886 resultados para Diffusion in liquids
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In this work a multidisciplinary study of the December 26th, 2004 Sumatra earthquake has been carried out. We have investigated both the effect of the earthquake on the Earth rotation and the stress field variations associated with the seismic event. In the first part of the work we have quantified the effects of a water mass redistribution associated with the propagation of a tsunami wave on the Earth’s pole path and on the length-of-day (LOD) and applied our modeling results to the tsunami following the 2004 giant Sumatra earthquake. We compared the result of our simulations on the instantaneous rotational axis variations with some preliminary instrumental evidences on the pole path perturbation (which has not been confirmed yet) registered just after the occurrence of the earthquake, which showed a step-like discontinuity that cannot be attributed to the effect of a seismic dislocation. Our results show that the perturbation induced by the tsunami on the instantaneous rotational pole is characterized by a step-like discontinuity, which is compatible with the observations but its magnitude turns out to be almost one hundred times smaller than the detected one. The LOD variation induced by the water mass redistribution turns out to be not significant because the total effect is smaller than current measurements uncertainties. In the second part of this work of thesis we modeled the coseismic and postseismic stress evolution following the Sumatra earthquake. By means of a semi-analytical, viscoelastic, spherical model of global postseismic deformation and a numerical finite-element approach, we performed an analysis of the stress diffusion following the earthquake in the near and far field of the mainshock source. We evaluated the stress changes due to the Sumatra earthquake by projecting the Coulomb stress over the sequence of aftershocks taken from various catalogues in a time window spanning about two years and finally analyzed the spatio-temporal pattern. The analysis performed with the semi-analytical and the finite-element modeling gives a complex picture of the stress diffusion, in the area under study, after the Sumatra earthquake. We believe that the results obtained with the analytical method suffer heavily for the restrictions imposed, on the hypocentral depths of the aftershocks, in order to obtain the convergence of the harmonic series of the stress components. On the contrary we imposed no constraints on the numerical method so we expect that the results obtained give a more realistic description of the stress variations pattern.
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Although rational models of formal planning have been seriously criticized by strategy literature, they not only remain a widely used organizational practice in private firms, but they have increasingly been entering public, professional organizations too, as part of public sector managerial reforms. This research addresses this apparent paradox, exploring the meaning of formal planning in public sector professional work. Curiously, this is an issue that remains under-investigated in the literature: the long debate on formal planning in strategy research devoted scant attention to its diffusion in the public sector, and public sector studies have scrutinized the introduction of other management tools in professional work, but very limitedly formal planning itself. In fact, little is known on the actual meaning of formal planning in public, professional services. This research is based upon a case of adoption of formal planning tools in a public hospital. Embracing a discourse analytical lens, it examines which formal planning discourse entered professional work, to what extent, and how professionals interpret it and engage with it in their practice. The analysis uncovers dynamics of social construction of meaning where, eventually, a formal planning discourse both shapes and is shaped by professional practice. In particular, it is found that formal planning rationality largely penetrated professional work, but not to the detriment of professional values. Morevover, formal planning ‘fails’ as a tool for rational decision making, but it takes up a knowledge work and a social value in professional work, as a tool for explicitation of action courses and for dialogue between otherwise more disconnected parts of the organization.
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A broad variety of solid state NMR techniques were used to investigate the chain dynamics in several polyethylene (PE) samples, including ultrahigh molecular weight PEs (UHMW-PEs) and low molecular weight PEs (LMW-PEs). Via changing the processing history, i.e. melt/solution crystallization and drawing processes, these samples gain different morphologies, leading to different molecular dynamics. Due to the long chain nature, the molecular dynamics of polyethylene can be distinguished in local fluctuation and long range motion. With the help of NMR these different kinds of molecular dynamics can be monitored separately. In this work the local chain dynamics in non-crystalline regions of polyethylene samples was investigated via measuring 1H-13C heteronuclear dipolar coupling and 13C chemical shift anisotropy (CSA). By analyzing the motionally averaged 1H-13C heteronuclear dipolar coupling and 13C CSA, the information about the local anisotropy and geometry of motion was obtained. Taking advantage of the big difference of the 13C T1 relaxation time in crystalline and non-crystalline regions of PEs, the 1D 13C MAS exchange experiment was used to investigate the cooperative chain motion between these regions. The different chain organizations in non-crystalline regions were used to explain the relationship between the local fluctuation and the long range motion of the samples. In a simple manner the cooperative chain motion between crystalline and non-crystalline regions of PE results in the experimentally observed diffusive behavior of PE chain. The morphological influences on the diffusion motion have been discussed. The morphological factors include lamellar thickness, chain organization in non-crystalline regions and chain entanglements. Thermodynamics of the diffusion motion in melt and solution crystallized UHMW-PEs is discussed, revealing entropy-controlled features of the chain diffusion in PE. This thermodynamic consideration explains the counterintuitive relationship between the local fluctuation and the long range motion of the samples. Using the chain diffusion coefficient, the rates of jump motion in crystals of the melt crystallized PE have been calculated. A concept of "effective" jump motion has been proposed to explain the difference between the values derived from the chain diffusion coefficients and those in literatures. The observations of this thesis give a clear demonstration of the strong relationship between the sample morphology and chain dynamics. The sample morphologies governed by the processing history lead to different spatial constraints for the molecular chains, leading to different features of the local and long range chain dynamics. The knowledge of the morphological influence on the microscopic chain motion has many implications in our understanding of the alpha-relaxation process in PE and the related phenomena such as crystal thickening, drawability of PE, the easy creep of PE fiber, etc.
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Aerosolpartikel beeinflussen das Klima durch Streuung und Absorption von Strahlung sowie als Nukleations-Kerne für Wolkentröpfchen und Eiskristalle. Darüber hinaus haben Aerosole einen starken Einfluss auf die Luftverschmutzung und die öffentliche Gesundheit. Gas-Partikel-Wechselwirkunge sind wichtige Prozesse, weil sie die physikalischen und chemischen Eigenschaften von Aerosolen wie Toxizität, Reaktivität, Hygroskopizität und optische Eigenschaften beeinflussen. Durch einen Mangel an experimentellen Daten und universellen Modellformalismen sind jedoch die Mechanismen und die Kinetik der Gasaufnahme und der chemischen Transformation organischer Aerosolpartikel unzureichend erfasst. Sowohl die chemische Transformation als auch die negativen gesundheitlichen Auswirkungen von toxischen und allergenen Aerosolpartikeln, wie Ruß, polyzyklische aromatische Kohlenwasserstoffe (PAK) und Proteine, sind bislang nicht gut verstanden.rn Kinetische Fluss-Modelle für Aerosoloberflächen- und Partikelbulk-Chemie wurden auf Basis des Pöschl-Rudich-Ammann-Formalismus für Gas-Partikel-Wechselwirkungen entwickelt. Zunächst wurde das kinetische Doppelschicht-Oberflächenmodell K2-SURF entwickelt, welches den Abbau von PAK auf Aerosolpartikeln in Gegenwart von Ozon, Stickstoffdioxid, Wasserdampf, Hydroxyl- und Nitrat-Radikalen beschreibt. Kompetitive Adsorption und chemische Transformation der Oberfläche führen zu einer stark nicht-linearen Abhängigkeit der Ozon-Aufnahme bezüglich Gaszusammensetzung. Unter atmosphärischen Bedingungen reicht die chemische Lebensdauer von PAK von wenigen Minuten auf Ruß, über mehrere Stunden auf organischen und anorganischen Feststoffen bis hin zu Tagen auf flüssigen Partikeln. rn Anschließend wurde das kinetische Mehrschichtenmodell KM-SUB entwickelt um die chemische Transformation organischer Aerosolpartikel zu beschreiben. KM-SUB ist in der Lage, Transportprozesse und chemische Reaktionen an der Oberfläche und im Bulk von Aerosol-partikeln explizit aufzulösen. Es erforder im Gegensatz zu früheren Modellen keine vereinfachenden Annahmen über stationäre Zustände und radiale Durchmischung. In Kombination mit Literaturdaten und neuen experimentellen Ergebnissen wurde KM-SUB eingesetzt, um die Effekte von Grenzflächen- und Bulk-Transportprozessen auf die Ozonolyse und Nitrierung von Protein-Makromolekülen, Ölsäure, und verwandten organischen Ver¬bin-dungen aufzuklären. Die in dieser Studie entwickelten kinetischen Modelle sollen als Basis für die Entwicklung eines detaillierten Mechanismus für Aerosolchemie dienen sowie für das Herleiten von vereinfachten, jedoch realistischen Parametrisierungen für großskalige globale Atmosphären- und Klima-Modelle. rn Die in dieser Studie durchgeführten Experimente und Modellrechnungen liefern Beweise für die Bildung langlebiger reaktiver Sauerstoff-Intermediate (ROI) in der heterogenen Reaktion von Ozon mit Aerosolpartikeln. Die chemische Lebensdauer dieser Zwischenformen beträgt mehr als 100 s, deutlich länger als die Oberflächen-Verweilzeit von molekularem O3 (~10-9 s). Die ROIs erklären scheinbare Diskrepanzen zwischen früheren quantenmechanischen Berechnungen und kinetischen Experimenten. Sie spielen eine Schlüsselrolle in der chemischen Transformation sowie in den negativen Gesundheitseffekten von toxischen und allergenen Feinstaubkomponenten, wie Ruß, PAK und Proteine. ROIs sind vermutlich auch an der Zersetzung von Ozon auf mineralischem Staub und an der Bildung sowie am Wachstum von sekundären organischen Aerosolen beteiligt. Darüber hinaus bilden ROIs eine Verbindung zwischen atmosphärischen und biosphärischen Mehrphasenprozessen (chemische und biologische Alterung).rn Organische Verbindungen können als amorpher Feststoff oder in einem halbfesten Zustand vorliegen, der die Geschwindigkeit von heterogenen Reaktionenen und Mehrphasenprozessen in Aerosolen beeinflusst. Strömungsrohr-Experimente zeigen, dass die Ozonaufnahme und die oxidative Alterung von amorphen Proteinen durch Bulk-Diffusion kinetisch limitiert sind. Die reaktive Gasaufnahme zeigt eine deutliche Zunahme mit zunehmender Luftfeuchte, was durch eine Verringerung der Viskosität zu erklären ist, bedingt durch einen Phasenübergang der amorphen organischen Matrix von einem glasartigen zu einem halbfesten Zustand (feuchtigkeitsinduzierter Phasenübergang). Die chemische Lebensdauer reaktiver Verbindungen in organischen Partikeln kann von Sekunden bis zu Tagen ansteigen, da die Diffusionsrate in der halbfesten Phase bei niedriger Temperatur oder geringer Luftfeuchte um Größenordnungen absinken kann. Die Ergebnisse dieser Studie zeigen wie halbfeste Phasen die Auswirkung organischeer Aerosole auf Luftqualität, Gesundheit und Klima beeinflussen können. rn
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Gels are elastic porous polymer networks that are accompanied by pronounced mechanical properties. Due to their biocompatibility, ‘responsive hydrogels’ (HG) have many biomedical applications ranging from biosensors and drug delivery to tissue engineering. They respond to external stimuli such as temperature and salt by changing their dimensions. Of paramount importance is the ability to engineer penetrability and diffusion of interacting molecules in the crowded HG environment, as this would enable one to optimize a specific functionality. Even though the conditions under which biomedical devices operate are rather complex, a bottom-up approach could reduce the complexity of mutually coupled parameters influencing tracer mobility. The present thesis focuses on the interaction-induced tracer diffusion in polymer solutions and their homologous gels, probed by means of Fluorescence Correlation Spectroscopy (FCS). This is a single-molecule-sensitive technique having the advantage of optimal performance under ultralow tracer concentrations, typically employed in biosensors. Two different types of hydrogels have been investigated, a conventional one with broad polydispersity in the distance between crosslink points and a so-called ‘ideal’, with uniform mesh size distribution. The former is based on a thermoresponsive polymer, exhibiting phase separation in water at temperatures close to the human body temperature. The latter represents an optimal platform to study tracer diffusion. Mobilities of different tracers have been investigated in each network, varying in size, geometry and in terms of tracer-polymer attractive strength, as perturbed by different stimuli. The thesis constitutes a systematic effort towards elucidating the role of the strength and nature of different tracer-polymer interactions, on tracer mobilities; it outlines that interactions can still be very important even in the simplified case of dilute polymer solutions; it also demonstrates that the presence of permanent crosslinks exerts distinct tracer slowdown, depending on the tracer type and the nature of the tracer-polymer interactions, expressed differently by each tracer with regard to the selected stimulus. In aqueous polymer solutions, the tracer slowdown is found to be system-dependent and no universal trend seems to hold, in contrast to predictions from scaling theory for non-interacting nanoparticle mobility and empirical relations concerning the mesh size in polymer solutions. Complex tracer dynamics in polymer networks may be distinctly expressed by FCS, depending on the specific synergy among-at least some of - the following parameters: nature of interactions, external stimuli employed, tracer size and type, crosslink density and swelling ratio.
Resumo:
Hydrogels are composed of cross-linked networks of hydrophilic polymers that are biocompatible due to their high water content. Mass transfer through hydrogels has been suggested as an effective method of drug delivery, specifically in degradable polymers to minimize lasting effects within the body. Diffusion of small molecules in poly (ethylene glycol) diacrylate (PEG-DA) and dextran methacrylate (dex-MA) hydrogels was characterized in a microfluidic device and by complementary techniques. Microfluidic devices were prepared by crosslinking a formulation of hydrogel and photo-initiator, with and without visible dye, using photolithography to define a central microchannel. Channel sizes within the devices were approximately 600 ¿m to simulate vessels within the body. The microfluidic technique allows for both image and effluent analyses. To visualize the diffusive behavior within the dextran hydrogel, methylene blue and sulforhodamine 101 dyes were used in both elution and uptake experiments. Three analysis techniques for measuring diffusion coefficients were used to quantify the diffusion of solute in the hydrogel, including optical microscopy, characterization of device effluent, and NMR analyses. The optical microscopy technique analyzes images of the dye diffusion captured by a stereomicroscope to generate dye concentration v. position profiles. The data was fit to a diffusion model to determine diffusion coefficients and the dye release profile. In a typical elution experiment, aqueous solution is pumped through the microchannel and dye diffuses out of the hydrogel and into the aqueous phase. During elution, images are taken at regular time intervals and the effluent was collected. Analysis of the device effluent was performed using ultraviolet-visible (UV/Vis) spectroscopy to determine the effluent dye concentration and thus a short-time diffusion coefficient. Nuclear magnetic resonance (NMR) was used to determine a free diffusion coefficient of molecules in hydrogel without the effect of a concentration gradient. Diffusion coefficients for methylene blue and sulforhodamine 101 dyes in dex-MA hydrogel calculated using the three analysis methods all agree well. It was determined that utilizing a combination of the three techniques offers greater insight into molecular diffusion in hydrogels than employing each technique individually. The use of the same microfluidic devices used to measure diffusion is explored in the use of studying the degradation of dex-MA hydrogels. By combining what is known about the degradation rate in regards to the effect of pH and crosslinking and the ability to use a dye solution in contrast to establish the hydrogel boundaries could be a novel approach to studying hydrogel degradation.
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PURPOSE: To prospectively evaluate feasibility and reproducibility of diffusion-weighted (DW) and blood oxygenation level-dependent (BOLD) magnetic resonance (MR) imaging in patients with renal allografts, as compared with these features in healthy volunteers with native kidneys. MATERIALS AND METHODS: The local ethics committee approved the study protocol; patients provided written informed consent. Fifteen patients with a renal allograft and in stable condition (nine men, six women; age range, 20-67 years) and 15 age- and sex-matched healthy volunteers underwent DW and BOLD MR imaging. Seven patients with renal allografts were examined twice to assess reproducibility of results. DW MR imaging yielded a total apparent diffusion coefficient including diffusion and microperfusion (ADC(tot)), as well as an ADC reflecting predominantly pure diffusion (ADC(D)) and the perfusion fraction. R2* of BOLD MR imaging enabled the estimation of renal oxygenation. Statistical analysis was performed, and analysis of variance was used for repeated measurements. Coefficients of variation between and within subjects were calculated to assess reproducibility. RESULTS: In patients, ADC(tot), ADC(D), and perfusion fraction were similar in the cortex and medulla. In volunteers, values in the medulla were similar to those in the cortex and medulla of patients; however, values in the cortex were higher than those in the medulla (P < .05). Medullary R2* was higher than cortical R2* in patients (12.9 sec(-1) +/- 2.1 [standard deviation] vs 11.0 sec(-1) +/- 0.6, P < .007) and volunteers (15.3 sec(-1) +/- 1.1 vs 11.5 sec(-1) +/- 0.5, P < .0001). However, medullary R2* was lower in patients than in volunteers (P < .004). Increased medullary R2* was paralleled by decreased diffusion in patients with allografts. A low coefficient of variation in the cortex and medulla within subjects was obtained for ADC(tot), ADC(D), and R2* (<5.2%), while coefficient of variation within subjects was higher for perfusion fraction (medulla, 15.1%; cortex, 8.6%). Diffusion and perfusion indexes correlated significantly with serum creatinine concentrations. CONCLUSION: DW and BOLD MR imaging are feasible and reproducible in patients with renal allografts.
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Titanium oxide is an important semiconductor, which is widely applied for solar cells. In this research, titanium oxide nanotube arrays were synthesized by anodization of Ti foil in the electrolyte composed of ethylene glycol containing 2 vol % H2O and 0.3 wt % NH4F. The voltages of 40V-50V were employed for the anodizing process. Pore diameters and lengths of the TiO2 nanotubes were evaluated by field emission scanning electron microscope (FESEM). The obtained highly-ordered titanium nanotube arrays were exploited to fabricate photoelectrode for the Dye-sensitized solar cells (DSSCS). The TiO2 nanotubes based DSSCS exhibited an excellent performance with a high short circuit current and open circuit voltage as well as a good power conversion efficiency. Those can be attributed to the high surface area and one dimensional structure of TiO2 nanotubes, which could hold a large amount of dyes to absorb light and help electron percolation process to hinder the recombination during the electrons diffusion in the electrolyte.
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PURPOSE: To prospectively assess the potential of noninvasive diffusion-weighted magnetic resonance (MR) imaging to depict changes in microperfusion and diffusion in patients with acute unilateral ureteral obstruction. MATERIALS AND METHODS: The local ethics committee approved the study protocol. Informed consent was obtained. Diffusion-weighted MR imaging was performed in 21 patients (two women, 19 men; mean age, 43 years +/- 10 [standard deviation]) with acute unilateral ureteral obstruction due to a calculus diagnosed at unenhanced computed tomography. A control group (one woman, 15 men; mean age, 44 years +/- 12) underwent the same MR protocol. Standard processing yielded an apparent diffusion coefficient (ADC) ADCT; the separation of microperfusion and diffusion contributions yielded the perfusion fraction FP and the pure diffusion coefficient ADCD. ADCT, ADCD, and FP were compared between obstructed and contralateral unobstructed kidneys and with control values. For statistical analysis, nonparametric rank tests were used. A P value of less than .05 was considered significant. RESULTS: No significant differences were observed between the ADCT of the medulla or cortex of the obstructed and unobstructed kidneys. Compared with control kidneys, only medullary ADCT was slightly increased in the obstructed kidney (P < .04). However, the ADCD in the medulla of the obstructed and unobstructed kidneys was significantly higher than that in control subjects (201 x 10(-5) mm2/sec +/- 16 and 199 x 10(-5) mm2/sec +/- 20 vs 189 x 10(-5) mm2/sec +/- 12; P < .008 and P < .03, respectively). FP of the cortex of the obstructed kidney was significantly lower than that in the unobstructed kidney (20.2% +/- 4.8 vs 24.0% +/- 5.8; P < .002); FP of the medulla was slightly lower in the obstructed kidney than in the unobstructed kidney (18.3% +/- 5.9 vs 20.7% +/- 6.4; P = .05). CONCLUSION: Diffusion-weighted MR imaging allows noninvasive detection of changes in renal perfusion and diffusion during acute unilateral ureteral obstruction, as exemplified in patients with a ureteral calculus.
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Transport of volatile hydrocarbons in soils is largely controlled by interactions of vapours with the liquid and solid phase. Sorption on solids of gaseous or dissolved comPounds may be important. Since the contact time between a chemical and a specific sorption site can be rather short, kinetic or mass-transfer resistance effects may be relevant. An existing mathematical model describing advection and diffusion in the gas phase and diffusional transport from the gaseous phase into an intra-aggregate water phase is modified to include linear kinetic sorption on ps-solid and water-solid interfaces. The model accounts for kinetic mass transfer between all three phases in a soil. The solution of the Laplace-transformed equations is inverted numerically. We performed transient column experiments with 1,1,2-Trichloroethane, Trichloroethylene, and Tetrachloroethylene using air-dry solid and water-saturated porous glass beads. The breakthrough curves were calculated based on independently estimated parameters. The model calculations agree well with experimental data. The different transport behaviour of the three compounds in our system primarily depends on Henry's constants.
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In any physicochemical process in liquids, the dynamical response of the solvent to the solutes out of equilibrium plays a crucial role in the rates and products: the solvent molecules react to the changes in volume and electron density of the solutes to minimize the free energy of the solution, thus modulating the activation barriers and stabilizing (or destabilizing) intermediate states. In charge transfer (CT) processes in polar solvents, the response of the solvent always assists the formation of charge separation states by stabilizing the energy of the localized charges. A deep understanding of the solvation mechanisms and time scales is therefore essential for a correct description of any photochemical process in dense phase and for designing molecular devices based on photosensitizers with CT excited states. In the last two decades, with the advent of ultrafast time-resolved spectroscopies, microscopic models describing the relevant case of polar solvation (where both the solvent and the solute molecules have a permanent electric dipole and the mutual interaction is mainly dipole−dipole) have dramatically progressed. Regardless of the details of each model, they all assume that the effect of the electrostatic fields of the solvent molecules on the internal electronic dynamics of the solute are perturbative and that the solvent−solute coupling is mainly an electrostatic interaction between the constant permanent dipoles of the solute and the solvent molecules. This well-established picture has proven to quantitatively rationalize spectroscopic effects of environmental and electric dynamics (time-resolved Stokes shifts, inhomogeneous broadening, etc.). However, recent computational and experimental studies, including ours, have shown that further improvement is required. Indeed, in the last years we investigated several molecular complexes exhibiting photoexcited CT states, and we found that the current description of the formation and stabilization of CT states in an important group of molecules such as transition metal complexes is inaccurate. In particular, we proved that the solvent molecules are not just spectators of intramolecular electron density redistribution but significantly modulate it. Our results solicit further development of quantum mechanics computational methods to treat the solute and (at least) the closest solvent molecules including the nonperturbative treatment of the effects of local electrostatics and direct solvent−solute interactions to describe the dynamical changes of the solute excited states during the solvent response.
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Voluntary environmental actions, such as the adoption of ISO 14001, are gaining increasing attention in developing countries. This study examines the mechanism of ISO 14001 diffusion in a developing economy on the basis of a unique corporate survey of manufacturing sectors in Malaysia. Product-related environmental regulations, such as REACH, are contributing to this diffusion indirectly by promoting quality control standards such as ISO 9001. The importance of foreign direct investment and global value chains for ISO 14001 diffusion is also confirmed.
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In this work we present results of zinc diffusion in GaAs using the liquid phase epitaxy technique from liquid solutions of Ga‐As‐Zn and Ga‐As‐Al‐Zn. Using silicon‐doped n‐GaAs substrates, working at a diffusion temperature of 850 °C, and introducing a dopant concentration ranging 1018–1019 cm−3, the most important findings regarding the diffusion properties are as follows: (a) zinc concentration in the solid depends on the square root of zinc atomic fraction in the liquid; (b) the diffusion is dominated by the interstitial‐substitutional process; (c) the diffusivity D varies as about C3 in the form D=2.9×10−67C3.05; (d) aluminum plays the role of the catalyst of the diffusion process, if it is introduced in the liquid solution, since it is found that D varies as (γAsXlAs)−1; (e) the zinc interstitial is mainly doubly ionized (Zn++i); (f) the zinc diffusion coefficient in Al0.85 Ga0.15 As is about four times greater than in GaAs; (g) by means of all these results, it is possible to control zinc diffusion processes in order to obtain optimized depth junctions and doping levels in semiconductor device fabrication.