Reaction-rate kinetics and distribution of activation energies
Reaction rate kinetics characteristics from isothermal data, investigating relationship to activation energy distribution
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Reaction rate kinetics characteristics from isothermal data, investigating relationship to activation energy distribution
Anomalously small annealing rate constant observed in SiE centers explained by assuming activation energy distribution
One method being used to determine energy level(s) and electrical activity of impurities in silicon is described. The method is called capacitance transient spectroscopy (CTS). It can be classified into three basic categories: the thermally stimulated capacitance method, the voltage-stimulated capacitance method, and the light-stimulated capacitance method; the first two categories are discussed. From the total change in capacitance and the time constant of the capacitance response, emission rates, energy levels, and trap concentrations can be determined. A major advantage of using CTS is its ability to detect the presence of electrically active impurities that are invisible to other techniques, such as Zeeman effect atomic absorption, and the ability to detect more than one electrically active impurity in a sample. Examples of detection of majority and minority carrier traps from gold donor and acceptor centers in silicon using the capacitance transient spectrometer are given to illustrate the method and its sensitivity.
A number of observed characteristics of OB associations, including their positive total energies and subgroup structure, are explained by the hypothesis that an association is composed of stars formed by compression of interstellar clouds in blast waves of several generations of supernovae. The later-generation supernovae are simply the most massive stars formed by this mechanism in the earlier generations. This supernova cascade process may also be responsible for giant loops such as the North Polar Spur. Enhanced high-energy gamma-ray emission is expected from the loops.
Teaming is so common in today's project management environment that most of us assume it comes naturally. We further assume that when presented with meaningful and challenging work, project teams will naturally engage in productive activity to complete their tasks. This assumption is expressed in the simple (but false) equation: Team + Work = Teamwork. Although this equation appears simple and straightforward, it is far from true for most project organizations whose reality is a complex web of institutional norms based on individual achievement and rewards. This is illustrated by the very first successful team experience from my early Air Force career. As a young lieutenant, I was sent to Squadron Officer School, which was the first in the series of Air Force professional military education courses I was required to complete during my career. We were immediately formed into teams of twelve officers. Much of the course featured competition between these teams. As the most junior member of my team, I quickly observed the tremendous pressure to show individual leadership capability. At one point early in the course, almost everyone in our group was vying to become the team leader. This conflict was so intense that it caused us to fail miserably in our first outdoor team building exercise. We spent so much time fighting over leadership that we were unable to complete any of the events on the outdoor obstacle course. This complete lack of success was so disheartening to me that I gave our team little hope for future success. What followed was a very intense period of bickering, conflict, and even shouting matches as our dysfunctional team tried to cope with our early failures and find some way to succeed. British physician and researcher Wilfred Bion (Experiences in Groups, 1961) discovered that there are powerful psychological forces inherent in all groups that divert from accomplishing their primary tasks. To overcome these restraining forces and use the potential power of the team, greater emphasis must be placed on establishing and maintaining group cohesiveness. This relationship is expressed in the revised (true) mathematical equation: Team + Work (on the Team) = Teamwork.
Time of flight mass spectrometric technique for measuring rate constants of hydroxyl radical reactions with hydrogen and carbon monoxide
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A summary of a literature review on thermal decomposition of HMX and RDX is presented. The decomposition apparently fits first order kinetics. Recommended values for Arrhenius parameters for HMX and RDX decomposition in the gaseous and liquid phases and for decomposition of RDX in solution in TNT are given. The apparent importance of autocatalysis is pointed out, as are some possible complications that may be encountered in interpreting extending or extrapolating kinetic data for these compounds from measurements carried out below their melting points to the higher temperatures and pressure characteristic of combustion.
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The procedures described by Danchenko et al. (1980) are applied to devices of RCA's Z-process (100,000 rad-hard). A thermal annealing investigation of the Z-process reveals an annealing behavior of the p-channels that is anomalous when compared with the p-channels of the commercial and J-processes. It is noted that the thermal annealing-induced shift of the threshold potential extends far below the original value; this necessitated the development of a new mathematical treatment, the treatment presented in the paper.
Schottky barrier diodes were fabricated on Zn doped InP Wafers. The diodes were radiation damaged with 2 MeV protons to a dose of 2 x 10(exp 12)cm(sup -2). The damage was analyzed by DLTS (deep level transient spectroscopy) using the double correlation technique. Capture cross sections were measured directly. Two major defects were observed in the DLTS spectra. The first defect, was H4 at Ev + 0.29 eV, with capture cross section 1.1 x 10(exp -17)cm(sup 2). The second defect, was H5 at Ev + 0.53 eV. Its capture cross section varied with temperature as described by the relationship sigma = sigma(sub 0) exp(delta(E)/kT) where sigma(sub 0) = 1.3 x 10(exp -19)cm(sup 2) and delta(E) = .08 eV. This relationship yields a sigma of 5.9 x 10(exp -21)cm(sup 2) at room temperature. The surprisingly small capture cross section of H5 and its temperature dependence are discussed in terms of the multiphonon emission process for carrier capture at the defect. The advantages of the improved experimental techniques used are also discussed.
The interface between two immiscible liquids with immobilized photosynthetic pigments can serve as the simplest model of a biological membrane convenient for the investigation of photoprocesses accompanied by spatial separation of charges. As it follows from thermodynamics, if the resolvation energies of substrates and products are very different, the interface between two immiscible liquids may act as a catalyst. Theoretical aspects of charge transfer reactions at oil/water interfaces are discussed. Conditions under which the free energy of activation of the interfacial reaction of electron transfer decreases are established. The activation energy of electron transfer depends on the charges of the reactants and dielectric permittivity of the non-aqueous phase. This can be useful when choosing a pair of immiscible solvents to decrease the activation energy of the reaction in question or to inhibit an undesired process. Experimental interfacial catalytic systems are discussed. Amphiphilic molecules such as chlorophyll or porphyrins were studied as catalysts of electron transfer reactions at the oil/water interface.
The flashback of hydrogen-oxygen-nitrogen flames was studied as a function of pressure, burner diameter, equivalence ratio, and oxidant strength. The results were treated on the assumption that the product of the critical boundary velocity gradient for flashback and the initial concentration of that reactant which is not in excess is proportional to a mean reaction rate associated with the flame zone. It was further assumed that this reaction rate can be expressed in terms of initial concentrations and flame temperature. Measurements at constant flame temperature yield orders of reaction with respect to hydrogen and oxygen. These do not vary with flame temperature. Measurements in which pressure is varied for several values of oxidant strength at constant equivalence ratio yield a total order of reaction and a function describing the dependence of the mean reaction rate on flame temperature. The total reaction order is independent of flame temperature and equal to the sum of the orders for hydrogen and oxygen. The dependence of the reaction rate on flame temperature cannot be described by a constant activation energy. The activation energy obtained apparently increases with flame temperature. Flashback results can be described by a single rate constant which is independent of equivalence ratio. Values were estimated for this rate constant as a function of flame temperature.
Crystalline silicon carbide (SiC) substrates and epilayers, undoped as well as n- and p-doped, have been electrically characterized by performing Hall effect and resistivity measurements (van der Pauw) over the temperature range of approximately 85 K to 650 K (200 K to 500 K for p-type sample). By fitting the measured temperature dependent carrier concentration data to the single activation energy theoretical model: (1) the activation energy for the nitrogen donor ranged from 0.078 eV to 0.101 eV for a doping concentration range of 10(exp 17) cm(exp -3) to 10(exp 18) cm(exp -3) and (2) the activation energy for the aluminum acceptor was 0.252 eV for a doping concentration of 4.6 x 10(exp 18) cm(exp -3). By fitting the measured temperature dependent carrier concentration data to the double activation energy level theoretical model for the nitrogen donor: (1) the activation energy for the hexagonal site was 0.056 eV and 0.093 eV corresponding to doping concentrations of 3.33 x 10 (exp 17) cm(exp -3) and 1.6 x 10(exp 18) cm(exp -3) and (2) the activation energy for the cubic site was 0.113 and 0.126 eV corresponding to doping concentrations of 4.2 x 10(exp 17) cm(exp -3) and 5.4 x 10(exp 18) cm(exp -3).
An analysis of the reaction of Au and Au-In alloys with InP has permitted the identification of the mechanisms occurring during the first two stages of the Au-InP interaction. The first stage of the interaction, during which the Au is converted to a saturated Au (In) solution, is controlled by the vacancy-generation rate at the free surface of the metallization. The activation energy for this process is the activation energy for Au self-diffusion. Evidence is presented for the existence of large localized variations in this value due to surface related effects. At the completion of stage I stage II becomes active and continues until the metallization is converted to Au3In. This process, proceeding via an interstitial interchange mechanism, is many orders of magnitude slower than stage I. The rate-limiting step, with an activation energy of 2.8 eV, is shown to be the diffusion of In from the InP-metal interface. The P atoms that are released when In enters the metallization during stage I leave the system without reacting, whereas in stage II they form a compound (Au2P3) at the InP-metal interface. The presence of the Au2P3 severely retards the stage II interaction rate.
By measuring from active-region magnetograms a proxy of the free energy in the active region fs magnetic field, it has been found previously that (1) there is an abrupt upper limit to the free energy the field can hold that increases with the amount of magnetic field in the active region, the active region fs magnetic flux content, and (2) the free energy is usually near its limit when the field explodes in a CME/flare eruption. That is, explosive active regions are concentrated in a main-sequence path bordering the free-energy ]limit line in (flux content, free-energy proxy) phase space. Here, from measurement of Marshall Space Flight Center vector magnetograms, we find the magnetic condition that underlies the free ]energy limit and the accompanying main sequence of explosive active regions. Using a suitable free ]energy proxy measured from vector magnetograms of 44 active regions, we find that (1) in active regions at and near their free ]energy limit, the ratio of magnetic-shear free energy to the non ]free magnetic energy the potential field would have is approximately 1 in the core field, the field rooted along the neutral line, and (2) this ratio is progressively less in active regions progressively farther below their free ]energy limit. This shows that most active regions in which this core-field energy ratio is much less than 1 cannot be triggered to explode; as this ratio approaches 1, most active regions become capable of exploding; and when this ratio is 1 or greater, most active regions are compelled to explode. From these results we surmise the magnetic condition that determines the free ]energy limit is the ratio of the free magnetic energy to the non-free energy the active region fs field would have were it completely relaxed to its potential ]field configuration, and that this ratio is approximately 1 at the free-energy limit and in the main sequence of explosive active regions.
The 1100 to 1500 K slow plastic strain rate compressive properties of <001> oriented NiAl-3.6Ti single crystals have been measured, and the results suggests that two deformation processes exist. While the intermediate temperature/faster strain rate mechanism is uncertain, plastic flow at elevated temperature/slower strain rates in NiAl-3.6Ti appears to be controlled by solute drag as described by the Cottrell-Jaswon solute drag model for gliding b = a(sub 0)<101> dislocations. While the calculated activation energy of deformation is much higher (approximately 480 kJ/mol) than the activation energy for diffusion (approximately 290 kJ/mol) used in the Cottrell-Jaswon creep model, a forced temperature compensated - power law fit using the activation energy for diffusion was able to adequately (greater than 90%) predict the observed creep properties. Thus we conclude that the rejection of a diffusion controlled mechanism can not be simply based on a large numerical difference between the activation energies for deformation and diffusion.
Electrical response measurements from 10 Hz to 100 kHz between 120 and 540 C were made on potassium-silicate glasses with alkali oxide contents of 2, 3, 5 and 10 mol percent. Low alkali content glasses were chosen in order to try to reduce the Coulombic interactions between alkali ions to the point that frozen structural effects from the glass could be observed. Conductivity and electrical relaxation responses for both annealed and quenched glasses of the same composition were compared. Lower DC conductivity (sigma(sub DC)) activation energies were measured for the quenched compared to the annealed glasses. The two glasses with the lowest alkali contents exhibited a non-Arrhenius concave up curvature in the log(sigma(sub DC)) against 1/T plots, which decreased upon quenching. A sharp decrease in sigma(sub DC) was observed for glasses containing K2O concentrations of 5 mol percent or less. The log modulus loss peak (M'') maximum frequency plots against 1/T all showed Arrhenius behavior for both annealed and quenched samples. The activation energies for these plots closely agreed with the sigma(sub DC) activation energies. A sharp increase in activation energy was observed for both series as the potassium oxide concentration decreased. Changes in the electrical response are attributed to structural effects due to different alkali concentrations. Differences between the annealed and quenched response are linked to a change in the distribution of activation energies (DAE).