanol was chosen because both components are transparent models for metallic solidification, as opposed to the other known succinonitrile-based monotectics.

Kaukler, W. F.↗

Interfacial Surgery Determination of Succinonitrile and Succinonitrile-Acetone Alloy Using Surface Light Scattering Spectrometer

The objectives of this ground based research is to measure the liquid/vapor interfacial surface energies of succinonitrile (SCN) and alloys of succinonitrile and acetone using Surface Light Scattering Spectrometer. Liquid/vapor interfacial energy measurements will be made near and above the melting point and are the primary goal of this proposal. A measurement of viscosity also results from the Surface Light Scattering technique employed. Interfacial free energies between the phases enters into many analysis of phase transformation and flow, including nucleation, dendritic growth, interface stability, Ostwald ripening, and Marangoni flow. Succirionitrile (SCN) is useful as a model for the study of metal solidification, although it is an organic material, it has a BCC crystal structure and solidifies dendriticly like a metal. It is also transparent and has a low melting point (58.08 C). Succinonitrile has been and is being used extensively in NASAs Microgravity Materials Science and Fluid Physics programs and as well as in several ground-based and microgravity studies including the Isothermal Dendritic Growth Experiment (IDGE) due to Glicksman and coworkers and subsequently in several theoretical and numerical studies of dendritic growth. Previous measurements of succinonitrile (SCN) and alloys of succinonitrile and acetone surface tensions are extremely limited. We believe the data sought through this proposal have significant basic physical property data value and thus the work proposed will provide needed data in support of NASAs Microgravity program research.

Tin, Padetha↗

Directional Solidification of Pure Succinonitrile and a Succinonitrile-Acetone Alloy

An experimental study of the horizontal Bridgman growth of pure succinonitrile (SCN) and of a succinonitrile-1.0 mol.% acetone alloy (SCN-1.0 mol.% ACE) has been performed. Experiments involving both a stationary thermal field (no-growth case) and a translating thermal field (growth case) were conducted. Growth rates of 2 and 40 micrometers/s were investigated. For the pure SCN experiments, the velocity field in the melt was estimated using video images of seed particles in the melt. Observations of the seed particles indicate that a primary longitudinal convective cell is formed. The maximum velocity of two different particles which traveled along similar paths was the same and equal to 1.49 +/- 0.01 mm/s. The general accuracy of velocity measurements is estimated to be +/- 0.08 mm/s, though the data shows consistency to within +/- 0.02 mm/s. The shape of the solid/liquid interface was also quantitatively determined. The solid/liquid interface was stable (non-dendritic and non-cellular) but not flat; rather it was significantly distorted by the influence of convection in (he melt and, for the growth case, by the moving temperature boundary conditions along the ampoule. It was found that the interface shape and position were highly dependent on the alignment of the ampoule in the apparatus. Consequently, the ampoule was carefully aligned for all experiments. The values for front location agree with those determined in previous experiments. For the alloy experiments, the solid/liquid interface was determined to be unstable at growth rates greater than 2.8 micrometers/s, but stable for the cases of no-growth and growth at 2 micrometers/s. When compared to the shape of the pure SCN interface, the alloy interface forms closer to the cold zone, indicating that the melting temperature decreased due to the alloying element. Extensive temperature measurements were performed on the outside of the ampoule containing pure SCN. The resulting thermal profiles are presented in detail in the results section. It is intended that the interface shape, thermal boundary condition and velocity data presented in this paper be used to test numerical simulations.

Simpson, James E.↗

Directional Solidification of Pure Succinonitrile and a Succinonitrile-Acetone Alloy

An experimental study of the horizontal Bridgman growth of pure succinonitrile (SCN) and of a succinonitrile-1.0 mol% acetone alloy (SCN-1.0 mol.% ACE) has been performed. Experiments involving both a stationary thermal field (no-growth case) and a translating thermal field (growth case) were conducted. Growth rates of 2 and 40 micrometers/sec were investigated. For the pure SCN experiments, the velocity field in the melt was estimated using video images of seed particles in the melt. Observations of the seed particles indicate that a primary longitudinal convective cell is formed. The maximum velocity of two different particles which traveled along similar paths was the same and equal to 1.49 +/- 0.01 mm/s. The general accuracy of velocity measurements is estimated to be +/-0.08 mm/s, though the data shows consistency to within +/- 0.02 mm/s. The shape of the solid/liquid interface was also quantitatively determined. The solid/liquid interface was stable (non-dendritic and non-cellular) but not flat: rather it was significantly distorted by the influence of connection in the melt and, for the growth case, by the moving temperature boundary conditions along the ampoule. It was found that the interface shape and position were highly dependent on the alignment of the ampoule in the apparatus. Consequently, the ampoule was carefully aligned for all experiments. The values for front location agree with those determined in previous experiments. For the alloy experiments, the solid/liquid interface was determined to be unstable at growth rates greater than 2.8 micrometers/sec, but stable for the cases of no-growth and growth at 2 micrometers/sec. When compared to the shape of the pure SCN interface, the alloy interface forms closer to the cold zone, indicating that the melting temperature decreased due to the alloying element. Extensive temperature measurements were performed on the outside of the ampoule containing pure SCN. The resulting thermal profiles are presented in detail in the results section. It is intended that the interface shape, thermal boundary condition, and velocity data presented in this paper be used to test numerical simulations.

Simpson, James E.↗

Convective and interfacial instabilities during solidification of succinonitrile containing ethanol

Even though slow convective flow is difficult to detect in solidifying metals, it can readily be observed in transparent materials by observing the motion of small neutrally buoyant particles. Succinonitrile, which solidifies with an unfaceted solid/liquid interface and has well characterized physical properties, is considered an excellent material for such studies. For studies of solute-induced convection, ethanol is a useful addition to succinonitrile since it has a lower density and a somewhat similar molecular structure. Samples of high purity and ethanol-doped succinonitrile are unidirectionally solidified in a vertical temperature gradient. Latex mimcrospheres 2 microns in diameter are suspended in the liquid to reveal the convective flow. Convective and morphological stability is observed as a function of solute concentration and growth velocity. These measurements are compared with theoretical calculations that predict the transition from stability to instability as a function of solidification conditions. The predicted transitions occur at low concentrations and solidification velocities; for this reason, extreme care must be taken in order to eliminate the effects of impurities or thermally induced convection.

Schaefer, R. J.↗

Succinonitrile Purification Facility

The Succinonitrile (SCN) Purification Facility provides succinonitrile and succinonitrile alloys to several NRA selected investigations for flight and ground research at various levels of purity. The purification process employed includes both distillation and zone refining. Once the appropriate purification process is completed, samples are characterized to determine the liquidus and/or solidus temperature, which is then related to sample purity. The lab has various methods for measuring these temperatures with accuracies in the milliKelvin to tenths of milliKelvin range. The ultra-pure SCN produced in our facility is indistinguishable from the standard material provided by NIST to well within the stated +/- 1.5mK of the NIST triple point cells. In addition to delivering material to various investigations, our current activities include process improvement, characterization of impurities and triple point cell design and development. The purification process is being evaluated for each of the four vendors to determine the efficacy of each purification step. We are also collecting samples of the remainder from distillation and zone refining for analysis of the constituent impurities. The large triple point cells developed will contain SCN with a melting point of 58.0642 C +/- 1.5mK for use as a calibration standard for Standard Platinum Resistance Thermometers (SPRTs).

Source record↗

A redetermination of the succinonitrile-water phase diagram

The phase diagram of the water/succinonitrile system often used in modeling binary metallic alloys is determined experimentally using a laser scattering method. Triply distilled and zone-refined succinonitrile is placed in a jacketed water-cooled vessel with a magnetic mixer and a copper-constantan thermocouple, and the melting point is determined under vacuum and under Ar by observing the response of a photodiode placed opposite a laser source as the chamber is cooled and reheated. Then water is added, and the eutectic and monotectic temperatures and the entire phase diagram are determined under Ar. The results are presented in a table and graph and compared to those of Schreinemakers (1897): significant discrepancies are noted and attributed to impurities in the succinonitrile used by Schreinemakers. The importance of accurate phase diagrams for modeling binary alloys is stressed.

Smith, J. E., Jr.↗

Direct Observation of Controlled Melting and Resolidification of Succinonitrile Mixtures in a Microgravity Environment

In support of the Pore Formation and Mobility Investigation (PFMI) direct observation of experiments on the controlled melting and subsequent resolidification of succinonitrile were conducted in the glovebox facility (GBX) of the International Space Station (ISS). Samples were prepared on ground by filling glass tubes, 1 cm ID and approximately 30 cm in length, with pure succinonitrile (SCN) and SCN-Water mixtures under 450 millibar of nitrogen. Experimental processing parameters of temperature gradient and translation speed, as well as camera settings, were remotely monitored and manipulated from the ground Telescience Center (TSC) at the Marshall Space Flight Center. Sample temperatures are monitored by six in situ thermocouples. Real time visualization during melt back revealed bubbles of different sizes initiating at the solid/liquid interface, their release, interactions, and movement into the temperature field ahead of them. Subsequent re-solidification examined planar interface breakdown and the transition to steady-state dendritic growth. A preliminary analysis of the observed phenomena and its implication to future microgravity experiments is presented and discussed.

Grugel, R. N.↗

Measurement of the diffusion coefficient of acetone in succinonitrile at its melting point

The diffusion coefficient of acetone in liquid succinonitrile at 331.1 K was determined using the method of McBain and Dawson (1935). Only dilute mixtures of SCN-acetone were studied. The interdiffusion constant was determined to be 0.0000127 sq cm/s and was essentially independent of the acetone concentration over the range investigated (0.5 to 18 mol pct acetone).

Chopra, M. A.↗

Non-ideality near the monotectic composition of a miscibility-gap type system - Succinonitrile-water

Differential scanning calorimetry (DSC) of near monotectic succinonitrile-water solutions, fast-quenched in hydrophilic and hydrophobic DSC pans, indicate, by degree of undercooling, thst there may be significant dependence of final ingot microstructure on the pre-quench equilibration temperature. Partial molal-volume determinations from density data, along with DSC data, suggest the nature of temperature dependent component associations from 20 to 55 C in homogeneous solutions. The undercooling profile in a hydrophilic container is explained in terms of solution-composition shifts arising from the Gibbs surface excess. The evidence shows that temperature-dependent preferred component aggregates may modulate surface-composition gradients. Similar effects may be present through intermetallic compound formation in metallic monotectic alloys.

Frazier, D. O.↗

Interface Shape and Convection During Solidification and Melting of Succinonitrile

An experimental study was conducted of the crystal growth of succinonitrile during solidification, melting, and no-growth conditions using a horizontal Bridgman furnace and square glass ampoule. For use as input boundary conditions to numerical codes, thermal profiles on the outside of the ampoule at five locations around its periphery were measured along the ampoule's length. Temperatures inside the ampoule were also measured. The shapes of the s/l interface in various two dimensional planes were quantitatively determined. Though interfaces were nondendritic and noncellular, they were not flat, but were highly curved and symmetric in only one unique longitudinal y-z plane (at x=O). The shapes of the interface were dominated by the primary longitudinal flow cell characteristic of shallow cavity flow in horizontal Bridgman; this flow cell was driven by the imposed furnace temperature gradient and caused a 'radical' thermal gradient such that the upper half of the ampoule was hotter than the bottom half. We believe that due to the strong convection, the release of latent heat does not significantly influence the thermal conditions near the interface. We hope that the interface shape and thermal data presented in this paper can be used to optimize crystal growth processes and validate numerical models.

Degroh, Henry C., III↗

Computer Simulation of the Forces Acting on a Submerged Polystyrene Probe as it Approaches the Succinonitrile Melt-Solid Interface

A Modeling approach to simulate both mesoscale and microscopic forces acting in a typical AFM experiment is presented. A mesoscale level interaction between the cantilever tip and the sample surface is primarily described by the balance of attractive Van der Waals and repulsive forces. Ultimately, the goal is to measure the forces between a particle and the crystal-melt interface. Two modes of AFM operation are considered in this paper - a stationary and a "tapping" one. The continuous mechanics approach to model tip-surface interaction is presented. At microscopic levels, tip contamination and details of tip-surface interaction are modeled using a molecular dynamics approach for the case of polystyrene - succinonitrile contact. Integration of the mesoscale model with a molecular dynamic model is discussed.

Bune, Andris V.↗

Numerical and Experimental Study of Transport Phenomena in Directional Solidification of Succinonitrile

A numerical and experimental study of the growth of succinonitrile (SCN) using a horizontal Bridginan furnace and transparent glass ampoule was conducted. Two experiments were considered: one in which the temperature profile was fixed relative to the ampoule (no-growth case); and a second in which the thermal profile was translated at a constant rate (steady growth case). Measured temperature profiles on the outer surface of the ampoule were used as thermal boundary conditions for the modelling. The apparent heat capacity formulation combined with the variable viscositymeth~ was used to model the phase change in SeN. Both 2-D and 3-D models were studied and numerical solutions obtained using the commercial finite element code, FIDAP1. Comparison of the numerical results to experimental data showed excellent agreement. The complex 3-D shallow-cavity flow in the melt, differences between 2-D and 3-D models, effects of natural convection on the thermal gradient and shape of the solid/liquid interface, and the sensitivity of simulations to specific assumptions, are also discussed.

de Groh, Henry C., III↗

Surface effects on phase distributions of a fast-quenched miscibility gap type system - Succinonitrile-water

If a binary homogeneous melt is cooled into an immiscible region, the newly formed second phase will generally have a density different from the parent phase, and will separate readily by sedimentation. Observation of solidification processes in microgravity indicates that outside of sedimentation, at least two other important effets can separate the phases: (1) preferential wetting, and (2) thermal migration of second-phase droplets due to interfacial tension gradients. The latter effect would drive the minority phase along the thermal gradient toward the hottest part (assuming the interfacial tension decreases with increasing temperature), which is usually away from the crucible wall. On the other hand, if the minority phase preferentially wets the crucible, a minority phase layer which thickens as initial solution compositions approach critical, will form adjacent to the solid surface and remain in the coldest region of the ingot. This study presents compelling preliminary evidence that these two effects do exist and that they compete with one another. However, the temperature dependence of preferential wetting below T(c) for the current system of study is, as yet, undetermined. These effects are sensitive to the initial concentration of a hypermonotectic solution cooling through a miscibility gap.

Frazier, D. O.↗

Study of natural convection and interface shape in directional solidification of succinonitrile

Flow visualization experiments in a Bridgman furnace at zero growth velocity have been performed. The experiments were intended to investigate if the photochromic dye activation method could be used in a crystal growth study. The results from this work have confirmed that with a carefully designed experimental setup, the photochromic-dye method permits qualitative and quantitative evaluation of the flow field near the interface in crystal growth experiments. For the horizontal orientation of a 6 mm x 6 mm ampoule and an axial temperature gradient of 26.5 C/cm, velocity profiles have been obtained accurately at various positions near the interface. The maximum velocity of 1.29 mm/sec was measured in the central vertical plane and the flow was symmetrical about that plane. A flow inversion point was also noted, above which the flow was towards the interface and below it, away from the interface. The results obtained are useful for validating 3-dimensional numerical models and establishing a link between the macroscopic processing conditions and the formation of crystalline defects.

Kawaji, M.↗

Computer Simulation of the Forces Acting on the Polystyrene Probe Submerged into the Succinonitrile Near Phase Transition

Modeling approach to simulate both mesoscale and microscopic forces acting in a typical AFM experiment is presented. At mesoscale level interaction between the cantilever tip and the sample surface is primarily described by the balance of attractive Van der Waals and repulsive forces. The model of cantilever oscillations is applicable to both non-contact and "tapping" AFM. This model can be farther enhanced to describe nanoparticle manipulation by cantilever. At microscopic level tip contamination and details of tip-surface interaction can be simulated using molecular dynamics approach. Integration of mesoscale model with molecular dynamic model is discussed.

Bune, Andris V.↗