969 resultados para WATER-VAPOR BARRIER


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Chemical vapor deposition (CVD) is widely utilized to synthesize graphene with controlled properties for many applications, especially when continuous films over large areas are required. Although hydrocarbons such as methane are quite efficient precursors for CVD at high temperature (∼1000 °C), finding less explosive and safer carbon sources is considered beneficial for the transition to large-scale production. In this work, we investigated the CVD growth of graphene using ethanol, which is a harmless and readily processable carbon feedstock that is expected to provide favorable kinetics. We tested a wide range of synthesis conditions (i.e., temperature, time, gas ratios), and on the basis of systematic analysis by Raman spectroscopy, we identified the optimal parameters for producing highly crystalline graphene with different numbers of layers. Our results demonstrate the importance of high temperature (1070 °C) for ethanol CVD and emphasize the significant effects that hydrogen and water vapor, coming from the thermal decomposition of ethanol, have on the crystal quality of the synthesized graphene.

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We report here on a series of laboratory experiments on plumes, undertaken with the object of simulating the effect of the heat release that occurs in clouds on condensation of water vapor. The experimental technique used for this purpose relies on ohmic heating generated in an electrically conducting plume fluid subjected to a suitable alternating voltage across specified axial stations in the plume flow [Bhat et al., 1989]. The present series of experiments achieves a value of the Richardson number that is toward the lower end of the range that characteristics cumulus clouds. It is found that the buoyancy enhancement due to heating disrupts the eddy structures in the flow and reduces the dilution owing to entrainment of ambient fluid that would otherwise have occurred in the central region of the plume. Heating also reduces the spread rate of the plume, but as it accelerates the flow as well, the overall specific mass flux in the plume does not show a very significant change at the heat input employed in the experiment. However, there is some indication that the entrainment rate (proportional to the streamwise derivative of the mass flux) is slightly higher immediately after heat injection and slightly lower farther downstream. The measurements support a previous proposal for a cloud scenario [Bhat and Narasimha, 1996] and demonstrate how fresh insights into certain aspects of the fluid dynamics of clouds may be derived from the experimental techniques employed here.

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The present study investigated the potato starches and polyols which were used to prepare edible films. The amylose content and the gelatinization properties of various potato starches extracted from different potato cultivars were determined. The amylose content of potato starches varied between 11.9 and 20.1%. Onset temperatures of gelatinization of potato starches in excess water varied independently of the amylose content from 58 to 61°C determined using differential scanning calorimetry (DSC). The crystallinity of selected native starches with low, medium and high amylose content was determined by X-ray diffraction. The relative crystallinity was found to be around 10 13% in selected native potato starches containing 13 17% water. The glass transition temperature, crystallization melting behavior and relaxations of polyols, erythritol, sorbitol and xylitol, were determined using (DSC), dielectric analysis (DEA) and dynamic mechanical analysis (DMA). The glass transition temperatures of xylitol and sorbitol decreased as a result of water plasticization. Anhydrous amorphous erythritol crystallized rapidly. Edible films were obtained from solutions containing gelatinized starch, plasticizer (polyol or binary polyol mixture) and water by casting and evaporating water at 35°C. The present study investigated effects of plasticizer type and content on physical and mechanical properties of edible films stored at various relative water vapor pressures (RVP). The crystallinity of edible films with low, medium and high amylose content was determined by X-ray diffraction and they were found to be practically amorphous. Water sorption and water vapor permeability (WVP) of films was affected by the type and content of plasticizer. Water vapor permeability of films increased with increasing plasticizer content and storage RVP. Generally, Young's modulus and tensile strength decreased with increasing plasticizer and water content with a concurrent increase in elongation at break of films. High contents of xylitol and sorbitol resulted in changes in physical and mechanical properties of films probably due to phase separation and crystallization of xylitol and sorbitol which was not observed when binary polyol mixtures were used as plasticizers. The mechanical properties and the water vapor permeability (WVP) of the films were found to be independent of the amylose content.

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Mannans are abundant plant polysaccharides found in the endosperm of certain leguminous seeds (guar gum galactomannan, GG; locust bean gum galactomannan, LBG), in the tuber of the konjac plant (konjac glucomannan, KGM), and in softwoods (galactoglucomannan, GGM). This study focused on the effects of the chemical structure of mannans on their film-forming and emulsion-stabilizing properties. Special focus was on spruce GGM, which is an interesting new product from forest biorefineries. A plasticizer was needed for the formation of films from mannans other than KGM and the optimal proportion was 40% (w/w of polymers) glycerol or sorbitol. Galactomannans with lower galactose content (LBG, modified GG) produced films with higher elongation at break and tensile strength. The mechanical properties of GG-based films were improved by decreasing the degree of polymerization of the polysaccharide with moderate mannanase treatments. The improvement of mechanical properties of GGM-based films was sought by blending GGM with each of poly(vinyl alcohol) (PVOH), corn arabinoxylan (cAX), and KGM. Adding other polymers increased the elongation at break of GGM blend films. The tensile strength of films increased with increasing amounts of PVOH and KGM, but the effect of cAX was the opposite. Dynamic mechanical analysis showed two separate loss modulus peaks for blends of GGM and PVOH, but a single peak for all other films. Optical and scanning electron microscopy confirmed good miscibility of GGM with cAX and KGM. In contrast, films blended from GGM and PVOH showed phase separation. GGM and KGM were mixed with cellulose nanowhiskers (CNW) to form composite films. Addition of CNW to KGM-based films induced the formation of fiberlike structures with lengths of several millimeters. In GGM-based films, rodlike structures with lengths of tens of micrometers were formed. Interestingly, the notable differences in the film structure did not appear to be related to the mechanical and thermal properties of the films. Permeability properties of GGM-based films were compared to those of films from commercial mannans KGM, GG, and LBG. GGM-based films had the lowest water vapor permeability when compared to films from other mannans. The oxygen permeability of GGM films was of the same magnitude as that of commercial polyethylene / ethylene vinyl alcohol / polyethylene laminate film. The aroma permeability of GGM films was low. All films were transparent in the visible region, but GGM films blocked the light transmission in the ultraviolet region of the spectra. The stabilizing effect of GGM on a model beverage emulsion system was studied and compared to that of GG, LBG, KGM, and cAX. In addition, GG was enzymatically modified in order to examine the effect of the degree of polymerization and the degree of substitution of galactomannans on emulsion stability. Use of GGM increased the turbidity of emulsions both immediately after preparation and after storage of up to 14 days at room temperature. GGM emulsions had higher turbidity than the emulsions containing other mannans. Increasing the storage temperature to +45 ºC led to rapid emulsion breakdown, but a decrease in storage temperature increased emulsion stability after 14 days. A low degree of polymerization and a high degree of substitution of the modified galactomannans were associated with a decrease in emulsion turbidity.

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Inadvertent climate modification has led to an increase in urban temperatures compared to the surrounding rural area. The main reason for the temperature rise is the altered energy portioning of input net radiation to heat storage and sensible and latent heat fluxes in addition to the anthropogenic heat flux. The heat storage flux and anthropogenic heat flux have not yet been determined for Helsinki and they are not directly measurable. To the contrary, turbulent fluxes of sensible and latent heat in addition to net radiation can be measured, and the anthropogenic heat flux together with the heat storage flux can be solved as a residual. As a result, all inaccuracies in the determination of the energy balance components propagate to the residual term and special attention must be paid to the accurate determination of the components. One cause of error in the turbulent fluxes is the fluctuation attenuation at high frequencies which can be accounted for by high frequency spectral corrections. The aim of this study is twofold: to assess the relevance of high frequency corrections to water vapor fluxes and to assess the temporal variation of the energy fluxes. Turbulent fluxes of sensible and latent heat have been measured at SMEAR III station, Helsinki, since December 2005 using the eddy covariance technique. In addition, net radiation measurements have been ongoing since July 2007. The used calculation methods in this study consist of widely accepted eddy covariance data post processing methods in addition to Fourier and wavelet analysis. The high frequency spectral correction using the traditional transfer function method is highly dependent on relative humidity and has an 11% effect on the latent heat flux. This method is based on an assumption of spectral similarity which is shown not to be valid. A new correction method using wavelet analysis is thus initialized and it seems to account for the high frequency variation deficit. Anyhow, the resulting wavelet correction remains minimal in contrast to the traditional transfer function correction. The energy fluxes exhibit a behavior characteristic for urban environments: the energy input is channeled to sensible heat as latent heat flux is restricted by water availability. The monthly mean residual of the energy balance ranges from 30 Wm-2 in summer to -35 Wm-2 in winter meaning a heat storage to the ground during summer. Furthermore, the anthropogenic heat flux is approximated to be 50 Wm-2 during winter when residential heating is important.

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Nucleation is the first step in the formation of a new phase inside a mother phase. Two main forms of nucleation can be distinguished. In homogeneous nucleation, the new phase is formed in a uniform substance. In heterogeneous nucleation, on the other hand, the new phase emerges on a pre-existing surface (nucleation site). Nucleation is the source of about 30% of all atmospheric aerosol which in turn has noticeable health effects and a significant impact on climate. Nucleation can be observed in the atmosphere, studied experimentally in the laboratory and is the subject of ongoing theoretical research. This thesis attempts to be a link between experiment and theory. By comparing simulation results to experimental data, the aim is to (i) better understand the experiments and (ii) determine where the theory needs improvement. Computational fluid dynamics (CFD) tools were used to simulate homogeneous onecomponent nucleation of n-alcohols in argon and helium as carrier gases, homogeneous nucleation in the water-sulfuric acid-system, and heterogeneous nucleation of water vapor on silver particles. In the nucleation of n-alcohols, vapor depletion, carrier gas effect and carrier gas pressure effect were evaluated, with a special focus on the pressure effect whose dependence on vapor and carrier gas properties could be specified. The investigation of nucleation in the water-sulfuric acid-system included a thorough analysis of the experimental setup, determining flow conditions, vapor losses, and nucleation zone. Experimental nucleation rates were compared to various theoretical approaches. We found that none of the considered theoretical descriptions of nucleation captured the role of water in the process at all relative humidities. Heterogeneous nucleation was studied in the activation of silver particles in a TSI 3785 particle counter which uses water as its working fluid. The role of the contact angle was investigated and the influence of incoming particle concentrations and homogeneous nucleation on counting efficiency determined.

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Interaction between forests and the atmosphere occurs by radiative and turbulent transport. The fluxes of energy and mass between surface and the atmosphere directly influence the properties of the lower atmosphere and in longer time scales the global climate. Boreal forest ecosystems are central in the global climate system, and its responses to human activities, because they are significant sources and sinks of greenhouse gases and of aerosol particles. The aim of the present work was to improve our understanding on the existing interplay between biologically active canopy, microenvironment and turbulent flow and quantify. In specific, the aim was to quantify the contribution of different canopy layers to whole forest fluxes. For this purpose, long-term micrometeorological and ecological measurements made in a Scots pine (Pinus sylvestris) forest at SMEAR II research station in Southern Finland were used. The properties of turbulent flow are strongly modified by the interaction between the canopy elements: momentum is efficiently absorbed in the upper layers of the canopy, mean wind speed and turbulence intensities decrease rapidly towards the forest floor and power spectra is modulated by spectral short-cut . In the relative open forest, diabatic stability above the canopy explained much of the changes in velocity statistics within the canopy except in strongly stable stratification. Large eddies, ranging from tens to hundred meters in size, were responsible for the major fraction of turbulent transport between a forest and the atmosphere. Because of this, the eddy-covariance (EC) method proved to be successful for measuring energy and mass exchange inside a forest canopy with exception of strongly stable conditions. Vertical variations of within canopy microclimate, light attenuation in particular, affect strongly the assimilation and transpiration rates. According to model simulations, assimilation rate decreases with height more rapidly than stomatal conductance (gs) and transpiration and, consequently, the vertical source-sink distributions for carbon dioxide (CO2) and water vapor (H2O) diverge. Upscaling from a shoot scale to canopy scale was found to be sensitive to chosen stomatal control description. The upscaled canopy level CO2 fluxes can vary as much as 15 % and H2O fluxes 30 % even if the gs models are calibrated against same leaf-level dataset. A pine forest has distinct overstory and understory layers, which both contribute significantly to canopy scale fluxes. The forest floor vegetation and soil accounted between 18 and 25 % of evapotranspiration and between 10 and 20 % of sensible heat exchange. Forest floor was also an important deposition surface for aerosol particles; between 10 and 35 % of dry deposition of particles within size range 10 30 nm occurred there. Because of the northern latitudes, seasonal cycle of climatic factors strongly influence the surface fluxes. Besides the seasonal constraints, partitioning of available energy to sensible and latent heat depends, through stomatal control, on the physiological state of the vegetation. In spring, available energy is consumed mainly as sensible heat and latent heat flux peaked about two months later, in July August. On the other hand, annual evapotranspiration remains rather stable over range of environmental conditions and thus any increase of accumulated radiation affects primarily the sensible heat exchange. Finally, autumn temperature had strong effect on ecosystem respiration but its influence on photosynthetic CO2 uptake was restricted by low radiation levels. Therefore, the projected autumn warming in the coming decades will presumably reduce the positive effects of earlier spring recovery in terms of carbon uptake potential of boreal forests.

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The Earth s climate is a highly dynamic and complex system in which atmospheric aerosols have been increasingly recognized to play a key role. Aerosol particles affect the climate through a multitude of processes, directly by absorbing and reflecting radiation and indirectly by changing the properties of clouds. Because of the complexity, quantification of the effects of aerosols continues to be a highly uncertain science. Better understanding of the effects of aerosols requires more information on aerosol chemistry. Before the determination of aerosol chemical composition by the various available analytical techniques, aerosol particles must be reliably sampled and prepared. Indeed, sampling is one of the most challenging steps in aerosol studies, since all available sampling techniques harbor drawbacks. In this study, novel methodologies were developed for sampling and determination of the chemical composition of atmospheric aerosols. In the particle-into-liquid sampler (PILS), aerosol particles grow in saturated water vapor with further impaction and dissolution in liquid water. Once in water, the aerosol sample can then be transported and analyzed by various off-line or on-line techniques. In this study, PILS was modified and the sampling procedure was optimized to obtain less altered aerosol samples with good time resolution. A combination of denuders with different coatings was tested to adsorb gas phase compounds before PILS. Mixtures of water with alcohols were introduced to increase the solubility of aerosols. Minimum sampling time required was determined by collecting samples off-line every hour and proceeding with liquid-liquid extraction (LLE) and analysis by gas chromatography-mass spectrometry (GC-MS). The laboriousness of LLE followed by GC-MS analysis next prompted an evaluation of solid-phase extraction (SPE) for the extraction of aldehydes and acids in aerosol samples. These two compound groups are thought to be key for aerosol growth. Octadecylsilica, hydrophilic-lipophilic balance (HLB), and mixed phase anion exchange (MAX) were tested as extraction materials. MAX proved to be efficient for acids, but no tested material offered sufficient adsorption for aldehydes. Thus, PILS samples were extracted only with MAX to guarantee good results for organic acids determined by liquid chromatography-mass spectrometry (HPLC-MS). On-line coupling of SPE with HPLC-MS is relatively easy, and here on-line coupling of PILS with HPLC-MS through the SPE trap produced some interesting data on relevant acids in atmospheric aerosol samples. A completely different approach to aerosol sampling, namely, differential mobility analyzer (DMA)-assisted filter sampling, was employed in this study to provide information about the size dependent chemical composition of aerosols and understanding of the processes driving aerosol growth from nano-size clusters to climatically relevant particles (>40 nm). The DMA was set to sample particles with diameters of 50, 40, and 30 nm and aerosols were collected on teflon or quartz fiber filters. To clarify the gas-phase contribution, zero gas-phase samples were collected by switching off the DMA every other 15 minutes. Gas-phase compounds were adsorbed equally well on both types of filter, and were found to contribute significantly to the total compound mass. Gas-phase adsorption is especially significant during the collection of nanometer-size aerosols and needs always to be taken into account. Other aims of this study were to determine the oxidation products of β-caryophyllene (the major sesquiterpene in boreal forest) in aerosol particles. Since reference compounds are needed for verification of the accuracy of analytical measurements, three oxidation products of β-caryophyllene were synthesized: β-caryophyllene aldehyde, β-nocaryophyllene aldehyde, and β-caryophyllinic acid. All three were identified for the first time in ambient aerosol samples, at relatively high concentrations, and their contribution to the aerosol mass (and probably growth) was concluded to be significant. Methodological and instrumental developments presented in this work enable fuller understanding of the processes behind biogenic aerosol formation and provide new tools for more precise determination of biosphere-atmosphere interactions.

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Floating in the air that surrounds us is a number of small particles, invisible to the human eye. The mixture of air and particles, liquid or solid, is called an aerosol. Aerosols have significant effects on air quality, visibility and health, and on the Earth's climate. Their effect on the Earth's climate is the least understood of climatically relevant effects. They can scatter the incoming radiation from the Sun, or they can act as seeds onto which cloud droplets are formed. Aerosol particles are created directly, by human activity or natural reasons such as breaking ocean waves or sandstorms. They can also be created indirectly as vapors or very small particles are emitted into the atmosphere and they combine to form small particles that later grow to reach climatically or health relevant sizes. The mechanisms through which those particles are formed is still under scientific discussion, even though this knowledge is crucial to make air quality or climate predictions, or to understand how aerosols will influence and will be influenced by the climate's feedback loops. One of the proposed mechanisms responsible for new particle formation is ion-induced nucleation. This mechanism is based on the idea that newly formed particles were ultimately formed around an electric charge. The amount of available charges in the atmosphere varies depending on radon concentrations in the soil and in the air, as well as incoming ionizing radiation from outer space. In this thesis, ion-induced nucleation is investigated through long-term measurements in two different environments: in the background site of Hyytiälä and in the urban site that is Helsinki. The main conclusion of this thesis is that ion-induced nucleation generally plays a minor role in new particle formation. The fraction of particles formed varies from day to day and from place to place. The relative importance of ion-induced nucleation, i.e. the fraction of particles formed through ion-induced nucleation, is bigger in cleaner areas where the absolute number of particles formed is smaller. Moreover, ion-induced nucleation contributes to a bigger fraction of particles on warmer days, when the sulfuric acid and water vapor saturation ratios are lower. This analysis will help to understand the feedbacks associated with climate change.

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We present a laser-based system to measure the refractive index of air over a long path length. In optical distance measurements it is essential to know the refractive index of air with high accuracy. Commonly, the refractive index of air is calculated from the properties of the ambient air using either Ciddor or Edlén equations, where the dominant uncertainty component is in most cases the air temperature. The method developed in this work utilises direct absorption spectroscopy of oxygen to measure the average temperature of air and of water vapor to measure relative humidity. The method allows measurement of temperature and humidity over the same beam path as in optical distance measurement, providing spatially well matching data. Indoor and outdoor measurements demonstrate the effectiveness of the method. In particular, we demonstrate an effective compensation of the refractive index of air in an interferometric length measurement at a time-variant and spatially non-homogenous temperature over a long time period. Further, we were able to demonstrate 7 mK RMS noise over a 67 m path length using 120 s sample time. To our knowledge, this is the best temperature precision reported for a spectroscopic temperature measurement.

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Absorption due to immersion in aqueous media consisting of either saline or seawater or due to exposure to water vapor conditions and the attendant effect on the compressive properties of syntactic foam reinforced with E-glass fibers in the form of chopped strands were studied. Whereas the compressive strength decreased in samples exposed to water vapor, the saline or seawater immersed samples showed increase when compared to the dry sample. The decrease in strength in the vapor-exposed case is ascribed to higher absorption of water and to debonding and damaged features for interfaces. The enhancement of strength values for the samples immersed in saltish media is traced to the larger size of the chloride ion and resultant changes in the stress state around the fiber-bearing regions. Recourse to an analysis of scanning electron microscopic pictures of the compression-failed samples is taken to explain the observed trends.

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This paper describes the near surface characteristics and vertical variations based on the observations made at 17.5degreesN and 89degreesE from ORV Sagar Kanya in the north Bay of Bengal during the Bay of Bengal Monsoon Experiment (BOBMEX) carried out in July-August 1999. BOBMEX captured both the active and weak phases of convection. SST remained above the convection threshold throughout the BOBMEX. While the response of the SST to atmospheric forcing was clearly observed, the response of the atmosphere to SST changes was not clear. SST decreased during periods of large scale precipitation, and increased during a weak phase of convection. It is shown that the latent heat flux at comparable wind speeds was about 25-50% lower over the Bay during BOBMEX compared to that over the Indian Ocean during other seasons and tropical west Pacific. On the other hand, the largest variations in the surface daily net heat flux are observed over the Bay during BOBMEX. SST predicted using observed surface fluxes showed that 1-D heat balance model works sometime but not always, and horizontal advection is important. The high resolution Vaisala radiosondes launched during BOBMEX could clearly bring out the changes in the vertical structure of the atmosphere between active and weak phases of convection. Convective Available Potential Energy of the surface air decreased,by 2-3 kJ kg(-1) following convection, and recovered in a time period of one or two days. The mid tropospheric relative humidity and water vapor content, and wind direction show the major changes between the active and weak phases of convection.

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The possible chemical reactions that take place during the growth of single crystal films of silicon on sapphire (SOS) are analyzed thermodynamically. The temperature for the growth of good quality epitaxial films is dependent on the extent of water vapor present in the carrier gas. The higher the water vapor content the higher the temperature needed to grow SOS films. Due to the interaction of silicon with sapphire at elevated temperatures, SOS films are doped with aluminum. The extent of doping is dependent on the conditions of film growth. The doping by aluminum from the substrate increases with increasing growth temperatures and decreasing growth rates. The equilibrium concentrations of aluminum at the silicon-sapphire interface are calculated as a function of deposition temperature, assuming that SiO2 or Al6Si2O13 are the products of reaction. It is most likely that the product could be a solid solutio n of Al2O3 in SiO2. The total amount of aluminum released due to the interaction between silicon and sapphire will account only for the formation of not more than one monolayer of reaction product unless the films are annealed long enough at elevated temperatures. This value is in good agreement with the recently reported observations employing high resolution transmission electron microscopy.

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Structure and phase transition of LaO1−xF1+2x, prepared by solid-state reaction of La2O3 and LaF3, was investigated by X-ray powder diffraction and differential scanning calorimetry for both positive and negative values of the nonstoichiometric parameter x. The electrical conductivity was investigated as a function of temperature and oxygen partial pressure using AC impedance spectroscopy. Fluoride ion was identified as the migrating species in LaOF by coulometric titration and transport number determined by Tubandt technique and EMF measurements. Activation energy for conduction in LaOF was 58.5 (±0.8) kJ/mol. Conductivity increased with increasing fluorine concentration in the oxyfluoride phase, suggesting that interstitial fluoride ions are more mobile than vacancies. Although the values of ionic conductivity of cubic LaOF are lower, the oxygen partial pressure range for predominantly ionic conduction is larger than that for the commonly used stabilized-zirconia electrolytes. Thermodynamic analysis shows that the oxyfluoride is stable in atmospheres containing diatomic oxygen. However, the oxyfluoride phase can degrade with time at high temperatures in atmospheres containing water vapor, because of the higher stability of HF compared with H2O.

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The high-temperature oxidation behavior of modified 304 austenitic stainless steels in a water vapor atmosphere was investigated. Samples were prepared by various thermo mechanical treatments to result in different grain sizes in the range 8-30 mu m. Similar I 3 pound grain boundary fraction was achieved to eliminate any grain-boundary characteristics effect. Samples were oxidized in an air furnace at 700 A degrees C with 20 % water vapor atmosphere. On the fine-grained sample, a uniform Cr2O3 layer was formed, which increased the overall oxidation resistance. Whereas on the coarse-grained sample, an additional Fe2O3 layer formed on the Cr-rich oxide layer, which resulted in a relatively high oxidation rate. In the fine-grained sample, grain boundaries act as rapid diffusion paths for Cr and provided enough Cr to form Cr2O3 oxide on the entire sample surface.