Soil Solution as Affected by Plant Residues and Nitrogen Rates

Cation mobility in acidic soils with low organic-matter contents depends not only on sorption intensity but also on the solubility of the species present in soil solution. In general, the following leaching gradient is observed: potassium (K+) magnesium (Mg2+) calcium (Ca2+) aluminum (Al3+). To minimize nutrient losses and ameliorate the subsoil, soil solution must be changed, favoring higher mobility of M2+ (metal ions) forms. This would be theoretically possible if plant residues were kept on the soil surface. An experiment was conducted in pots containing a Distroferric Red Latosol, with soil solution extractors installed at two depths. Pearl millet, black oat, and oilseed radish residues were laid on the soil surface, and nitrogen (as ammonium nitrate) was applied at rates ranging from 0 to 150mgkg-1. Corn was grown for 52 days. Except for K+ and ammonium (NH4 +), nitrogen rates and plant residues had little effect upon the concentrations and forms of the elements in the soil solution. Presence of cover crop residues on soil surface decreased the effect of nitrogen fertilizer on Ca leaching. More than 90% of the Ca2+, Mg2+, and K+ were found as free ions. The Al3+ was almost totally complexed as Al(OH3)0. Nitrogen application increased the concentrations of almost all the ions in soil solution, including Al3+, although there was no modification in the leaching gradient.

MONITORING NITROGEN NUTRITION IN COTTON

Both N excess and deficiency may affect cotton yield and quality. It would therefore be useful to base the N management fertilization on the monitoring of the nutritional status. This study investigated the correlations among the following determination methods of the N nutritional status of cotton (Gossypium hirsutum L., var. Latifolia): chlorophyll readings (SPAD-502 (R), Minolta), specific-ion nitrate meter (Nitrate Meter C-141, Horiba-Cardy (R)), and laboratory analysis (conventional foliar diagnosis). Samples were taken weekly from two weeks before flowering to the fifth week after the first flower. The experiment was conducted on the Fazenda Santa Tereza, Itapeva, State of São Paulo, Brazil. The crop was fertilized with 40 kg ha(-1) N at planting and 0, 30, 60, 90, and 120 kg ha(-1) of side-dressed N. The range of leaf N contents reported as adequate for samples taken 80-90 days after plant emergence (traditional foliar diagnosis) may be used as reference from the beginning of flowering when the plant is not stressed. Specific-ion nitrate meter readings can be used as a nutritional indicator of cotton nutrition from one week after pinhead until the third week of flowering. In this case, plants are well-nourished when readings exceed 8,000 mg L(-1) NO(3)(-). The chlorophyll meter can also be used to estimate the nutritional status of cotton from the third week of flowering. In this case the readings should be above 48 in well-nourished plants.

Effect of target bias on magnetic field enhanced plasma immersion ion implantation

Recent studies have demonstrated that sheath dynamics in plasma immersion ion implantation (PIII) is significantly affected by an external magnetic field, especially in the case when the magnetic field is parallel to the workpiece surface or intersects it at small angles. In this work we report the results from two-dimensional, particle-in-cell (PIC) computer simulations of magnetic field enhanced plasma immersion implantation system at different bias voltages. The simulations begin with initial low-density nitrogen plasma, which extends with uniform density through a grounded cylindrical chamber. Negative bias voltage is applied to a cylindrical target located on the axis of the vacuum chamber. An axial magnetic field is created by a solenoid installed inside the target holder. A set of simulations at a fixed magnetic field of 0.0025 T at the target surface is performed. Secondary electron emission from the target subjected to ion bombardment is also included. It is found that the plasma density around the cylindrical target increases because of intense background gas ionization by the electrons drifting in the crossed E x B fields. Suppression of the sheath expansion and increase of the implantation current density in front of the high-density plasma region are observed. The effect of target bias on the sheath dynamics and implantation current of the magnetic field enhanced PIII is discussed. (C) 2007 Elsevier B.V. All rights reserved.

Amorphous carbon nitrogenated films prepared by plasma immersion ion implantation and deposition

In this work, an investigation was conducted on amorphous hydrogenated-nitrogenated carbon films prepared by plasma immersion ion implantation and deposition. Glow discharge was excited by radiofrequency power (13.56 MHz, 40 W) whereas the substrate-holder was biased with 25 kV negative pulses. The films were deposited from benzene, nitrogen and argon mixtures. The proportion of nitrogen in the chamber feed (R-N) was varied against that of argon, while keeping the total pressure constant (1.3 Pa). From infrared reflectance-absorbance spectroscopy it was observed that the molecular structure of the benzene is not preserved in the film. Nitrogen was incorporated from the plasma while oxygen arose as a contaminant. X-ray photoelectron spectroscopy revealed that N/C and O/C atomic ratios change slightly with R-N. Water wettability decreased as the proportion of N in the gas phase increased while surface toughness underwent just small changes. Nanoindentation measurements showed that film deposition by means of ion bombardment was beneficial to the mechanical properties of the film-substrate interface. The intensity of the modifications correlates well with the degree of ion bombardment. (c) 2006 Elsevier B.V. All rights reserved.

Numerical simulation of magnetic field enhanced plasma immersion ion implantation

The behavior of plasma and sheath characteristics under the action of an applied magnetic field is important in many applications including plasma probes and material processing. Plasma immersion ion implantation (PIII) has been developed as a fast and efficient surface modification technique of complex shaped three-dimensional objects. The PIII process relies on the acceleration of ions across a high-voltage plasma sheath that develops around the target. Recent studies have shown that the sheath dynamics is significantly affected by an external magnetic field. In this work we describe a two-dimensional computer simulation of magnetic field enhanced plasma immersion implantation system. Negative bias voltage is applied to a cylindrical target located on the axis of a grounded cylindrical vacuum chamber filled with uniform nitrogen plasma. An axial magnetic field is created by a solenoid installed inside the cylindrical target. The computer code employs the Monte Carlo method for collision of electrons and neutrals in the plasma and a particle-in-cell (PIC) algorithm for simulating the movement of charged particles in the electromagnetic field. Secondary electron emission from the target subjected to ion bombardment is also included. It is found that a high-density plasma region is formed around the cylindrical target due to the intense background gas ionization by the magnetized electrons drifting in the crossed ExB fields. An increase of implantation current density in front of high density plasma region is observed. (C) 2007 Elsevier B.V. All rights reserved.

Corrosion behavior of Ti-6Al-4V alloy treated by plasma immersion ion implantation process

Ti-6Al-4V alloy is one of the most frequently used Ti alloys with diverse applications in aerospace and biomedical areas due to its favorable mechanical properties, corrosion resistance and biocompatibility. Meanwhile, its surface can stiffer intense corrosion caused by wear processes due to its poor tribological properties. Thus in the present study, PIII processing of Ti-6Al-4V alloy was carried out to evaluate its corrosion resistance in 3.5% NaCl solution. Two different sets of Ti-6Al-4V samples were PIII treated, varying the plasma gases and the treatment time. The corrosion behavior is correlated with the surface morphology, and the nitrogen content. SEM micrographs of the untreated sample reveal a typical two-phase structure. PIII processing promotes surface sputtering and the surface morphology is completely different for samples treated with N-2/H-2 mixture and N-2 only. The highest penetration of nitrogen (similar to 88 nm), corresponding to 33% of N-2 was obtained for the sample treated with N-2/H-2 mixture for 1:30 h. The corrosion behavior of the samples was investigated by a potentiodynamic polarization method. A large passive region of the polarization curves (similar to 1.5 V), associated with the formation of a protective film, was observed for all samples. The passive current density (similar to 3 x 10(-6) A cm(-2)) of the PIII-treated Ti-6Al-4V samples is about 10 times higher than for the untreated sample. This current value is still rather low and maintains good corrosion resistance. The anodic branches of the polarization curves for all treated Ti-6Al-4V samples demonstrate also that the oxide films break down at approximately 1.6 V, forming an active region. Although the sample treated by N-2/H-2 mixture for 1.30 It has thicker nitrogen enriched layer, better corrosion resistance is obtained for the PIII process performed with N, gas only. (c) 2007 Elsevier B.V. All rights reserved.

Nanohardness and contact angle of Si wafers implanted with N and C and Al alloy with N by plasma ion implantation

Surfaces of silicon wafers implanted with N and C, respectively, and aluminum 5052 implanted with N alone by plasma immersion ion implantation WHO were probed by a nanoindentor and analyzed by the contact-angle method to provide information on surface nanohardness and wettability. Silicon nitride and silicon carbide are important ceramic materials for microelectronics, especially for high-temperature applications. These compounds can be synthesized by high-dose ion implantation. The nanohardness of a silicon sample implanted with 12-keV nitrogen PIII (with 3 X 10(17) cm(-2) dose) increased by 10% compared to the unimplanted sample, in layers deeper than the regions where the formation of the Si,N, compound occurred. A factor of 2.5 increase in hardness was obtained for C-implanted Si wafer at 35 keV (with 6 X 10(17) cm(-2) dose), again deeper than the SiC-rich layer, Both compounds are in the amorphous state and their hardness is much lower than that of the crystalline compounds, which require an annealing process after ion implantation. In the same targets, the contact angle increased by 65% and 35% for N- and C-implanted samples, respectively. Compared to the Si target, the nitrogen PIII-irradiated Al 5052 (wish 15 keV) showed negligible change in its hydrophobic character after ion implantation. Its near-surface nanohardness measurement showed a slight increase for doses of 1 X 10(17) cm(-2). We have been searching for an AlN layer of the order of 1000 A thick, using such a low-energy PIII process, but oxide formation during processing has precluded its synthesis. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Effect of electron magnetic trapping in a plasma immersion ion implantation system

In this work we describe a two-dimensional computer simulation of magnetic field enhanced plasma immersion implantation system. Negative bias voltage of 10.0 kV is applied to a cylindrical target located on the axis of a grounded vacuum chamber filled with uniform nitrogen plasma. A pair of external coils creates a static magnetic field with main vector component along the axial direction. Thus, a system of crossed ExB field is generated inside the vessel forcing plasma electrons to rotate in azimuthal direction. In addition, the axial variation of the magnetic field intensity produces magnetic mirror effect that enables axial particle confinement. It is found that high-density plasma regions are formed around the target due to intense background gas ionization by the trapped electrons. Effect of the magnetic field on the sheath dynamics and the implantation current density of the PIII system is investigated. By changing the magnetic field axial profile (varying coils separation) an enhancement of about 30% of the retained dose can be achieved. The results of the simulation show that the magnetic mirror configuration brings additional benefits to the PIII process, permitting more precise control of the implanted dose.

Insights into metal ion binding in phospholipases A(2): ultra high-resolution crystal structures of an acidic phospholipase A(2) in the Ca2+ free and bound states

The electrophile Ca2+ is an essential multifunctional co-factor in the phospholipase A(2) mediated hydrolysis of phospholipids. Crystal structures of an acidic phospholipase A(2) from the venom of Bothrops jararacussu have been determined both in the Ca2+ free and bound states at 0.97 and 1.60 angstrom resolutions, respectively. In the Ca2+ bound state, the Ca2+ ion is penta-coordinated by a distorted pyramidal cage of oxygen and nitrogen atoms that is significantly different to that observed in structures of other Group I/II phospholipases A(2). In the absence of Ca2+, a water molecule occupies the position of the Ca2+ ion and the side chain of Asp49 and the calcium-binding loop adopts a different conformation. (c) 2005 Elsevier SAS. All rights reserved.

Numerical simulation of magnetic-field-enhanced plasma immersion ion implantation in cylindrical geometry

Recent studies have demonstrated that the sheath dynamics in plasma immersion ion implantation (PIII) is significantly affected by an external magnetic field. In this paper, a two-dimensional computer simulation of a magnetic-field-enhanced PHI system is described. Negative bias voltage is applied to a cylindrical target located on the axis of a grounded vacuum chamber filled with uniform molecular nitrogen plasma. A static magnetic field is created by a small coil installed inside the target holder. The vacuum chamber is filled with background nitrogen gas to form a plasma in which collisions of electrons and neutrals are simulated by the Monte Carlo algorithm. It is found that a high-density plasma is formed around the target due to the intense background gas ionization by the magnetized electrons drifting in the crossed E x B fields. The effect of the magnetic field intensity, the target bias, and the gas pressure on the sheath dynamics and implantation current of the PHI system is investigated.

Effects of the high-temperature plasma immersion ion-implantation treatment on corrosion behavior of Ti-6Al1-4V

Nitrogen implantation into Ti alloys at higher temperatures improves their mechanical and corrosion resistance properties by forming a thicker nitride layer. In this paper, two different sets of Ti-6Al-4V samples were plasma immersion ion implantation (PIII)-treated using nitrogen plasma, varying the treatment time from 30 to 150 min (800 degrees C) and the process temperature from 400 degrees C to 800 degrees C (t = 60 min). Nanoindentation measurements of the PIII-treated samples at 800 C during 150 min showed the highest hardness value, 24 GPa, which is about four times bigger than untreated sample hardness. The N penetration at these conditions reached approximately 150 nm as analyzed by Auger spectroscopy. on the other hand, the lowest passive current density (3 x 10(-7) A. cm(-2)) was obtained for a PIII-treated sample during 30 min at higher temperature (800 degrees C). The corrosion resistance of this sample is almost the same as for the untreated specimen. Corrosion behavior evidenced that in strong oxidizing media, all PIII-treated samples are more corrosion resistant than the untreated one. PIII processing at higher temperatures promotes smoothing of the sample surface as observed by scanning electron microscopy (SEM). Grazing incidence X-ray diffraction analyses of the untreated samples identified the two typical Ti phases, Ti alpha and Ti beta. After the implantation, Ti2N and TiO2 phases were also detected.

Influence of sugar cane burning on aerosol soluble ion composition in Southeastern Brazil

Seasonal variability in the major soluble ion composition of atmospheric particulate matter in the principal sugar cane growing region of central São Paulo State indicates that pre-harvest burning of sugar cane plants is an important influence on the regional scale aerosol chemistry. Samples of particulate matter were collected between April 1999 and February 2001 in coarse (> 3.5 mum) and fine (< 3.5 mum) fractions, and analysed for HCOO-, CH3COO-, C2C42-, SO42- . Results indicated that the principal sources of the aerosols investigated NO3-, Cl-, Na+, K+, NH4+, Mg2+ and Ca2+ were local or regional in nature (scale of tens to a few hundreds of km), and that differences between air masses of varying origins were small. Fine particles were typically acidic, containing secondary nitrates, sulphates and organic species. Coarse fraction concentrations were mainly influenced by physical parameters (wind speed, movement of vehicles and surface condition) affecting rates of re-suspension, although secondary nitrate and sulphate were also present in the larger particles.Concentrations of all measured species except sodium and chloride were higher during the burning season. Although concentrations were lower than often found in polluted urban environments, the massive increases during much of the year, due to a single anthropogenic activity (sugar cane burning) are indicative of a very large perturbation of the lower troposphere in the region relative to the natural condition. These aerosols are suspected of promoting respiratory disease. They also represent an important mechanism for the tropospheric transport of species relevant to surface acidification (sulphates, nitrates, ammonium and organic acids) and soil nutrient status (potassium, nitrogen, ammonium, calcium), so their impact on fragile natural ecosystems (following deposition) needs to be considered. (C) 2004 Elsevier Ltd. All rights reserved.

Two dimensional computer simulation of plasma immersion ion implantation

The biggest advantage of plasma immersion ion implantation (PIII) is the capability of treating objects with irregular geometry without complex manipulation of the target holder. The effectiveness of this approach relies on the uniformity of the incident ion dose. Unfortunately, perfect dose uniformity is usually difficult to achieve when treating samples of complex shape. The problems arise from the non-uniform plasma density and expansion of plasma sheath. A particle-in-cell computer simulation is used to study the time-dependent evolution of the plasma sheath surrounding two-dimensional objects during process of plasma immersion ion implantation. Before starting the implantation phase, steady-state nitrogen plasma is established inside the simulation volume by using ionization of gas precursor with primary electrons. The plasma self-consistently evolves to a non-uniform density distribution, which is used as initial density distribution for the implantation phase. As a result, we can obtain a more realistic description of the plasma sheath expansion and dynamics. Ion current density on the target, average impact energy, and trajectories of the implanted ions were calculated for three geometrical shapes. Large deviations from the uniform dose distribution have been observed for targets with irregular shapes. In addition, effect of secondary electron emission has been included in our simulation and no qualitative modifications to the sheath dynamics have been noticed. However, the energetic secondary electrons change drastically the plasma net balance and also pose significant X-ray hazard. Finally, an axial magnetic field has been added to the calculations and the possibility for magnetic insulation of secondary electrons has been proven.

Effects of high temperature plasma immersion ion implantation on wear resistance of Ti-Si-B sintered alloys

Although titanium and its alloys own good mechanical properties and excellent corrosion resistance, these materials present poor tribological properties for specific applications that require wear resistance. In order to produce wear-resistant surfaces, this work is aimed at achieving improvement of wear characteristics in Ti-Si-B alloys by means of high temperature nitrogen plasma immersion ion implantation (PIII). These alloys were produced by powder metallurgy using high energy ball milling and hot pressing. Scanning electron microscopy (SEM) and X-ray diffraction identified the presence of α-titanium, Ti6Si2B, Ti5Si3, TiB and Ti3Si phases. Wear tests were carried out with a ball-on-disk tribometer to evaluate the friction coefficient and wear rate in treated and untreated samples. The worn profiles were measured by visible light microscopy and examined by SEM in order to determine the wear rates and wear mechanisms. Ti-7.5Si-22.5B alloy presented the highest wear resistance amongst the untreated alloys produced in this work. High temperature PIII was effective to reduce the wear rate and friction coefficient of all the Ti-Si-B sintered alloys. © 2013 Elsevier B.V.

Improvements of plasma immersion ion implantation (PIII) and deposition (PIII&D) processing for materials surface modification

Plasma immersion ion implantation (PIII) process is a three dimensional surface modification method that is quite mature and well known to the surface engineering community nowadays, especially to those working in the field of plasma-materials interaction, aiming at both industrial and academic applications. More recently, deposition methods have been added to PIII, the PIII&D, opening possibilities of broader range of applications of these techniques. So, PIII&D is becoming a routine method of surface modification, with the advantage of pushing up the retained dose levels limited by the sputtering due to ion implantation. Therefore, well adherent, thick, three-dimensional films without stress are possible to be achieved, at relatively low cost, using PIII&D. In this paper, we will discuss about a few PIII and PIII&D experiments that have been performed recently to achieve surface improvements in different materials: 1 - high temperature nitrogen PIII in Ti6Al4V alloy in which a deep nitrogen rich treated layer resulted in surface improvements as increase of hardness, corrosion resistance and resistance to wear of the Ti alloy; 2 - nanostructures in ZnO films, obtained by PIII&D of vaporized & ionized Zn source; 3 - combined implantation and deposition of calcium for biomaterial activity of Ti alloy (PIII&D), allowing the growth of hydroxyapatite in a body solution; 4 - magnetron sputtering deposition of Cr that was enhanced by the glow discharge Ar plasma to allow implantation and deposition of Cr on SAE 1070 steel (PIII&D) resulting in surfaces with high resistance to corrosion; and 5 - implantation of nitrogen by ordinary PIII into this Cr film, which improved resistance to corrosion, while keeping the tribological properties as good as for the SAE 1070 steel surface. © 2012 Elsevier B.V.