Engineering topics
Publications and source records attributed to Moacanin, J..
The mechanism of deactivation of energy of excitation in a resin system was investigated on optical excitation as well as excitation by high energy electrons. This mechanism involves formation of excited state complexes, known as exciplexes which have a considerable charge transfer character. This mechanism will be used to develop a degradation model for epoxy matrix materials deployed in a space environment.
Transient emission studies following pulse radiolysis of solid poly(1-vinyl naphthalene) show existence of excited monomers and two excimers. Quenching experiments indicate that excimers are not formed directly by recombination of ions but probably by trapping of migrating monomeric excitation in preformed traps whose density is approximately one in 1000.
Models of primary processes leading to deactivation of energy deposited by a pulse of high energy electrons were derived for epoxy matrix materials and polyl-vinyl naphthalene. The basic conclusion is that recombination of initially formed charged states is complete within 1 nanosecond, and subsequent degradation chemistry is controlled by the reactivity of these excited states. Excited states in both systems form complexes with ground state molecules. These excimers or exciplexes have their characteristics emissive and absorptive properties and may decay to form separated pairs of ground state molecules, cross over to the triplet manifold or emit fluorescence. ESR studies and chemical analyses subsequent to pulse radiolysis were performed in order to estimate bond cleavage probabilities and net reaction rates. The energy deactivation models which were proposed to interpret these data have led to the development of radiation stabilization criteria for these systems.
A study was made on the stress relaxation behavior at 25 C of poly(methyl methacrylate) in uniaxial tension as a function of physical aging at both room temperature and 60 C. Test specimens were compression molded at 165 C, then quenched to room temperature and allowed to age for up to 30 days prior to testing. Stress relaxation curves measured after different aging times could be superposed to a single master curve for each aging temperature. Superposition was achieved by applying vertical and horizontal shifts. Hence, the shape of the response curves was not changed by aging. This is in accordance with observations made by Struik for tensile creep curves. Volume changes as a function of physical aging were also determined. Simple exponential relationships were observed between volume and both horizontal and vertical shifts. The horizontal shift implies a shift in the effective time scale caused by a change in free volume. The vertical shifts could be correlated with changes in Young's modulus caused by a change in density. For the range of aging studied, the response time scale varied over nearly two decades of log-time. For the same conditions modulus varied by 30 percent.
A theoretical analysis of the tensile stress-strain relation of elastomers at constant strain rate is presented which shows that the time and the stress effect are separable if the experimental time scale coincides with a segment of the relaxation modulus that can be described by a single power law. It is also shown that time-strain separability is valid if the strain function is linearly proportional to the Cauchy strain, and that when time-strain separability holds, two strain-dependent quantities can be obtained experimentally. In the case where time and strain effect are not separable, superposition can be achieved only by using temperature and strain-dependent shift factors.
A method and apparatus for detecting optical radiation by optically monitoring temperature changes in a microvolume caused by absorption of the optical radiation to be detected is described. More specifically, a thermal lens forming material is provided which has first and second opposite, substantially parallel surfaces. A reflective coating is formed on the first surface, and a radiation absorbing coating is formed on the reflective coating. Chopped, incoming optical radiation to be detected is directed to irradiate a small portion of the radiation absorbing coating. Heat generated in this small area is conducted to the lens forming material through the reflective coating, thereby raising the temperature of a small portion of the lens forming material and causing a thermal lens to be formed therein.
Broadband IR detector integrated into compact package for pollution monitoring and weather prediction is small, highly responsive, and immune to high noise. Sensing material is transparent sheet metalized with reflecting coating and overcoated with black material on same side. Pulse produced by chopping of infrared source beam creates transient "thermal lens" that temporarily defocuses laser beam probe. Detector monitoring beam measures defocusing which parallels infrared intensity.
A sample material was irradiated by relatively high power, short pulses from a dye laser. Energy from the pulses was absorbed by the sample material, thereby forming a thermal lens in the area of absorption. The pulse repetition rate was chosen so that the thermal lens is substantially dissipated by the time the next pulse reaches the sample material. A probe light beam, which in a specific embodiment is a relatively low power, continuous wave (cw) laser beam, irradiated the thermal lens formed in the sample material. The intensity characteristics of the probe light beam subsequent to irradiation of the thermal lens is related to changes in the refractive index of the sample material as the thermal lens is formed and dissipated.
A technique has been developed for rapidly casting from solution under vacuum smooth, bubble-free, clear-white and uniformly thick (about 0.20 cm) sheets of a segmented polyurethane elastomer. The casting is carried out from dimethylformamide solutions inside temperature-controlled air-circulated ovens in order to minimize the establishment of thermal gradients throughout the casting solution. The technique produces quality sheets in 9 days, compared with 40-45 days for an inferior film produced in open pans.
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A novel pulsed dual-beam thermal lens technique for the determination of thermal diffusivity of liquids and solids was developed. In this technique a transient thermal lens is formed in the test specimen by using a dye laser pulse as a heating source and the thermal lens decay is monitored by means of a CW He-Ne laser. The technique is fast and contactless and avoids some of the major difficulties of conventional methods. Thermal diffusivities for water and a polycarbonate plastic were measured and found to be in agreement with literature values. Considerable simplification and minimization of certain errors was achieved by use of a reference material.
Closed expression for volume as function of pressure and temperature has been verified for over 250 liquids. Equation can assist chemical engineers, soild-state researchers, and others with interest in thermodynamic behavior of liquids.
In an extension of "thermal lens" effect to new applications and better resolution, two laser beams combine to rapidly measure thermal diffusivity and other molecular dynamic properties. New double-beam technique handles very small samples unlike classical techniques for measuring diffusivity. It can be used for measurements on samples undergoing stress, making it applicable to data collection for structural engineering.
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Historically, chemicals from biomass have been and are expected to be economical in three major areas: byproducts, specialty items and polymers. Assessments of producing major chemicals from biomass in a processing plant based on the available conversion techniques indicate that they are not economically attractive, with the possible exception of conversion to ammonia and ethanol. The deterrents are the heavy capital investments, dependability of raw material supply and transportation costs for large plants, lack of operation experience, inadaptability of market variations, and competition from petroleum and coal. More importantly, it is also shown that even if chemicals from biomass were economical today, the resultant savings in petroleum would be far less than those achieved through other options available for the utilization of biomass as fuel and structural material. Thus, it is concluded that near-term research and development must be toward improved conversion processes, recovery of valuable products from waste streams at existing plants, more efficient use of biomass of energy and more efficient production of superior material products.
Bubble formation and layering, which often plague vacuum-evaporated films, are prevented by properly regulating process parameters. Vacuum casting may be applicable to forming thick films of other polymer/solvent solutions.
An analytical model was developed which quantifies effects on organic composite matrix materials of high energy electrons and of UV as well as interactions between the two radiations. Literature data on polyethylene were used to construct a degradation kinetics scheme corresponding to an Earth orbit at L=3. Analysis of the model showed that steady state concentrations of radicals put limits on accelerated test conditions. These conclusions were validated by an experimental study on polymethylmethacrylate using UV laser excitation. Relationships for balancing electron and UV radiations to equal acceleration factors are derived. Pulse radiolysis using an electron-beam along with time-resolved spectroscopy is shown to be able to separate primary form secondary reactions. Implications of these reactions to changes in engineering material properties are indicated. The use of mechanistic studies is discussed in the context of general test strategies for evaluating materials for space applications.
A series of hybrid fluorochemicals of general structure R(1)R(2)R(3)CR(4) was prepared where the R(i)'s (i=1,2,3) is a saturated fluoroalkyl group of formula C sub N F sub 2n+1, and R(4) is an alkyl group C sub n H sub 2n+1 or a related moiety containing amino, ether, or ester functions but no CF bonds. Compounds of this class containing approximately eight to twenty carbons total have physical properties suitable for use as the oxygen carrying phase of fluorochemical emulsion artificial blood. The chemical synthesis, and physical and biological testing of pure single isomers of the proposed artificial blood candidate compounds are included. Significant results are given.