Structure and properties of low temperature plasma carburized austenitic stainless steels

Austenitic stainless steels cannot be conventionally surface treated at temperatures close to 550 degrees C due to intense precipitation of nitrides or carbides. Plasma carburizing allows introducing carbon in the steel at temperatures below 500 degrees C without carbide precipitation. Plasma carburizing of AISI 316L was carried out at 480 degrees C and 400 degrees C, during 20 h, using CH(4) as carbon carrier gas. The results show that carbon expanded austenite (gamma(c)), 20 mu m in depth, was formed on the surface after the 480 degrees C treatment. Carbon expanded austenite (gamma(c)), 8 mu m in depth, was formed on the surface after the 400 degrees C treatment. DRX results showed that the austenitic FCC lattice parameter increases from 0.358 nm to 0.363 nm for the 400 degrees C treatment and to 0.369 nm for the 480 degrees C treatment, giving an estimation of circa 10 at.% carbon content for the latter. Lattice distortion, resulting from the expansion and the associated compressive residual stresses increases the surface hardness to 1040 HV(0.025). Micro-scale tensile tests were conducted on specimens prepared with the conditions selected above, which has indicated that the damage imposed to the expanded austenite layer was more easily related to each separated grain than to the overall macro-scale stresses imposed by the tensile test. (C) 2009 Elsevier B.V. All rights reserved.

The study of ternary carbides formation during SPS consolidation process in the WC-Co-steel system

Tungsten carbide has a wide range of applications, mainly cemented carbides made of WC and Co, as wear resistant materials. However, the high cost of WC-Co powders encourages the use of a substrate to manufacture a functionally graded material (FGM) tool made of WC-Co and a tool steel. These materials join the high wear resistance of the cemented carbide and the toughness of the steel. This work deals with the study interaction of the WC-Co and H13 steel to design a functionally graded material by means of spark plasma sintering (SPS). The SPS, a novel sintering technique reaching the consolidation of the powders at relatively low temperatures and short dwell times, is a promising technique in processing materials. In this study, WC, H13 steel, WC-Co, WC-H13 steel and WC-Co-H13 steel bulk samples were investigated using scanning electron microscopy and X-ray diffraction techniques to evaluate the phase transformations involved during SPS consolidation process. The W(2)C and W(3)Fe(3)C precipitation were identified after the SPS consolidation of the WC and WC-H13 steel samples, respectively. The precipitation Of W(4)Co(2)C was also identified in the WC-Co and WC-Co-H13 steel samples. The WC-H 13 steel and WC-Co-H13 steel were also evaluated after heat treatments at 1100 degrees C for 9 h, which enhanced the chemical interaction and the precipitation of W(3)Fe(3)C and W(4)Co(2)C, respectively. (C) 2009 Elsevier Ltd. All rights reserved.

Comparison of adsorbent films obtained by plasma polymerization of oxygenated organic compounds

Thin films obtained by plasma polymerization of ethyl ether, methyl or ethyl acetate, acetaldehyde, acetone and 2-propanol were compared. Infrared spectroscopy (FFIR), resistance to chemicals, contact angle measurements, X-ray photoelectron spectroscopy (XPS), optical and scanning electron microscopy (SEM), and quartz crystal microbalance (QCM) were carried out. For all films FTIR showed high intensity for polar bonds yet the films are not resistant to polar solvents. Contact angle measurements revealed hydrophilic and organophilic surfaces and XPS pointed out a high proportion of oxygenated bonds. All films showed good step coverage and peeling was significant only with acetone and 2-propanol. All films are adsorbent for organic compounds in a large scale of polarity but acetaldehyde and 2-propanol act like a selective membrane. Also, deposition of these films on hydrophobic substrates leads to island formation. A possible model to explain the results must consider the hydrogen bridge formation on 2-propanol and acetaldehyde films. Ethyl ether, ethyl and methyl acetate showed good characteristics for development of sensor and sample pretreatment using miniaturized devices. (C) 2007 Elsevier B.V. All rights reserved.

Magnetic losses evolution of a semi-processed steel during forced aging treatments

An ultra-low carbon steel (30 ppm after decarburization) containing Al and Si was aged for distinct soaking times at 210 degrees C. The core loss increased continuously until around 24 h. After that, only slight changes were verified. It was found that only the hysteresis loss component changed during the aging treatment. By internal friction test and transmission electron microscopy it was seen that carbon precipitation caused the magnetic aging. By scanning electron microscopy it could be concluded that the increase of aging index was attributed to the high number of carbides larger than 0.1 mu m. (C) 2008 Elsevier B. V. All rights reserved.

Corrosion resistant and adsorbent plasma polymerized thin film

Adsorbent and corrosion resistant films are useful for sensor development. Therefore, the aim of this work is the production and characterization of plasma polymerized fluorinated organic ether thin films for sensor development. The polymerized reactant was methyl nonafluoro(iso)butyl ether. Infrared Spectroscopy showed fluorinated species and eventually CO but CH(n) is a minor species. Contact angle measurements indicated that the film is hydrophobic and organophilic but oleophobic. Optical microscopy reveals not only a good adherence on metals and acrylic but also resistance for organic solvents, acid and basic aqueous solution exposure. Double layer and intermixing are possible and might lead to island formation. Quartz Crystal Microbalance showed that 2-propanol permeates the film but there is no sensitivity to n-hexane. The microreactor manufactured using a 73 cm long microchannel can retain approximately 9 X 10(-4) g/cm(2) of 2-propanol in vapor phase. Therefore, the film is a good candidate for preconcentration of volatile organic compounds even in corrosive environment. (C) 2009 Elsevier B.V. All rights reserved.

Influence of substrate surface topography in the deposition of nanostructured diamond-like carbon films by high density plasma chemical vapor deposition

In this work, we have studied the influence of the substrate surface condition on the roughness and the structure of the nanostructured DLC films deposited by High Density Plasma Chemical Vapor Deposition. Four methods were used to modify the silicon wafers surface before starting the deposition processes of the nanostructured DLC films: micro-diamond powder dispersion, micro-graphite powder dispersion, and roughness generation by wet chemical etching and roughness generation by plasma etching. The reference wafer was only submitted to a chemical cleaning. It was possible to see that the final roughness and the sp(3) hybridization degree strongly depend on the substrate surface conditions. The surface roughness was observed by AFM and SEM and the hybridization degree of the DLC films was analyzed by Raman Spectroscopy. In these samples, the final roughness and the sp(3) hybridization quantity depend strongly on the substrate surface condition. Thus, the effects of the substrate surface on the DLC film structure were confirmed. These phenomena can be explained by the fact that the locally higher surface energy and the sharp edges may induce local defects promoting the nanostructured characteristics in the DLC films. (C) 2008 Elsevier B.V. All rights reserved.

Improved moisture and hydrocarbons barrier of epoxy resin-based coating

To improve the surface characteristics of epoxy resin coatings, a treatment by fluorine-containing plasma was used to develop a coating with low surface free energy and improved chemical resistance. Through the coating analysis it was possible to verify information about the CF(n) bond formation and the fluorination depth. The best plasma process parameters presented the best fluorination depth, 90 nm, and fluorine concentration was nearly 30%. The improvement in contact angle of water was 50% and of raw petroleum was 130%. Salt spray test proves that the coating fluorination decreases the chance of substrate corrosion.

Structure and properties of an austenitic stainless steel AISI 316L grade ASTM F138 after low temperature plasma nitriding

Austenitic stainless steels cannot be conventionally nitrided at temperatures near 550 degrees C due to the intense precipitation of chromium nitrides in the diffusion zone. The precipitation of chro-mium nitrides increases the hardness but severely impairs corrosion resistance. Plasma nitriding allows introducing nitrogen in the steel at temperatures below 450 degrees C, forming pre-dominantly expanded austenite (gamma(N)), with a crystalline structure best represented by a special triclin-ic lattice, with a very high nitrogen atomic concentration promoting high compressive residual stresses at the surface, increasing substrate hardness from 4 GPa up to 14 GPa on the nitrided case.

Structural and physicochemical characterization of RS prepared using hydrolysis and heat treatments of chickpea starch

The aim of this study was to evaluate the production and the structural and physicochemical properties of RS obtained by molecular mass reduction (enzyme or acid) and hydrothermal treatment of chickpea starch. Native and gelatinized starch were submitted to acid (2 M HCl for 2.5 h) or enzymatic hydrolysis (pullulanase, 40 U/g per 10 h), autoclaved (121 degrees C/30 min), stored under refrigeration (4 degrees C/24 h), and lyophilized. The hydrolysis of starch increased the RS content from 16% to values between 20 and 32%, and the enzymatic treatment of the gelatinized starch was the most efficient. RS showed an increase in water absorption and water solubility indexes due to hydrolytic and thermal process. The processes for obtaining RS changed the crystallinity pattern from C to B. Hydrolysis treatments caused an increase in relative crystallinity due to the greater retrogradation caused by the reduction in MW. RS obtained from hydrolysis showed a reduction in viscosity, indicating the rupture of molecules. The viscosity seemed to be inversely proportional to the RS content in the sample.

A positive growth response to NaCl applications in Eucalyptus plantations established on K-deficient soils

Contrasting responses of Eucalyptus trees to K fertilizer applications have been reported on soils with low K contents. A complete randomized block experiment was set up in Brazil to test the hypothesis that large atmospheric deposits of NaCl in coastal regions might lead to a partial substitution of K by Na in Eucalyptus physiology and enhance tree growth. Treatments with application of 1.5, 3.0, 4.5 kmol K ha(-1) (K(1.5), K(3.0), 1(4.5, respectively) as KCl, 3.0 kmol K ha(-1) applied as K(2)SO(4), 3.0 kmol Na ha(-1) (Na(3.0)) as NaCl commercialized for cattle feeding, and a mixture of 1.5 kmol K + 1.5 kmol Na ha(-1) (K(1.5) + Na(1.5)) were compared to a control treatment (C) with no K and Na applications. All the plots were fertilized with large amounts of the other nutrients. A positive effect of NaCl applications on the growth of E. grandis trees was observed. NaCl and KCl additions in treatments Na(3.0) and K(3.0) increased above-ground biomass by 56% and 130% three years after planting, respectively, in comparison with the C treatment. By contrast, accumulated litterfall up to age 3 years was not significantly modified. NaCl applications in the Na(3.0) treatment significantly increased Na accumulation in above-ground tree components but did not modify K accumulation, whatever the sampling age. A partial substitution of K by Na in tree physiology, as observed for various agricultural crops, might explain this behaviour. Our results suggest the possibility of applying inexpensive K fertilizers, which are less purified in Na, and explain why high yields are achieved without K fertilizer applications in areas with large dry depositions of marine aerosols. Further investigations are necessary to identify the processes involving Na in Eucalyptus tree physiology. (C) 2009 Elsevier B.V. All rights reserved.

Production and carbon allocation in a clonal Eucalyptus plantation with water and nutrient manipulations

We examined resource limitations on growth and carbon allocation in a fast-growing, clonal plantation of Eucalyptus grandis x urophylla in Brazil by characterizing responses to annual rainfall, and response to irrigation and fertililization for 2 years. Productivity measures included gross primary production (GPP), total belowground carbon allocation (TBCA), bole growth, and net ecosystem production (NEP). Replicate plots within a single plantation were established at the midpoint of the rotation (end of year 3), with treatments of no additional fertilization or irrigation, heavy fertilization (to remove any nutrient limitation), irrigation (to remove any water limitation), and irrigation plus fertilization. Rainfall was unusually high in the first year (1769mm) of the experiment, and control plots had high rates of GPP (6.64 kg C m(-2) year(-1)), TBCA (2.14 kg C m(-2) year(-1)), and bole growth (1.81 kg C m(-2) year). Irrigation increased each of these rates by 15-17%. The second year of the experiment had average rainfall (1210 mm), and lower rainfall decreased production in control plots by 46% (GPP), 52% (TBCA), and 40% (bole growth). Fertilization treatments had neglible effects. The response to irrigation was much greater in the drier year, with irrigated plots exceeding the production in control plots by 83% (GPP), 239% (TBCA), and 24% (bole growth). Even though the rate of irrigation ensured no water limitation to tree growth, the high rainfall year showed higher production in irrigated plots for both GPP (38% greater than in drier year) and bole growth (23% greater). Varying humidity and supplies of water led to a range in NEP of 0.8-2.7 kg C m(-2) year. This difference between control and irrigated treatments, combined with differences between drier and wetter years, indicated a strong response of these Eucalyptus trees to both water supply and atmospheric humidity during the dry season. The efficiency of converting light energy into fixed carbon ranged from a low of 0.027 mol C to a high of 0.060 mol C per mol of absorbed photosynthetically active radiation (APAR), and the efficiency of bolewood production ranged from 0.78 to 1.98 g wood per MJ of APAR. Irrigation increased the efficiency of wood production per unit of water used from 2.55 kg wood m(-3) in the rainfed plot to 3.51 kg m(-3) in irrigated plots. Detailed information on the response of C budgets to environmental conditions and resource supplies will be necessary for accurate predictions of plantation yields across years and landscapes. (V) 2007 Elsevier B.V. All rights reserved.

Postharvest harpin or Bacillus thuringiensis treatments suppress citrus black spot in `Valencia` oranges

Citrus black spot (CBS) caused by Guignardia citricarpa represents an important threat to citriculture in Brazil. Limited information is available regarding potential biological control agents and new alternative compounds that may provide protection of orange fruits against the disease. In this study, the effects of commercial products based on Bacillus thuringiensis var. kurstaki (Bt) bacterium, Bt pure isolates and Harpin protein (Messenger (R)) on the postharvest control of CBS, were evaluated in `Valencia` sweet orange fruits harvested for three consecutive years in a citrus grove. The fruits were sprayed with the following products: DiPel (R) WP (Bt, subspecies, kurstaki strain HD-1,16,000 International Units mg(-1), 32 g active ingredient kg(-1)) (1, 20 and 50 mg ml(-1)), Dimy Pel (R) WP (Bt, subspecies, kurstaki, strain HD-1, 17,600 IU mg(-1), 26 g active ingredient l(-1)) (2, 20 and 50 mg ml(-1)), Messenger (R) (3% harpin protein) (1 and 2 mg ml(-1)) and fungicide Tecto (R) Flowable SC (thiabendazole, 485 gl(-1)) (0.8g active ingredient l(-1)), besides the Bt isolates, Bt- HD-567, Bt- DiPel and Bt- Dimy (9 x 10(8) CFU ml(-1)). Ten days after treatment, the number of newly developed CBS lesions and pycnidia produced were evaluated using fifty fruits per treatment. The Dimy Pel (R) and Messenger (R) reduced the number of new developed CBS lesions on fruits in up to 67% and 62%, respectively. All applied treatments drastically decreased the number of pycnidia produced in the CBS lesions on orange fruits with 85% to 96% reductions compared to the untreated control. Volatile compounds produced by the isolates Bt- HD-567, Bt- Dimy and Bt- DiPel, reduced the number of lesions on treated fruits by 70%, 65% and 71% compared to the control, respectively. In addition, the survival of Bt isolates on orange fruit surfaces were evaluated by recovering and quantifying the number of CFU every seven days for up to 28 days. The declines in survival rates on orange fruit surfaces were drastic for the three strains of Bt in the first week. The CFU numbers of all applied isolates declined by 4 to 5 orders of magnitude after storage at room temperature for 28 days. In vitro assays revealed that the Bt isolates significantly reduced the mycelial growth of the pathogen, ranging from 32% to 51%, compared to the control, whereas no inhibitory effect was observed in the presence of Messenger (R). (C) 2010 Elsevier Ltd. All rights reserved.

Atmospheric Absorption of Fluoride by Cultivated Species. Leaf Structural Changes and Plant Growth

Fluoride (F) is an air pollutant that causes phytotoxicity. Besides the importance of this, losses of agricultural crops in the vicinity of F polluting industries in Brazil have been recently reported. Injuries caused to plant leaf cell structures by excess F are not well characterized. However, this may contribute to understanding the ways in which plant physiological and biochemical processes are altered. A study evaluated the effects of the atmospheric F on leaf characteristics and growth of young trees of sweet orange and coffee exposed to low (0.04 mol L(-1)) or high (0.16 mol L(-1)) doses of HF nebulized in closed chamber for 28 days plus a control treatment not exposed. Gladiolus and ryegrass were used as bioindicators in the experiment to monitor F exposure levels. Fluoride concentration and dry mass of leaves were evaluated. Leaf anatomy was observed under light and electron microscopy. High F concentrations (similar to 180 mg kg(-1)) were found in leaves of plants exposed at the highest dose of HF. Visual symptoms of F toxicity in leaves of citrus and coffee were observed. Analyses of plant tissue provided evidence that F caused degeneration of cell wall and cytoplasm and disorganization of bundle sheath, which were more evident in Gladiolus and coffee. Minor changes were observed for sweet orange and ryegrass. Increase on individual stomatal area was also marked for the Gladiolus and coffee, and which were characterized by occurrence of opened ostioles. The increased F absorption by leaves and changes at the structural and ultrastructural level of leaf tissues correlated with reduced plant growth.

Microbial Metabolic Potential Affected by Surplus Wastewater Irrigation in Tropical Soil Cultivated with Tifton 85 Bermuda Grass (Cynodon dactylon Pers. X C. niemfuensis Vanderyst)

Agricultural reuse of treated sewage effluent (TSE) is an environmental and economic practice; however, little is known about its effects on the characteristics and microbial function in tropical soils. The effect of surplus irrigation of a pasture with TSE, in a period of 18 months, was investigated, considering the effect of 0% surplus irrigation with TSE as a control. In addition, the experiment consisted of three surplus treatments (25%, 50%, and 100% excess) and a nonirrigated pasture area (SE) to compare the soil microbial community level physiological profiles, using the Biolog method. The TSE application increased the average substrate consumption of the soil microbial community, based on the kinetic parameters of the average well color development curve fitting. There were no significant differences between the levels of surplus irrigation treatments. Surplus TSE pasture irrigation caused minor increases in the physiological status of the soil microbial community but no detectable damage to the pasture or soil.

Determination of heavy metals by inductively coupled plasma-optical emission spectrometry in fish from the Piracicaba River in Southern Brazil

A total of 202 fish, representing 16 species, were collected during 2008 (March-October) in the Tanquan region of the Piracicaba River using nets. Flesh samples were collected and analyzed, using inductively coupled plasma-optical emission spectroscopy for Al, As, Cd, Co Cr, Cu, Mn, Mo, Ni, Ph, Se, Sn, Sr, and Zn. The results showed that the flesh of these fish all contained extremely high levels of Al and Sr, and moderately high levels of Cr, As, Zn, Ni. Mn and Pb. The metals were higher in these fish during rainy season, with fish collected during the months of March and October being the highest. In addition, the accumulation of metals was species-dependent. Cascudos (Hypostomus punctatus) and piranhas (Serrasalmus spilopleura) exhibited high levels of almost all of the metals, while curimbata (Prochilodus lineatus) had moderate levels. A few species, including pacu (Piaractus mesopotamicus) and dourado (Salminus maxillosus), had very low levels of most metals. The results show that the Piracicaba River Basin is widely contaminated with high levels of many toxic heavy metals, and that human consumption of some fish species is a human health concern. (C) 2009 Elsevier B.V. All rights reserved.